CN106587433A - Chromium-containing waste water treatment system adopting double anion exchange columns and treatment method of system - Google Patents
Chromium-containing waste water treatment system adopting double anion exchange columns and treatment method of system Download PDFInfo
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- CN106587433A CN106587433A CN201611185696.5A CN201611185696A CN106587433A CN 106587433 A CN106587433 A CN 106587433A CN 201611185696 A CN201611185696 A CN 201611185696A CN 106587433 A CN106587433 A CN 106587433A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/02—Oxides or hydrates thereof
- C01G37/033—Chromium trioxide; Chromic acid
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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Abstract
The invention provides a chromium-containing waste water treatment system adopting double anion exchange columns and a treatment method of the system. The system comprises a filtering device, a cation exchange column, a first anion exchange column, a second anion exchange column and a sodium removing column, wherein, solution inlets and outlets of the filtering device, the cation exchange column, the first anion exchange column and the second anion exchange column are sequentially connected; and saturated liquid outlets of the first anion exchange column and the second anion exchange column are connected with a liquid inlet of the sodium removing column. According to the system, by means of the difference of the adsorbing appetency of resin on different ions and the selective adsorptivity of the resin, the purpose of removing, separating and recycling chromic acid is achieved. Meanwhile, by performing the coating treatment on ion exchange resin, the appetency of the ion exchange resin on corresponding ions is further improved, and therefore the recycling efficiency of hexavalent chromium is improved, and the service life of the ion exchange resin is prolonged.
Description
Technical field
Electroplating wastewater processing field of the present invention, is related to a kind of system for processing chrome-containing wastewater and its processing method, more particularly to
A kind of system for processing chrome-containing wastewater and its processing method of employing dianion exchange column.
Background technology
Cr (VI) is a kind of carcinogenic, teratogenesis and mutagenic extremely toxic substance, and toxicity is bigger than Cr (III) 100 times, national
It is classified as the pollutant of class control.Cr (VI) is in waste water with the difference of pH value respectively with CrO3、CrO4 2-And Cr2O7 2-Etc. form
Exist, due to harmful substance contents it is high, complicated component, it is larger to thus result in treatment technology difficulty, and surrounding environment is caused seriously
Threat.
In the chromate waste water of chrome-plating plant discharge, go out containing extremely toxic substance CrO4 2-Or Cr2O7 2-Outward, other are also contained
Ion, such as SO4 2-、Cl-、Fe3+And Cr3+Deng, while be also possible to be entrained into other mechanical admixtures and organic impurities etc., due to from
The diversity of son, traditional chromate waste water is processed, by reduction reaction, hexavalent chrome reduction into trivalent chromium, addition NaOH or
Person's calcium hydroxide, is adjusted to appropriate pH value, and precipitation reaction occurs.
CN 104030478A disclose a kind of chromium containing waste water treatment method, comprise the following steps：A, chromate waste water is added
Acid, pH is adjusted between 2～3；Add reducing agent in b, oxytropism chromate waste water, by hexavalent chromium be reduced into trivalent chromium from
Son；C, b step is processed after solution plus alkali, pH adjusted between 8～9, and trivalent chromic ion is changed into into chromium hydroxide precipitation.
CN 105753237A disclose a kind of chromium containing waste water treatment method, comprise the following steps：A, chromate waste water is added
Alkali, PH is adjusted to 12；B, in alkaline wastewater containing cr copperas solution is added, the content of its ferrous sulfate is the 16 of chromium content
Times；C, b step is processed after solution vapor heating, and its temperature is heated between 65 DEG C～75 DEG C, and be stirred 5～
13 minutes；D, step c is processed after solution carry out precipitate and separate, the supernatant of acquisition is discharged, and the sediment of acquisition is
Has magnetic ferrite.
But said method is required to the substantial amounts of medicament for adding, and can produce substantial amounts of sludge, the sexavalence in waste water
Chromium can not be effectively utilized.
The Technology development of chromate waste water comparative maturity, but with environmental requirement it is more and more stricter, it is useless containing chromium
Water harnessing has been enter into integrated control, recycles and the overall control stage.Simultaneously in response to national cleaner production policy, ion
Exchange process is shown one's talent as a kind of clearer production technology in the chromate waste water of China is processed.Ion-exchange is processed containing chromium
One of effective ways of waste water, compare other processing methods and have processing cost low, it is recyclable it is chromic a little.But at present
Ion-exchange treatment system and technique have that automaticity is low, the regeneration of resin and attended operation are complicated, are not suitable for big rule
There is trivalent chromium simultaneously in the wastewater treatment of mould, particularly waste water, it is never effective to the with serious pollution problem of resin
Solution.
Therefore, regeneration and the attended operation for how working out resin is simple, can mass produce, and can effectively reclaim useless
Chromic ion exchange treatment methods are the problems for needing to solve in water.
The content of the invention
Can not effectively reclaim in Cr VI, and existing ion exchange treatment methods for existing chromium containing waste water treatment method and set
The regeneration of fat and attended operation are complicated, the problems such as be not suitable for large-scale wastewater treatment, the invention provides one kind adopts jack to jack adapter
The system for processing chrome-containing wastewater and its processing method of ion exchange column.The present invention utilizes absorption affinity of the resin to different ions
Difference, using the Selective adsorption of resin, reach the purpose for removing and separating and recovering chromic acid.Meanwhile, by ion exchange
Resin is coated process, further increases affinity of the ion exchange resin to corresponding ion, and then improves Cr VI
Organic efficiency, extend ion exchange resin service life.
It is that, up to this purpose, the present invention is employed the following technical solutions：
In a first aspect, the invention provides a kind of system for processing chrome-containing wastewater, the system includes filter, cation
Exchange column, the first anion-exchange column, the second anion-exchange column and removing sodium post, wherein, filter, cation exchange column,
The solution of the first anion-exchange column and the second anion-exchange column is imported and exported and is sequentially connected, the first anion-exchange column and second
The saturated liquid outlet of anion-exchange column is connected with the liquid inlet of removing sodium post.
It is by the tradable group of ion exchange resin and chromate waste water using ion-exchange treatment chromate waste water
Anion (or cation) is exchanged with each other, and to remove or reclaim the harmful substance in waste water, anion exchange resin can only
Swap with the anion in waste water, cationic ion-exchange resin can only be swapped with the cation in waste water.And, it is this
Exchange reaction is typically all reversible, when yin and yang resin absorption reaches saturation, can be regenerated.
In the present invention, it is due in addition to containing anion and cation, going back in chromate waste water that filter is arranged first
A small amount of mechanical admixture may be carried secretly, one layer of dirt is easily covered rapidly on exchanger resin, in order to prevent such situation, first
Waste water is carried out into mechanical filter, then carries out ion exchange.
In the present invention, Cr is contained in chromate waste water3+And Fe3+Deng metal cation, if be directly entered in anion column
Raise may pH value, Precipitation, by resin stain, so need before anion-exchange column, plus cation exchange
Post, removes the cation impurity in waste water.
Jing cationic ion-exchange resin swap process after waste water in do not contain metal ion, comprise only acid (i.e. sun from
Son is H+, anion is various acid ions).Meanwhile, the contained H in solution Jing after cation resin exchange+, pH value of solution can be made
Further reduce, and then be conducive to the CrO in solution4 2-To Cr2O7 2-Conversion；Also, Jing cationic ion-exchange resins remove metal
After cation, hydroxide precipitation blocking resin will not be generated in solution.
In the present invention, when chromate waste water enters single anion exchange column, anion-exchange column presses its suction to anion
Attached affinity carries out layered adsorption (as shown in Figure 1), and the big upper end in anion-exchange column of affinity is adsorbed, affinity
The little lower end in anion-exchange column is adsorbed, if connected using two anion-exchange columns, can be by adsorption layer
It is respectively distributed in two anion-exchange columns (as shown in Figure 2), when the first anion-exchange column imports and exports Cr2O7 2-Concentration
When equal, show that the first anion-exchange column reaches saturation, pure chromium acid can be carried out regenerating and then be obtained, while switching second is cloudy
Ion exchange column is adsorbed, and the first anion-exchange column and the second anion-exchange column are used alternatingly.
Carry out in adsorption process in the first anion-exchange column, the second anion-exchange column can retain OH-, it is in H+Deposit
When, ultra-pure water can be obtained again.
It is following as currently preferred technical scheme, but not as the present invention provide technical scheme restriction, pass through
Technical scheme below, can preferably reach and realize the technical purpose and beneficial effect of the present invention.
It is the cation exchange column, the first anion-exchange column (3), second cloudy as currently preferred technical scheme
Regenerative agent throwing device is respectively provided with the liquid inlet of ion exchange column and removing sodium post.
The regenerative agent throwing device carries out cation exchange for adding hydrochloric acid in cation exchange column and removing sodium post
The regeneration of resin, and for adding NaOH to the first anion-exchange column and the second anion-exchange column, for the moon from
The regeneration of sub-exchange resin and generation sodium chromate.
Used as currently preferred technical scheme, the resin filled in the cation exchange column is the benzene second of H types 001 × 7
Alkene cation exchanger resin.
Preferably, the resin of first anion-exchange column (3) and the middle filling of the second anion-exchange column (4) is table
Face is attached with the D201 styrene series anion exchange resins of polyvinyl amidine and sulfonated polyether sulphone composition.
In the present invention, cationic ion-exchange resin used is storng-acid cation exchange resin, and its resin adsorption affinity is：
Th4+＞ Al3+＞ Ba2+＞ Na+
Ba2+＞ Sr2+＞ Ca2+＞ Mg2+
Anion exchange resin used is strong-base anion-exchange resin, and it is in low concentration aqueous solution and normal temperature is to certain
The selecting sequence of a little anion is as follows：
Cr2O7 2-＞ SO4 2-＞ NO3 -＞ CrO4 2-＞ Cl-＞ OH-
Cr2O7 2-＞ SO4 2-＞ NO3 -＞ Cl-＞ OH-
(note：Can in particular cases there is exception in above-mentioned selecting sequence) at some
In an ion-exchange reactions, reaction is carried out toward which direction actually, depending on ion exchange resin to solution
The difference of the relative affinity of middle concentrated ion.
In the present invention, ion exchange resin reply solute has high selectivity and water penetration, there is high saturating to solvent
The property crossed, and should have good chemical stability, heat resistance and certain mechanical strength.It is attached with anion exchange resin poly-
Vinyl amidine and the composition of sulfonated polyether sulphone, increased the roughness of ion exchange resin, increase surface area, so that
The water flux of ion exchange resin is significantly improved, and can for a long time maintain high through performance, improves ion exchange resin pair
The affinity of corresponding ion；The service life of ion exchange resin can also be extended simultaneously.
Preferably, the adhesion amount of the polyvinyl amidine and sulfonated polyether sulphone composition is 15mg/m2～30mg/m2, example
Such as 15mg/m2、17mg/m2、20mg/m2、23mg/m2、25mg/m2、27mg/m2Or 30mg/m2Deng it is not limited to cited
Numerical value, other unrequited numerical value are equally applicable in the number range, preferably 20mg/m2～30mg/m2, further preferably
For 25mg/m2。
In the present invention, the adhesion amount of the polyvinyl amidine and sulfonated polyether sulphone composition is not The more the better, and its is attached
The amount of wearing need to be controlled within the specific limits, it is excessive or it is very few all can to adsorb solution bring harmful effect.
Preferably, the mass ratio of the polyvinyl amidine and sulfonated polyether sulphone is (3～10):1, such as 3:1、4:1、5:
1、6:1、7:1、8:1、9:1 or 10:1 etc., it is not limited to other unrequited numbers in cited numerical value, the number range
Value is equally applicable, preferably (3～7):1, more preferably 5:1.
Preferably, the resin of filling is the styrene type cation exchange resin of H types 001 × 7 in the removing sodium post (5).
Second aspect, the invention provides a kind of chromium containing waste water treatment method, the method comprising the steps of：
(1) pH to the pH ＜ 4 of chromate waste water are adjusted；
(2) chromate waste water after pH will be adjusted in step (1) carries out ion-exchange treatment with cationic ion-exchange resin, removes
Metal cation in chromate waste water；
(3) waste water that metal cation is stripped of in step (2) is swapped with the first anion exchange resin, to
Cr in one anion exchange resin2O7 2-(i.e. Cr in the first anion exchange resin Inlet and outlet water is switched over when reaching saturation2O7 2
Concentration it is equal), make waste water and the second anion exchange resin swap process, while the first anion exchange to saturation
Resin is regenerated, and after the regeneration of the first anion exchange resin chromium acid sodium solution is flowed out；
(4) as Cr in the second anion exchange resin in step (3)2O7 2-Switching over when reaching saturation makes waste water with step
Suddenly the first anion exchange resin in (3) after regeneration swaps process, while the second anion exchange resin to saturation
Regenerated, after the regeneration of the second anion exchange resin chromium acid sodium solution is flowed out；
(5) chromium acid sodium solution obtained in step (3) and step (4) is carried out into removing sodium process with cationic ion-exchange resin,
Prepared chromic acid.
Wherein, it can be 3.9,3.5,3,2.5,2 or 1.5 etc. and lower that pH is adjusted in step (1), it is not limited to institute
Other unrequited numerical value are equally applicable in the numerical value enumerated, the number range.
In the present invention, the acid-base value of chromate waste water is to chromate CrO4 2-With dichromate ion Cr2O7 2-With considerable influence, such as
Into the waste water slant acidity of resin anion (R.A.) post, then strong to exchanging, exchange capacity is high；The waste water value of pH nearer it is to neutrality,
Exchange just relatively difficult, because pH value determines Cr VI ionic species present in water.
Cr VI in aqueous, mainly with CrO4 2-And Cr2O7 2-Form exist, the equilibrium relation between them is such as
Under：
When the pH value of waste water is higher, the Cr VI in waste water is mainly with CrO4 2-In the form of；Conversely, as the pH of waste water
When being worth low, the Cr VI in waste water is mainly with Cr2O7 2-Form is present, chromic existence form and pH value relation in waste water
It is shown in Table 1.
Table 1：CrO in the case of 15 DEG C of different pH value4 2-With Cr2O7 2-Relative percentage
It can be seen that, as chromate waste water PH ＜ 4, CrO4 2-Cr will be completely converted into2O7 2-。
The exchange process of anion-exchange column of the present invention has four-stage：
First stage：In ultra-pure water period, when there is adsorption layer cloudy post end, it is ultra-pure water (K ＜ now to discharge water
10us/cm)；
Second stage：Water up to standard flows out the stage, and continuing water flowing makes electrical conductivity constantly raise, as Cr in water body6+＜ 0.2mg/
L, is water up to standard, can be discharged, can reuse；
Phase III：Exceeded water, when continuing water flowing, electrical conductivity constantly rises, and works as Cr6+＞ 0.2mg/L, and with second the moon
Post is connected, and two cloudy posts are used simultaneously；
Fourth stage：The sodium chromate stage is reclaimed, continues water flowing, as the first anion-exchange column delivery port Cr2O7 2-Concentration
When equal, the first anion-exchange column is by Cr2O7 2-Saturation, closes the first anion-exchange column, and waste water is only handed over the second anion
Change post exchange.First anion-exchange column is regenerated, while repeating the first anion on second anion-exchange column
The said process of exchange column, two anion-exchange columns are used alternatingly.
As currently preferred technical scheme, before step (1) the regulation chromate waste water pH, chromate waste water is carried out pre-
Process.
Preferably, the pretreatment is mechanical filter.
Preferably, the mechanical filter be sand filtration, carbon filter or ultrafiltration in any one or at least two combination, described group
Closing typical case but non-limiting examples has：The combination of sand filtration and the combination of carbon filter, carbon filter and ultrafiltration, the group of sand filtration, carbon filter and ultrafiltration
Close etc..
In the present invention, due in chromate waste water in addition to containing anion and cation, it is also possible to carry a small amount of machinery secretly
Impurity and suspended contamination, easily cover rapidly one layer of dirt on exchanger resin, in order to prevent such situation, first will be useless
Water carries out mechanical filter, then carries out ion exchange.
Used as currently preferred technical scheme, cationic ion-exchange resin described in step (2) is the styrene of H types 001 × 7
Cation exchanger resin.
Preferably, cationic ion-exchange resin is pre-processed and made the transition before ion exchange is carried out described in step (2).
In the present invention, resin used in process of production easy residual organic solvent, low polymer and some have
Machine impurity, causes resin stain in transportation, thus resin used is being pre-processed and made the transition using front needs.
Preferably, the pretreatment and transition is comprised the following steps：
A () cleans water immersion 1h～2h that cationic ion-exchange resin temperature is 50 DEG C～60 DEG C, then deionized water
It is colourless to outflow water, its object is to remove part aqueous impurity；
B () drenches the hydrochloric acid solution that the cationic ion-exchange resin concentration after processing in step (a) is 2wt%～4wt%
Be washed till the pH ＜ 4 of outflow water, with hydrochloric acid solution that concentration is 2wt%～4wt% immersion 1h～5h, then deionized water clean to
The pH of outflow water is 5～6, its object is to the impurity that decapacitation is dissolved in acid；
C () is molten by the NaOH that the cationic ion-exchange resin concentration Jing after step (b) process is 4wt%～6wt%
The pH ＞ 10 of liquid drip washing to outflow water, with sodium hydroxide solution that concentration is 4wt%～6wt% immersion 1h～5h, then spend from
Sub- water clean to outflow water pH be 6～7, its object is to the impurity that decapacitation is dissolved in alkali；
D () drenches the hydrochloric acid solution that the cationic ion-exchange resin concentration Jing after step (c) process is 2wt%～4wt%
The pH ＜ 4 of outflow water are washed till, with hydrochloric acid solution immersion 1h～5h that concentration is 2wt%～4wt%, make Na type resins change into H
Type, then deionized water clean to outflow water pH be 5～6, complete the pretreatment and transition of cationic ion-exchange resin.
Wherein, the temperature of water described in step (a) can be 50 DEG C, 52 DEG C, 54 DEG C, 56 DEG C, 58 DEG C or 60 DEG C etc., but not
It is only limitted to other unrequited numerical value in cited numerical value, the number range equally applicable；Soak time described in step (a)
Can be 1h, 1.3h, 1.5h, 1.7h or 2h etc., it is not limited to other are unrequited in cited numerical value, the number range
Numerical value is equally applicable；The concentration of hydrochloric acid solution described in step (b) can for 2wt%, 2.5wt%, 3wt%, 3.5wt% or
4wt% etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range；Step (b)
The pH of middle drip washing outflow water can be 3.9,3.5,3,2.5,2 or 1.5 etc. and lower, it is not limited to cited numerical value,
Other unrequited numerical value are equally applicable in the number range；Soak time described in step (b) can be 1h, 2h, 3h, 4h or 5h
Deng it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range；In step (b)
It can be 5,5.2,5.4,5.6,5.8 or 6 etc. that ionized water is cleaned to the pH of outflow water, it is not limited to cited numerical value, should
Other unrequited numerical value are equally applicable in number range；The concentration of sodium hydroxide solution described in step (c) can for 4wt%,
4.5wt%, 5wt%, 5.5wt% or 6wt% etc., it is not limited to other are not arranged in cited numerical value, the number range
The numerical value of act is equally applicable；The pH of the outflow water of the drip washing can be 10.2,10.5,11,11.5,12 or 12.5 etc. and more
Height, it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range；Leaching in step (c)
The bubble time can be 1h, 2h, 3h, 4h or 5h etc., it is not limited to other are unrequited in cited numerical value, the number range
Numerical value is equally applicable；Outflow water pH of the cleaning of deionized water described in step (c) can be 6,6.2,6.4,6.6,6.8 or 7 etc., but
It is not limited in other unrequited numerical value in cited numerical value, the number range equally applicable；Hydrochloric acid described in step (d)
The concentration of solution can for 2wt%, 2.5wt%, 3wt%, 3.5wt% or 4wt% etc., it is not limited to cited numerical value,
Other unrequited numerical value are equally applicable in the number range；The pH of drip washing described in step (d) to outflow water can for 3.9,
3.5th, 3,2.5,2 or 1.5 etc. and lower, it is not limited to other are unrequited in cited numerical value, the number range
Numerical value is equally applicable；In step (d) soak time can for 1h, 2h, 3h, 4h or 5h etc., it is not limited to cited numerical value,
Other unrequited numerical value are equally applicable in the number range；In step (d) deionized water clean to outflow water pH can for 5,
5.2nd, 5.4,5.6,5.8 or 6 etc., it is not limited to other unrequited numerical value are same in cited numerical value, the number range
Sample is suitable for.
Preferably, step (b), step (c) and drip washing speed described in step (d) are respectively 5m/h～10m/h, for example
5m/h, 6m/h, 7m/h, 8m/h, 9m/h or 10m/h etc., it is not limited to cited numerical value, other are not in the number range
The numerical value enumerated is equally applicable.
Preferably, cationic ion-exchange resin described in step (2) is after saturation with the hydrochloric acid solution that concentration is 4～6wt%
Regenerated, regenerated Water Sproading.Wherein, the concentration of the hydrochloric acid can be 2wt%, 2.5wt%, 3wt%, 3.5wt% or 4wt%
Deng it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range.
As currently preferred technical scheme, the first anion exchange resin and the second anion described in step (3)
The D201 styrene series anions that exchanger resin is surface attachment and has polyvinyl amidine and sulfonated polyether sulphone composition are exchanged
Resin.
Preferably, the adhesion amount of the polyvinyl amidine and sulfonated polyether sulphone composition is 15mg/m2～30mg/m2, example
Such as 15mg/m2、17mg/m2、20mg/m2、23mg/m2、25mg/m2、27mg/m2Or 30mg/m2Deng it is not limited to cited
Numerical value, other unrequited numerical value are equally applicable in the number range, preferably 20mg/m2～30mg/m2, further preferably
For 25mg/m2；
Preferably, the mass ratio of the polyvinyl amidine and sulfonated polyether sulphone is (3～10):1, such as 3:1、4:1、5:
1、6:1、7:1、8:1、9:1 or 10:1 etc., it is not limited to other unrequited numbers in cited numerical value, the number range
Value is equally applicable, preferably (3～7):1, more preferably 5:1.
As currently preferred technical scheme, the first anion exchange resin and the second anion described in step (3)
Exchanger resin is pre-processed and made the transition before ion exchange is carried out.
Preferably, the pretreatment and transition is comprised the following steps：
(a ') cleans water immersion 1h～2h that anion exchange resin temperature is 50 DEG C～60 DEG C, then deionized water
It is colourless to outflow water, its object is to remove part aqueous impurity)；
(b ') by Jing step (a ') process after cationic ion-exchange resin concentration be 4wt%～6wt% NaOH
The pH ＞ 10 of solution drip washing to outflow water, with the sodium hydroxide solution that concentration is 4wt%～6wt% 1h～5h is soaked, then is spent
The pH of the outflow water of ionized water cleaning is 6～7, its object is to the impurity that decapacitation is dissolved in alkali；
(c ') is by hydrochloric acid solution that the cationic ion-exchange resin concentration after processing in step (b ') is 2wt%～4wt%
The pH ＜ 4 of drip washing to outflow water, are cleaned with hydrochloric acid solution immersion 1h～5h that concentration is 2wt%～4wt%, then deionized water
Outflow water pH be 5～6, its object is to decapacitation be dissolved in acid impurity；
(d ') by Jing step (c ') process after cationic ion-exchange resin concentration be 4wt%～6wt% NaOH
The pH ＞ 10 of solution drip washing to outflow water, with sodium hydroxide solution immersion 1h～5h that concentration is 4wt%～6wt%, make resin
Change into OH types, then the pH of the outflow water of deionized water cleaning is 8～9.5, complete cationic ion-exchange resin pretreatment and
Transition.
Wherein, the temperature of water described in step (a ') can be 50 DEG C, 52 DEG C, 54 DEG C, 56 DEG C, 58 DEG C or 60 DEG C etc., but and
It is not limited only to other unrequited numerical value in cited numerical value, the number range equally applicable；Soak described in step (a ')
Time can be 1h, 1.3h, 1.5h, 1.7h or 2h etc., it is not limited to other are not arranged in cited numerical value, the number range
The numerical value of act is equally applicable；The concentration of sodium hydroxide solution described in step (b ') can for 4wt%, 4.5wt%, 5wt%,
5.5wt% or 6wt% etc., it is not limited to other unrequited numerical value are equally fitted in cited numerical value, the number range
With；The pH of the outflow water of the drip washing can be 10.2,10.5,11,11.5,12 or 12.5 etc. and higher, it is not limited to
Other unrequited numerical value are equally applicable in cited numerical value, the number range；In step (b ') soak time can for 1h,
2h, 3h, 4h or 5h etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range；
Outflow water pH of the cleaning of deionized water described in step (b ') can be 6,6.2,6.4,6.6,6.8 or 7 etc., it is not limited to institute
Other unrequited numerical value are equally applicable in the numerical value enumerated, the number range；The concentration of hydrochloric acid solution described in step (c ')
Can be 2wt%, 2.5wt%, 3wt%, 3.5wt% or 4wt% etc., it is not limited to cited numerical value, the number range
Interior other unrequited numerical value are equally applicable；The pH of drip washing outflow water can be 3.9,3.5,3,2.5,2 or 1.5 etc. in step (c ')
And it is lower, it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range；Step
Soak time described in (c ') can be for 1h, 2h, 3h, 4h or 5h etc., it is not limited to cited numerical value, in the number range
Other unrequited numerical value are equally applicable；In step (c ') deionized water clean to outflow water pH can for 5,5.2,5.4,5.6,
5.8 or 6 etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range；Step
The concentration of sodium hydroxide solution described in (d ') can be for 4wt%, 4.5wt%, 5wt%, 5.5wt% or 6wt% etc., but and not only
It is limited to other unrequited numerical value in cited numerical value, the number range equally applicable；The pH of the outflow water of the drip washing can
For 10.2,10.5,11,11.5,12 or 12.5 etc. and higher, it is not limited to cited numerical value, in the number range
Other unrequited numerical value are equally applicable；In step (d ') soak time can for 1h, 2h, 3h, 4h or 5h etc., it is not limited to
Other unrequited numerical value are equally applicable in cited numerical value, the number range；Deionized water described in step (d ') is cleaned
PH to outflow water can be 8,8.3,8.5,8.7,9,9.3 or 9.5 etc., it is not limited to cited numerical value, the numerical value model
Other unrequited numerical value are equally applicable in enclosing.
Preferably, drip washing speed is respectively 5m/h～10m/h, example described in step (b '), step (c ') and step (d ')
Such as 5m/h, 6m/h, 7m/h, 8m/h, 9m/h or 10m/h, it is not limited in cited numerical value, the number range other
Unrequited numerical value is equally applicable.
Used as currently preferred technical scheme, carrying out regeneration to the first anion exchange resin described in step (3) makes
Regenerated with the sodium hydroxide solution that concentration is 4～6wt%, wherein the concentration of sodium hydroxide solution can for 4wt%,
4.5wt%, 5wt%, 5.5wt% or 6wt% etc., it is not limited to other are not arranged in cited numerical value, the number range
The numerical value of act is equally applicable.
Preferably, it is 4～6wt%'s described in step (4) the second anion exchange resin to be carried out regenerating concentration
Sodium hydroxide solution is regenerated, wherein the concentration of sodium hydroxide solution can for 4wt%, 4.5wt%, 5wt%, 5.5wt% or
6wt% etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range.
Preferably, removing sodium described in step (5) is processed as using cationic exchange resin adsorption Na+, it is desorbed H+, form chromium
Acid.
Preferably, obtained chromic acid carries out reuse Jing after collecting, concentrate and purify in step (5)；
Preferably, cationic ion-exchange resin described in step (5) is after saturation with the hydrochloric acid solution that concentration is 4～6wt%
Regenerated, regenerated Water Sproading, wherein, the concentration of hydrochloric acid solution can be 4wt%, 4.5wt%, 5wt%, 5.5wt% or 6wt%
Deng it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range.
As currently preferred technical scheme, the method comprising the steps of：
(1) chromate waste water feeding filter is carried out into mechanical filter, then adjusts pH to the pH ＜ 4 of chromate waste water；
(2) will pre-process and conversion with passing through in the middle chromate waste water feeding cation exchange column adjusted after pH of step (1)
Cationic ion-exchange resin carry out ion-exchange treatment, remove the metal cation in chromate waste water；
(3) waste water that metal cation is stripped of in step (2) is sent into into the first anion-exchange column and the first anion
Exchanger resin is swapped, the Cr into the first anion exchange resin2O7 2-(i.e. the first anion is switched over when reaching saturation
Cr in exchanger resin Inlet and outlet water2O7 2Concentration it is equal), make waste water enter the second anion-exchange column and the second anion exchange tree
Fat swaps process, while it is 4～6wt%'s to add concentration in the first anion-exchange column by regenerative agent throwing device
Sodium hydroxide solution regenerates to the first anion exchange resin of saturation, and after the regeneration of the first anion exchange resin chromium is flowed out
Acid sodium solution；
(4) as Cr in the second anion exchange resin in step (3)2O7 2-Switching over when reaching saturation enters waste water
First anion-exchange column swaps process with the first anion exchange resin after regeneration in step (3), while by again
Raw agent throwing device adds second of sodium hydroxide solution that concentration is 4～6wt% to saturation in the second anion-exchange column
Anion exchange resin is regenerated, and after the regeneration of the second anion exchange resin chromium acid sodium solution is flowed out；
(5) chromium acid sodium solution obtained in step (3) and step (4) is sent in removing sodium post to be entered with cationic ion-exchange resin
The process of row removing sodium, is obtained chromic acid.
Compared with prior art, the invention has the advantages that：
(1) system for processing chrome-containing wastewater high degree of automation of the present invention, high treating effect, floor space is little, can
To be applied to extensive water process；
(2) it is used alternatingly between system for processing chrome-containing wastewater dianion exchange column of the present invention, and by right
Ion exchange resin is coated process, and stable effluent quality can be made to keep Cr again6+＜ 0.2mg/L, chromic recovery effect
Rate is up to more than 98%, and effluent quality is excellent, can recycle, and can extend the service life of ion exchange resin；
(3) system for processing chrome-containing wastewater ion exchange resin of the present invention can be safeguarded effectively, can be with
Long-term stable operation, and whole process does not add extra chemical agent, does not produce waste residue, high financial profit yet.
Description of the drawings
Fig. 1 is the schematic diagram of layered adsorption in single anion exchange column；
Fig. 2 be connected using two anion-exchange columns in distribution layer schematic diagram；
Fig. 3 is the structural representation of system for processing chrome-containing wastewater of the present invention；
Wherein, 1- filters, 2- cation exchange columns, the anion-exchange columns of 3- first, the anion-exchange columns of 4- second,
5- removing sodium posts, 6- regenerative agent throwing devices.
Specific embodiment
For the present invention is better described, technical scheme is readily appreciated, below to the present invention further specifically
It is bright.But following embodiments is only the simple example of the present invention, the scope of the present invention is not represented or limits, this
Invention protection domain is defined by claims.
As shown in figure 3, specific embodiment of the invention part provides a kind of system for processing chrome-containing wastewater and its processing method,
The system includes filter 1, cation exchange column 2, the first anion-exchange column 3, the second anion-exchange column 4 and removing sodium
Post 5, wherein, the solution of filter 1, cation exchange column 2, the first anion-exchange column 3 and the second anion-exchange column 4 enters
Outlet is sequentially connected, and the saturated liquid of the first anion-exchange column 3 and the second anion-exchange column 4 exports the liquid with removing sodium post 5
Body entrance is connected.
The liquid of the cation exchange column 2, the first anion-exchange column 3, the second anion-exchange column 4 and removing sodium post 5
Porch is respectively provided with regenerative agent throwing device 6.
The method comprising the steps of：
(1) pH to the pH ＜ 4 of chromate waste water are adjusted；
(2) chromate waste water after pH will be adjusted in step (1) carries out ion-exchange treatment with cationic ion-exchange resin, removes
Metal cation in chromate waste water；
(3) waste water that metal cation is stripped of in step (2) is swapped with the first anion exchange resin, to
Cr in one anion exchange resin2O7 2-Switch over when reaching saturation, waste water is swapped with the second anion exchange resin
Process, while regenerating to the first anion exchange resin of saturation, after the regeneration of the first anion exchange resin chromic acid is flowed out
Sodium solution；
(4) as Cr in the second anion exchange resin in step (3)2O7 2-Switching over when reaching saturation makes waste water with step
Suddenly the first anion exchange resin in (3) after regeneration swaps process, while the second anion exchange resin to saturation
Regenerated, after the regeneration of the second anion exchange resin chromium acid sodium solution is flowed out, repeat step (3) and step (4) are to anion
Cr in exchanger resin outflow water6+Content ＜ 0.2mg/L；
(5) chromium acid sodium solution obtained in step (3) and step (4) is carried out into removing sodium process with cationic ion-exchange resin,
Prepared chromic acid.
It is below present invention typical case but non-limiting example：
Embodiment 1：
A kind of system for processing chrome-containing wastewater is present embodiments provided, the system includes filter 1, cation exchange column
2nd, the first anion-exchange column 3, the second anion-exchange column 4 and removing sodium post 5, wherein, filter 1, cation exchange column 2,
The solution of the first anion-exchange column 3 and the second anion-exchange column 4 is imported and exported and is sequentially connected, the He of the first anion-exchange column 3
The saturated liquid outlet of the second anion-exchange column 4 is connected with the liquid inlet of removing sodium post 5.
The liquid of the cation exchange column 2, the first anion-exchange column 3, the second anion-exchange column 4 and removing sodium post 5
Porch is respectively provided with regenerative agent throwing device 6.
Wherein, the resin filled in the cation exchange column 2 is the styrene type cation exchange resin of H types 001 × 7；
The resin filled in first anion-exchange column 3 and the second anion-exchange column 4 is surface attachment polyvinyl amidine and sulphur
Change the D201 styrene series anion exchange resins of polyether sulphone composition, the polyvinyl amidine and sulfonated polyether sulphone are combined
The adhesion amount of thing is 25mg/m2, the mass ratio 5 of the polyvinyl amidine and sulfonated polyether sulphone:1；Fill in the removing sodium post 5
Resin be the styrene type cation exchange resin of H types 001 × 7.
Embodiment 2：
A kind of system for processing chrome-containing wastewater is present embodiments provided, the system is except polyvinyl amidine and sulfonated polyether
The adhesion amount of sulfone composition is 20mg/m2, the mass ratio 3 of the polyvinyl amidine and sulfonated polyether sulphone:Outside 1, other structures
It is in the same manner as in Example 1.
Embodiment 3：
A kind of system for processing chrome-containing wastewater is present embodiments provided, the system is except polyvinyl amidine and sulfonated polyether
The adhesion amount of sulfone composition is 30mg/m2, the mass ratio 7 of the polyvinyl amidine and sulfonated polyether sulphone:Outside 1, other structures
It is in the same manner as in Example 1.
Embodiment 4：
A kind of system for processing chrome-containing wastewater is present embodiments provided, the system is except polyvinyl amidine and sulfonated polyether
The adhesion amount of sulfone composition is 15mg/m2, the mass ratio 10 of the polyvinyl amidine and sulfonated polyether sulphone:Outside 1, other structures
It is in the same manner as in Example 1.
Embodiment 5：
A kind of chromium containing waste water treatment method is present embodiments provided, methods described is entered using the system described in embodiment 1
OK, concrete grammar is as follows：
(1) chromate waste water is carried out after sand filtration, adjusts pH to the pH ＜ 4 of chromate waste water；
(2) cationic ion-exchange resin used is pre-processed and is made the transition, it is specific as follows：
A () cleans water immersion 1h～2h that cationic ion-exchange resin temperature is 50 DEG C～60 DEG C, then deionized water
It is colourless to outflow water；
B () drenches the hydrochloric acid solution that the cationic ion-exchange resin concentration after processing in step (a) is 2wt%～4wt%
Be washed till the pH ＜ 4 of outflow water, with hydrochloric acid solution that concentration is 2wt%～4wt% immersion 1h～5h, then deionized water clean to
The pH of outflow water is 5～6；
C () is molten by the NaOH that the cationic ion-exchange resin concentration Jing after step (b) process is 4wt%～6wt%
The pH ＞ 10 of liquid drip washing to outflow water, with sodium hydroxide solution that concentration is 4wt%～6wt% immersion 1h～5h, then spend from
It is 6～7 that sub- water is cleaned to the pH of outflow water；
D () drenches the hydrochloric acid solution that the cationic ion-exchange resin concentration Jing after step (c) process is 2wt%～4wt%
Be washed till the pH ＜ 4 of outflow water, with hydrochloric acid solution that concentration is 2wt%～4wt% immersion 1h～5h, then deionized water clean to
The pH of outflow water is 5～6, completes the pretreatment and transition of cationic ion-exchange resin；
Drip washing speed is respectively 5m/h～10m/h described in step (b), step (c) and step (d)；
Anion exchange resin used is pre-processed and made the transition, it is specific as follows：
(a ') cleans water immersion 1h～2h that anion exchange resin temperature is 50 DEG C～60 DEG C, then deionized water
It is colourless to outflow water；
(b ') by Jing step (a ') process after cationic ion-exchange resin concentration be 4wt%～6wt% NaOH
The pH ＞ 10 of solution drip washing to outflow water, with the sodium hydroxide solution that concentration is 4wt%～6wt% 1h～5h is soaked, then is spent
The pH of the outflow water of ionized water cleaning is 6～7；
(c ') is by hydrochloric acid solution that the cationic ion-exchange resin concentration after processing in step (b ') is 2wt%～4wt%
The pH ＜ 4 of drip washing to outflow water, are cleaned with hydrochloric acid solution immersion 1h～5h that concentration is 2wt%～4wt%, then deionized water
Outflow water pH be 5～6；
(d ') by Jing step (c ') process after cationic ion-exchange resin concentration be 4wt%～6wt% NaOH
The pH ＞ 10 of solution drip washing to outflow water, with the sodium hydroxide solution that concentration is 4wt%～6wt% 1h～5h is soaked, then is spent
The pH of the outflow water of ionized water cleaning is 8～9.5, completes the pretreatment and transition of cationic ion-exchange resin；
Drip washing speed is respectively 5m/h～10m/h described in step (b '), step (c ') and step (d ').
(3) chromate waste water after pH will be adjusted in step (1) carries out ion-exchange treatment with cationic ion-exchange resin, removes
Metal cation in chromate waste water；
(4) waste water that metal cation is stripped of in step (3) is swapped with the first anion exchange resin, to
Cr in one anion exchange resin2O7 2-Switch over when reaching saturation, waste water is swapped with the second anion exchange resin
Process, while being regenerated with the sodium hydroxide solution that concentration is 5wt% to the first anion exchange resin of saturation, first is cloudy
Chromium acid sodium solution is flowed out after ion exchange resin regeneration；
(5) as Cr in the second anion exchange resin in step (4)2O7 2-Switching over when reaching saturation makes waste water with step
Suddenly the first anion exchange resin in (4) after regeneration swaps process, while the second anion exchange resin to saturation
Regenerated with the sodium hydroxide solution that concentration is 5wt%, flowed out chromium acid sodium solution after the regeneration of the second anion exchange resin, weight
Step (4) and step (5) are answered to Cr in anion exchange resin outflow water6+Content ＜ 0.2mg/L；
(6) chromium acid sodium solution obtained in step (4) and step (5) is carried out into removing sodium process with cationic ion-exchange resin,
Chromic acid of the prepared concentration more than 95wt%, the cationic ion-exchange resin is entered after saturation with the hydrochloric acid solution that concentration is 5wt%
Row regeneration.
Chromic organic efficiency is 99.3% in the present embodiment.
Embodiment 6：
A kind of chromium containing waste water treatment method is present embodiments provided, methods described is entered using the system described in embodiment 2
OK, except being regenerated with the sodium hydroxide solution that concentration is 4wt% in step (4), step is concrete grammar with concentration in (5)
The sodium hydroxide solution of 4wt% is regenerated, regenerated with the hydrochloric acid solution that concentration is 4wt% in step (6) outside, other things
Material consumption is in the same manner as in Example 5 with processing method.
The concentration of chromic acid obtained in the present embodiment is more than 94wt%, and chromic organic efficiency is 98.9%
Embodiment 7：
A kind of chromium containing waste water treatment method is present embodiments provided, methods described is entered using the system described in embodiment 3
OK, except being regenerated with the sodium hydroxide solution that concentration is 6wt% in step (4), step is concrete grammar with concentration in (5)
The sodium hydroxide solution of 6wt% is regenerated, regenerated with the hydrochloric acid solution that concentration is 6wt% in step (6) outside, other things
Material consumption is in the same manner as in Example 5 with processing method.
The concentration of chromic acid obtained in the present embodiment is more than 94wt%, and chromic organic efficiency is 99%.
Comparative example 1：
This comparative example provides a kind of system for processing chrome-containing wastewater, and the system does not contain the second anion-exchange column 4, i.e., only
Containing an anion-exchange column, other structures are in the same manner as in Example 1.
The processing method of the system for processing chrome-containing wastewater described in this comparative example, except not carrying out the second anion-exchange column
Outside adsorption treatment, unclassified stores consumption is in the same manner as in Example 5 with processing method.
The concentration of chromic acid obtained in this comparative example is 89.3wt%, and chromic organic efficiency is 84%.
Comparative example 2：
This comparative example provides a kind of system for processing chrome-containing wastewater, and the system is except the first anion-exchange column 3 and the
The surface of two anion-exchange column 4 be not coated by polyvinyl amidine and sulfonated polyether sulphone combination beyond the region of objective existence, other structures with embodiment 1
In it is identical.
The processing method of the system for processing chrome-containing wastewater described in this comparative example is in the same manner as in Example 5.
The concentration of chromic acid obtained in this comparative example is 84.6wt%, and chromic organic efficiency is 86%.
Comparative example 3：
This comparative example provides a kind of system for processing chrome-containing wastewater, and the system is except the first anion-exchange column 3 and the
The surface of two anion-exchange column 4 is only adhered to outside polyvinyl amidine, and other structures are in the same manner as in Example 1.
The processing method of the system for processing chrome-containing wastewater described in this comparative example is in the same manner as in Example 5.
The concentration of chromic acid obtained in this comparative example is 87.1wt%, and chromic organic efficiency is 89%.
Comparative example 4：
This comparative example provides a kind of system for processing chrome-containing wastewater, and the system is except the first anion-exchange column 3 and the
The surface of two anion-exchange column 4 is only adhered to outside sulfonated polyether sulphone, and other structures are in the same manner as in Example 1.
The processing method of the system for processing chrome-containing wastewater described in this comparative example is in the same manner as in Example 5.
The concentration of chromic acid obtained in this comparative example is 89.1wt%, and chromic organic efficiency is 91.1%.
The result of integrated embodiment 1-7 and comparative example 1-4 can be seen that system for processing chrome-containing wastewater of the present invention certainly
Dynamicization degree is high, and high treating effect, floor space is little, can apply to extensive water process；Chromate waste water of the present invention
It is used alternatingly between processing system dianion exchange column, and by being coated process to ion exchange resin, can makes
Stable effluent quality keeps Cr again6+＜ 0.2mg/L, chromic organic efficiency is up to more than 98%, and effluent quality is excellent, can be with
Recycle, and the service life of ion exchange resin can be extended.
Meanwhile, system for processing chrome-containing wastewater ion exchange resin of the present invention can be safeguarded effectively, can
With long-term stable operation, and whole process does not add extra chemical agent, does not produce waste residue, high financial profit yet.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention not office by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Art
Technical staff it will be clearly understood that any improvement in the present invention, the equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (10)
1. a kind of system for processing chrome-containing wastewater, it is characterised in that the system includes filter (1), cation exchange column
(2), the first anion-exchange column (3), the second anion-exchange column (4) and removing sodium post (5), wherein, filter (1), sun from
The solution of sub- exchange column (2), the first anion-exchange column (3) and the second anion-exchange column (4) is imported and exported and is sequentially connected, and first
The saturated liquid outlet of anion-exchange column (3) and the second anion-exchange column (4) is connected with the liquid inlet of removing sodium post (5).
2. system for processing chrome-containing wastewater according to claim 1, it is characterised in that the cation exchange column (2), first
Regenerative agent is respectively provided with the liquid inlet of anion-exchange column (3), the second anion-exchange column (4) and removing sodium post (5) to add
Device (6).
3. system for processing chrome-containing wastewater according to claim 1 and 2, it is characterised in that in the cation exchange column (2)
The resin of filling is the styrene type cation exchange resin of H types 001 × 7；
Preferably, in first anion-exchange column (3) and the second anion-exchange column (4) resin of filling to be surface attached
The D201 styrene series anion exchange resins of polyvinyl amidine and sulfonated polyether sulphone composition；
Preferably, the adhesion amount of the polyvinyl amidine and sulfonated polyether sulphone composition is 15mg/m2～30mg/m2, preferably
20mg/m2～30mg/m2, more preferably 25mg/m2；
Preferably, the mass ratio of the polyvinyl amidine and sulfonated polyether sulphone is (3～10):1, preferably (3～7):1, enter
One step is preferably 5:1；
Preferably, the resin of filling is the styrene type cation exchange resin of H types 001 × 7 in the removing sodium post (5).
4. a kind of chromium containing waste water treatment method, it is characterised in that the method comprising the steps of：
(1) pH to the pH ＜ 4 of chromate waste water are adjusted；
(2) chromate waste water after pH will be adjusted in step (1) carries out ion-exchange treatment with cationic ion-exchange resin, and removing contains chromium
Metal cation in waste water；
(3) waste water that metal cation is stripped of in step (2) is swapped with the first anion exchange resin, it is cloudy to first
Cr in ion exchange resin2O7 2-Switch over when reaching saturation, make waste water and the second anion exchange resin swap place
Reason, while regenerating to the first anion exchange resin of saturation, after the regeneration of the first anion exchange resin sodium chromate is flowed out
Solution；
(4) as Cr in the second anion exchange resin in step (3)2O7 2-Switching over when reaching saturation makes waste water and step (3)
The first anion exchange resin after middle regeneration swaps process, while carrying out again to the second anion exchange resin of saturation
It is raw, flow out chromium acid sodium solution after the regeneration of the second anion exchange resin；
(5) chromium acid sodium solution obtained in step (3) and step (4) is carried out into removing sodium process with cationic ion-exchange resin, is obtained
Chromic acid.
5. chromium containing waste water treatment method according to claim 4, it is characterised in that step (1) the regulation chromate waste water
Before pH, chromate waste water is pre-processed；
Preferably, the pretreatment is mechanical filter；
Preferably, the mechanical filter be sand filtration, carbon filter or ultrafiltration in any one or at least two combination.
6. the chromium containing waste water treatment method according to claim 4 or 5, it is characterised in that cation described in step (2) is handed over
Resin is changed for the styrene type cation exchange resin of H types 001 × 7；
Preferably, cationic ion-exchange resin is pre-processed and made the transition before ion exchange is carried out described in step (2)；
Preferably, the pretreatment and transition is comprised the following steps：
A () cleans water immersion 1h～2h that cationic ion-exchange resin temperature is 50 DEG C～60 DEG C, then deionized water to stream
Water outlet is colourless；
B hydrochloric acid solution drip washing that cationic ion-exchange resin concentration after processing in step (a) is 2wt%～4wt% by () is extremely
The pH ＜ 4 of outflow water, are cleaned to outflow with hydrochloric acid solution immersion 1h～5h that concentration is 2wt%～4wt%, then deionized water
The pH of water is 5～6；
C () drenches the sodium hydroxide solution that the cationic ion-exchange resin concentration Jing after step (b) process is 4wt%～6wt%
The pH ＞ 10 of outflow water are washed till, with the sodium hydroxide solution that concentration is 4wt%～6wt% 1h～5h, then deionized water are soaked
It is 6～7 to clean to the pH of outflow water；
D hydrochloric acid solution drip washing that cationic ion-exchange resin concentration Jing after step (c) process is 2wt%～4wt% by () is extremely
The pH ＜ 4 of outflow water, are cleaned to outflow with hydrochloric acid solution immersion 1h～5h that concentration is 2wt%～4wt%, then deionized water
The pH of water is 5～6, completes the pretreatment and transition of cationic ion-exchange resin.
Preferably, step (b), step (c) and drip washing speed described in step (d) are respectively 5m/h～10m/h；
Preferably, cationic ion-exchange resin described in step (2) is carried out after saturation with the hydrochloric acid solution that concentration is 4～6wt%
Regeneration, regenerates Water Sproading.
7. the chromium containing waste water treatment method according to any one of claim 4-6, it is characterised in that described in step (3)
One anion exchange resin and the second anion exchange resin are surface attachment polyvinyl amidine and sulfonated polyether sulphone group
The D201 styrene series anion exchange resins of compound；
Preferably, the adhesion amount of the polyvinyl amidine and sulfonated polyether sulphone composition is 15mg/m2～30mg/m2, preferably
20mg/m2～30mg/m2, more preferably 25mg/m2；
Preferably, the mass ratio of the polyvinyl amidine and sulfonated polyether sulphone is (3～10):1, preferably (3～7):1, enter
One step is preferably 5:1.
8. the chromium containing waste water treatment method according to any one of claim 4-7, it is characterised in that described in step (3)
One anion exchange resin and the second anion exchange resin are pre-processed and made the transition before ion exchange is carried out；
Preferably, the pretreatment and transition is comprised the following steps：
(a ') cleans water immersion 1h～2h that anion exchange resin temperature is 50 DEG C～60 DEG C, then deionized water to stream
Water outlet is colourless；
(b ') by Jing step (a ') process after cationic ion-exchange resin concentration be 4wt%～6wt% sodium hydroxide solution
The pH ＞ 10 of drip washing to outflow water, with the sodium hydroxide solution that concentration is 4wt%～6wt% 1h～5h is soaked, then uses deionization
The pH of the outflow water of water cleaning is 6～7；
(c ') is by hydrochloric acid solution drip washing that the cationic ion-exchange resin concentration after processing in step (b ') is 2wt%～4wt%
To the pH ＜ 4 of outflow water, with hydrochloric acid solution immersion 1h～5h that concentration is 2wt%～4wt%, then deionized water cleaning and his like
The pH of water outlet is 5～6；
(d ') by Jing step (c ') process after cationic ion-exchange resin concentration be 4wt%～6wt% sodium hydroxide solution
The pH ＞ 10 of drip washing to outflow water, with the sodium hydroxide solution that concentration is 4wt%～6wt% 1h～5h is soaked, then uses deionization
The pH of the outflow water of water cleaning is 8～9.5, completes the pretreatment and transition of cationic ion-exchange resin.
Preferably, drip washing speed is respectively 5m/h～10m/h described in step (b '), step (c ') and step (d ').
9. the chromium containing waste water treatment method according to any one of claim 4-8, it is characterised in that right described in step (3)
First anion exchange resin carries out the sodium hydroxide solution that regeneration concentration is 4～6wt% and is regenerated；
Preferably, described in step (4) to the second anion exchange resin carry out regenerate concentration be 4～6wt% hydrogen-oxygen
Change sodium solution to be regenerated；
Preferably, removing sodium described in step (5) is processed as using cationic exchange resin adsorption Na+, it is desorbed H+, form chromic acid；
Preferably, obtained chromic acid carries out reuse Jing after collecting, concentrate and purify in step (5)；
Preferably, cationic ion-exchange resin described in step (5) is carried out after saturation with the hydrochloric acid solution that concentration is 4～6wt%
Regeneration, regenerates Water Sproading.
10. the chromium containing waste water treatment method according to any one of claim 4-9, it is characterised in that methods described include with
Lower step：
(1) chromate waste water is sent into into filter (1) carries out mechanical filter, then adjusts pH to the pH ＜ 4 of chromate waste water；
(2) will adjust in step (1) chromate waste water after pH send in cation exchange column (2) with through pretreatment and convert
Cationic ion-exchange resin carries out ion-exchange treatment, removes the metal cation in chromate waste water；
(3) waste water that metal cation is stripped of in step (2) is sent into into the first anion-exchange column (3) to hand over the first anion
Change resin to swap, the Cr into the first anion exchange resin2O7 2-Switch over when reaching saturation, make waste water enter second
Anion-exchange column (4) and the second anion exchange resin swap processs, while passing through regenerative agent throwing device (6) to the
The first anion exchange resin of sodium hydroxide solution that concentration is 4～6wt% to saturation is added in one anion-exchange column (3)
Regenerated, after the regeneration of the first anion exchange resin chromium acid sodium solution is flowed out；
(4) as Cr in the second anion exchange resin in step (3)2O7 2-Switching over when reaching saturation makes waste water cloudy into first
Ion exchange column (3) swaps process with the first anion exchange resin after regeneration in step (3), while passing through regenerative agent
Throwing device (6) adds of sodium hydroxide solution that concentration is 4～6wt% to saturation in the second anion-exchange column (4)
Two anion exchange resin are regenerated, and after the regeneration of the second anion exchange resin chromium acid sodium solution is flowed out；
(5) chromium acid sodium solution obtained in step (3) and step (4) is sent in removing sodium post (5) to be entered with cationic ion-exchange resin
The process of row removing sodium, is obtained chromic acid.
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| CN108977658A (en) * | 2018-08-03 | 2018-12-11 | 中国核动力研究设计院 | A kind of Ni-63 solution γ nucleic minimizing technology |
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| CN112452358B (en) * | 2020-10-27 | 2023-04-11 | 南京工业大学 | Process for separating sulfuric acid and aluminum sulfate from aluminate waste liquid by using double-column simulated moving bed |
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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 |
| CN115677090A (en) * | 2022-10-09 | 2023-02-03 | 泉州中节能水处理科技有限公司 | Method for recycling electroplating chromium-containing wastewater |
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| CN116143354B (en) * | 2023-04-19 | 2023-06-16 | 成都之和环保科技有限公司 | Pure water preparation process capable of improving process stability and water quality |
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