CN104628087B - Method for treating vanadium-chromium wastewater by using ion-exchange fibers - Google Patents
Method for treating vanadium-chromium wastewater by using ion-exchange fibers Download PDFInfo
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- CN104628087B CN104628087B CN201510006833.3A CN201510006833A CN104628087B CN 104628087 B CN104628087 B CN 104628087B CN 201510006833 A CN201510006833 A CN 201510006833A CN 104628087 B CN104628087 B CN 104628087B
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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
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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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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Abstract
The invention relates to a method for treating vanadium-chromium wastewater by using ion-exchange fibers, which comprises the following steps: adsorbing quintavalent vanadium ions and hexavalent chromium ions in vanadium-chromium wastewater by using strongly alkaline anion-exchange fibers as an adsorption medium to recover the quintavalent vanadium ions and hexavalent chromium ions; adding a resolving agent into the ion-exchange fibers to perform resolution to obtain a resolving solution, adding an alkaline matter, and carrying out vanadium precipitation to recover the vanadium element and chromium element. The strongly alkaline anion-exchange fibers are a product prepared by grafting polypropylene to styrene and then grafting quaternary amino group, and the functional group is -N＜+＞(CH3)3Cl＜-＞. The method can effectively recover the residual vanadium and chromium in the vanadium-chromium wastewater; the content of vanadium and chromium in the adsorption raffinate does not exceed 0.5 mg/L; the recovery rates of the vanadium and chromium are respectively greater than or equal to 99.9%; no wastewater or waste slag is generated in the whole process; and thus, the method conforms to the green clean production requirements, and has favorable industrialized application prospects.
Description
Technical field
The present invention relates to a kind of processing method containing contents of many kinds of heavy metal ion waste water, more particularly to one kind are handed over using ion
The method changing fiber treatment vanadium chrome waste water.
Background technology
Vanadium chrome waste water is vanadium slag through technique productions barium oxide processes such as sodium roasting-leaching filtration-acid ammonium salt precipitations
The industrial wastewater of middle generation, its pentavalent content of vanadium 50ppm-100ppm about, content of 6-valence Cr ions is more up to 500ppm-
Between 1000ppm, considerably beyond discharging standards.High price vanadium, chromium compound as serious pollution thing, such as outer row or leakage,
Can water body, soil environment be caused greatly to pollute, crops do great damage, and seriously jeopardize health, meanwhile, cause gold
Belong to the waste of resource.
At present, process this kind of waste water more efficiently method have several:
1. reduce neutralization precipitation method: such as number of patent application 201010591828.0 proposes to add reduction in vanadium wastewater
Agent (as sodium pyrosulfite, sodium sulfite etc.), makes pentavalent vanadium, hexavalent chromium Restore All are trivalent, then to after reduction
Alkali liquor is added, neutralization waste water solution makes chromium, vanadium ion formation hydrate be precipitated out from waste water solution simultaneously in waste water solution.
The method equipment is simple, treating capacity is larger, but exist vanadium chromium recovery ratio low, precipitation waste residue cannot directly reclaim vanadium chromium have valency unit
Element, medicament addition need the defects such as precise control manipulation difficulty is big, reagent consumption amount is big, long processing period, processing cost are higher.
2. conventional ion exchange process: even if spent ion exchange resin reclaims the anionic group in vanadium extracting waste water, such as specially
Sharp application number 20100570484 reports the vanadium effectively reclaiming in vanadium extracting waste water using d301 resin absorption, the new technology of chromium.
The method process route is simple, vanadium chromium adsorption rate is higher, but still suffers from the defect that many is difficult to avoid, and such as 1) amberlite
The adsorption rate of fat is slower, limited by disposal ability；2) after d301 resin absorption, adsorption tail liquid 2mg/l containing vanadium about, still surpass
Cross discharging standards (being less than 0.5mg/l containing vanadium) to require, still cannot directly discharge after process；3) ion exchange resin temperature tolerance
Can be very poor, between allowable temperature scope is 10 DEG C～80 DEG C, use at a higher temperature for a long time, easily swelling broken inactivation.And
Vanadium extracting waste water produces for boiling precipitation technique, and typical temperature is more than 90 DEG C, normally first using palpus for ensureing ion exchange resin
Waste water is cooled to less than 80 DEG C, then is adsorbed, and adsorb follow-up deamination technique and wastewater temperature must be risen to more than 95 DEG C,
First lower the temperature the process heating up afterwards, inevitably cause a large amount of wastes of heat energy；4) the optimum absorption ph to vanadium chromium for the d301 resin
=8, and the ph value of vanadium wastewater, generally between 2-3, needs before therefore adsorbing to add sodium carbonate to be neutralized, that is, increase flow process
Chain, increased the reagent cost of process again；5) although above-mentioned patent is pointed out, the vanadium parsing chromium is reclaimed, and unknown
Really point out that such high-alkali vanadium chromium desorbed solution carries out the concrete grammar of valuable element recycling.
Content of the invention
For problems of the prior art, the present invention provides one kind to process vanadium chromium using strong basic ion exchange fiber
The method of waste water.
For solving above-mentioned technical problem, the technical solution used in the present invention is: adopts strongly basic anion ion exchange fibre
As adsorbing medium, the pentavalent vanadium ion in vanadium chrome waste water and hexavalent chromium are adsorbed, reclaim pentavalent vanadium ion with
And hexavalent chromium；After absorption, ion-exchange fibre adds parsing agent to be parsed, and obtains desorbed solution, adds alkaline matter and carries out
Precipitation, heavy chromium, reclaims v element and chromium；Described strongly basic anion ion exchange fibre, is polypropylene grafted styrene
Grafting quaternary ammonium obtains product afterwards, and functional group is :-n+(ch3)3cl-.
The present invention comprises the following steps: 1) adsorbs: using strongly basic anion ion exchange fibre as adsorbing medium, to vanadium chromium
Pentavalent vanadium ion in waste water and hexavalent chromium are adsorbed completely；
Described absorption completely refers to for vanadium chrome waste water directly to pass through exchange fiber column, and which is by the pentavalent vanadium in waste water
Ion, hexavalent chromium adsorb simultaneously, and up to after absorption, tail washings contains vanadium and is higher than 0.5mg/l or contains chromium higher than after 0.5mg/l, stops
Absorption, after adsorb ion-exchange fibre and adsorb after tail washings；
2) parse: after above-mentioned absorption, ion-exchange fibre adds parsing agent to be parsed, and obtains vanadium chromium mixing pregnant solution；
After parsing, ion-exchange fibre uses as adsorbing medium again；
3) precipitation: in vanadium chromium mixing pregnant solution add alkaline matter, after stirring, filter, obtain vanadic acid calcium product and
Liquid after precipitation；Described alkaline matter is any one or a few in calcium oxide, calcium hydroxide powder or calcium hydroxide slurry；
4) sink chromium: select one and precipitate chromium from following two modes:
Method one: add in liquid after precipitation barium hydroxide or barium chloride any one powder or solution, obtain barium chromate
Liquid after product and heavy chromium；After heavy chromium, liquid can recycle as parsing agent；
Method two: add sulphuric acid to adjust ph value to 4-6 in liquid after precipitation, add reducing agent, by hexavalent chromium also
Former one-tenth trivalent chromic ion, adds naoh, adjusts ph value to 7-9, obtains liquid after chromic oxide gel product and heavy chromium.
The present invention comprises the following steps: 1) adsorbs: using strongly basic anion ion exchange fibre as adsorbing medium, to vanadium chromium
Pentavalent vanadium ion in waste water and hexavalent chromium carry out selectivity stepwise adsorption；
Described selectivity stepwise adsorption is directed to add sulphuric acid in waste water, adjusts waste water ph value to 1-1.5, fine by exchanging
Dimension post, until absorption after tail washings contain chromium be higher than 0.5mg/l, after adsorb ion-exchange fibre and adsorb after tail washings；
Add naoh in tail washings to after absorption, adjust its ph value to 2.5-3, by exchange fiber column, until tail washings contains after absorption
Vanadium be higher than 0.5mg/l, after adsorb ion-exchange fibre and adsorb after tail washings；
2) parse: after above-mentioned absorption, ion-exchange fibre adds parsing agent to be parsed, and obtains chromium pregnant solution；Ion is handed over
Changing fiber adds parsing agent to be parsed, and obtains vanadium enrichment liquid；Ion-exchange fibre, again conduct absorption Jie after parsing
Matter uses；
3) precipitation: add alkaline matter in vanadium enrichment liquid, after stirring, filter, after obtaining vanadic acid calcium product and precipitation
Liquid；Described alkaline matter is any one or a few in calcium oxide, calcium hydroxide powder or calcium hydroxide slurry；
4) sink chromium: select one and precipitate chromium from following two modes:
Method one: add in chromium pregnant solution barium hydroxide or barium chloride any one powder or solution, obtain barium chromate
Liquid after product and heavy chromium, after heavy chromium, liquid can recycle as parsing agent；
Method two: add sulphuric acid to adjust ph value to 4-6 in chromium pregnant solution, add reducing agent, by hexavalent chromium also
Former one-tenth trivalent chromic ion, adds naoh, adjusts ph value to 7-9, obtains liquid after chromic oxide gel product and heavy chromium.
After heavy chromium of the present invention liquid with absorption after tail washings mix or carries out respectively deamination, four-effect evaporation process after, follow
Ring utilizes.
After heavy chromium of the present invention, liquid can mix or carry out respectively deamination with tail washings after absorption, four-effect evaporation is processed
Afterwards, recycle.
Parsing agent of the present invention is any one in liquid after 1-5mol/l naoh aqueous solution or heavy chromium.Preferably
Ground, adopts 1-5mol/l naoh aqueous solution, liquid after the heavy chromium obtaining using previous flow process afterwards first；Preferably, parse agent
Adopt 2mol/l naoh aqueous solution first.
During precipitation of the present invention, the addition of alkaline matter is: by the amount of v element material in desorbed solution: alkali
Property material in the amount=0.8:1-1.2:1 of calcium constituent material add, reaction temperature 40-100 DEG C, response time 0.5-4h.
During heavy chromium of the present invention, barium hydroxide or barium chloride any one powder or after its solution presses precipitation
The amount of chromium material in liquid or chromium pregnant solution: in baric material, the amount of barium elemental substance=0.8:1-1.2:1 adds, reaction temperature
10-100 DEG C of degree, response time 0.5-4h.
During heavy chromium of the present invention, reducing agent be sulfur dioxide, sodium thiosulfate, sodium sulfite any one
Or it is several；Reducing agent is by the amount of chromium material in liquid after precipitation or chromium pregnant solution: the amount=2:1-1:2 of reducing agent material adds
Enter, reaction temperature 10-100 DEG C, response time 0.5-4h.
Strongly basic anion ion exchange fibre of the present invention, has extremely strong absorbability to high price vanadium chromium ion, can make suction
Attached tail washings contains vanadium and is less than 0.5mg/l, vanadium recovery more than 99.9%, and after absorption, tail washings contains chromium less than 0.5mg/l, chromium recovery ratio
More than 99.9%.
After absorption of the present invention, tail washings deamination, four-effect evaporation processing method are same domain general technology, and here is not carried out
Repeat.
Have the beneficial effects that using produced by technique scheme: be situated between as absorption using strong alkali anion exchange fiber
Matter, can reclaim the vanadium chromium of residual in vanadium chrome waste water effectively, and after absorption, tail washings contains vanadium, chromium all less than 0.5mg/l, and vanadium, chromium return
All >=99.9%, after absorption, tail washings can return leachate through subsequent treatment to yield.Adopt step-by-step precipitation method after parsing, carry out vanadium
The separation of chromium component, separates the calcium vanadate product purity obtaining up to more than 95%, can be directly used for former as smelting ferrovanadium
Material；Barium chromate product purity, up to more than 96%, can use directly as high-grade dyestuff；Chromic oxide gel product purity is up to 95%
More than, can be introduced in process for making as chromium additive.After heavy chromium, liquid can recycle as desorbed solution, both achieved
The separation of valuable element and comprehensive utilization, make whole flow process no waste water and dregs produce again, meet green clean manufacturing and require, tool
There is good industrial applications prospect.
Brief description
Fig. 1 is the process chart of the present invention.
Specific embodiment
With reference to specific embodiment, the present invention is further detailed explanation.
Embodiment 1:
Take the vanadium extraction tail washings 1l of Chengde iron and steel enterprise, after its before processing, main chemical compositions are shown in Table 1, according to vanadium chrome waste water
Absorbing process flow processing completely, after process, is fully achieved discharging standards and requires.Processing method is as follows:
1) adsorb: using strongly basic anion ion exchange fibre as adsorbing medium, to the pentavalent vanadium ion in vanadium chrome waste water
And hexavalent chromium is adsorbed completely；By vanadium chrome waste water directly pass through exchange fiber column, by the pentavalent vanadium in waste water from
Son, hexavalent chromium adsorb simultaneously, until tail washings vanadium or chromium content, higher than after 0.5mg/l, stop absorption, adsorbed after absorption
Afterwards ion-exchange fibre and absorption after tail washings；After after absorption, tail washings deamination, four-effect evaporation method are processed, recycle.
2) parse: after absorption, ion-exchange fibre adds parsing agent to be parsed, and obtains vanadium chromium mixing pregnant solution；Parsing
Ion-exchange fibre uses as adsorbing medium again afterwards.
Parsing agent is adopted to be 2mol/l naoh aqueous solution first, liquid after the heavy chromium obtaining using previous flow process afterwards.
3) precipitation: in vanadium chromium mixing pregnant solution, by the amount of v element material in desorbed solution: calcium constituent in calcium hydroxide slurry
The amount of material=0.8:1 adds calcium hydroxide slurry, after stirring, under the conditions of 80 DEG C of temperature, response time 1h, filters, obtains
The liquid to after vanadic acid calcium product and precipitation；
4) heavy chromium: add barium hydroxide solution in liquid after precipitation, by the amount of chromium material in liquid after precipitation: barium hydroxide
Amount 1.2:1 of middle barium elemental substance adds, and obtains liquid after barium chromate product and heavy chromium；After heavy chromium, liquid can be used as parsing agent circulation
Use；25 DEG C of reaction temperature, response time 2h.
Separating the calcium vanadate product purity obtaining is 95.48%, can be directly used for the raw material as smelting ferrovanadium；Barium chromate
Product purity is 97.06%, can use directly as high-grade dyestuff.
After table 1 vanadium chrome waste water before processing, main chemical compositions compare
| v5+(mg/l) | cr6+(mg/l) | ph | |
| Before processing | 57 | 660 | 1.9 |
| After process | 0.2 | 0.3 | 2.1 |
Table 2 vanadium chromium mixing pregnant solution main chemical compositions
| v5+(mg/l) | cr6+(mg/l) | ph |
| 533 | 16500 | 14 |
Embodiment 2:
Take the vanadium extraction tail washings 2l of Chengde iron and steel enterprise, after its before processing, main chemical compositions are shown in Table 3, according to vanadium chrome waste water
Absorbing process flow processing completely, after process, is fully achieved discharging standards and requires.Processing method is as follows:
1) adsorb: using strongly basic anion ion exchange fibre as adsorbing medium, to the pentavalent vanadium ion in vanadium chrome waste water
And hexavalent chromium is adsorbed completely；By vanadium chrome waste water directly pass through exchange fiber column, by the pentavalent vanadium in waste water from
Sub, hexavalent chromium adsorbs simultaneously, and up to after absorption, tail washings is higher than 0.5mg/l containing vanadium or contains chromium higher than after 0.5mg/l, stops suction
Attached, after being adsorbed ion-exchange fibre and absorption after tail washings；Tail washings deamination after described absorption, at four-effect evaporation method
After reason, recycle.
2) parse: after absorption, ion-exchange fibre adds parsing agent to be parsed, and obtains vanadium chromium mixing pregnant solution；Parsing
Ion-exchange fibre uses as adsorbing medium again afterwards；Parsing agent is 2.5mol/l naoh aqueous solution.
3) precipitation: add calcium hydroxide slurry in vanadium chromium mixing pregnant solution, by the amount of v element material in desorbed solution: hydrogen-oxygen
Amount=the 1:1 changing calcium constituent material in calcium slurry adds, after stirring, under the conditions of 90 DEG C of temperature, response time 2h, and filter,
Obtain liquid after vanadic acid calcium product and precipitation；
4) heavy chromium: add sulphuric acid to adjust ph value to 4 in liquid after precipitation, add reducing agent, hexavalent chromium is reduced into three
Valency chromium ion, adds naoh, adjusts ph value between 7, obtains liquid after chromic oxide gel product and heavy chromium；After heavy chromium, liquid can
Mix with tail washings after absorption and carry out deamination, four-effect evaporation process.
Reducing agent is sulfur dioxide；Reducing agent is by the amount of chromium material in liquid after precipitation: the amount=1:2 of reducing agent material
Add, 50 DEG C of reaction temperature, response time 1.5h.
Separating the calcium vanadate product purity obtaining is 96.75%, can be directly used for the raw material as smelting ferrovanadium；Hydroxide
Chromium product purity, up to 98.16%, can use directly as steel-making additive.
After table 3 vanadium chrome waste water before processing, main chemical compositions compare
| v5+(mg/l) | cr6+(mg/l) | ph | |
| Before processing | 50 | 653 | 1.9 |
| After process | 0.3 | 0.2 | 2.1 |
Table 4 vanadium chromium mixing pregnant solution main chemical compositions
| v5+(mg/l) | cr6+(mg/l) | ph |
| 628 | 15500 | 14 |
Embodiment 3:
Take the vanadium extraction tail washings 1l of Chengde iron and steel enterprise, after its before processing, main chemical compositions are shown in Table 5, according to vanadium chrome waste water
Absorbing process flow processing completely, after process, is fully achieved discharging standards and requires.Processing method is as follows:
1) adsorb: using strongly basic anion ion exchange fibre as adsorbing medium, to the pentavalent vanadium ion in vanadium chrome waste water
And hexavalent chromium is adsorbed completely；By vanadium chrome waste water directly pass through exchange fiber column, by the pentavalent vanadium in waste water from
Son, hexavalent chromium adsorb simultaneously, until vanadium or chromium content, higher than after 0.5mg/l, stop absorption, inhaled in tail washings after absorption
Tail washings after attached ion-exchange fibre and absorption；After after absorption, tail washings deamination, four-effect evaporation method are processed, recycle.
2) parse: after absorption, ion-exchange fibre adds parsing agent to be parsed, and obtains vanadium chromium mixing pregnant solution；Parsing
Ion-exchange fibre uses as adsorbing medium again afterwards.
Parsing agent is adopted to be 5mol/l naoh aqueous solution first, liquid after the heavy chromium obtaining using previous flow process afterwards.
3) precipitation: in vanadium chromium mixing pregnant solution, by the amount of v element material in desorbed solution: calcium constituent thing in lime powder
The amount of matter=1.2:1 adds lime powder, after stirring, under the conditions of 40 DEG C of temperature, response time 4h, filters, obtains vanadium
Liquid after sour calcium product and precipitation；
4) heavy chromium: add chlorination barium dust in liquid after precipitation, by the amount of chromium material in liquid after precipitation: in barium hydroxide
Amount 0.8:1 of barium elemental substance adds, and obtains liquid after barium chromate product and heavy chromium；After heavy chromium, liquid makes as parsing agent circulation
With；100 DEG C of reaction temperature, response time 0.5h.
Separating the calcium vanadate product purity obtaining is 95.69%, can be directly used for the raw material as smelting ferrovanadium；Barium chromate
Product purity is 98.11%, can use directly as high-grade dyestuff.
After table 5 vanadium chrome waste water before processing, main chemical compositions compare
| v5+(mg/l) | cr6+(mg/l) | ph | |
| Before processing | 57 | 660 | 1.9 |
| After process | 0.2 | 0.3 | 2.1 |
Table 6 vanadium chromium mixing pregnant solution main chemical compositions
| v5+(mg/l) | cr6+(mg/l) | ph |
| 536 | 16530 | 14 |
Embodiment 4:
Take the vanadium extraction tail washings 2l of Chengde iron and steel enterprise, after its before processing, main chemical compositions are shown in Table 7, according to vanadium chrome waste water
Absorbing process flow processing completely, after process, is fully achieved discharging standards and requires.Processing method is as follows:
1) adsorb: using strongly basic anion ion exchange fibre as adsorbing medium, to the pentavalent vanadium ion in vanadium chrome waste water
And hexavalent chromium is adsorbed completely；By vanadium chrome waste water directly pass through exchange fiber column, by the pentavalent vanadium in waste water from
Sub, hexavalent chromium adsorbs simultaneously, higher than 0.5mg/l or contains chromium higher than after 0.5mg/l containing vanadium, stop in the tail washings up to after absorption
Absorption, after adsorb ion-exchange fibre and adsorb after tail washings；Tail washings deamination, four-effect evaporation method after described absorption
After process, recycle.
2) parse: after absorption, ion-exchange fibre adds parsing agent to be parsed, and obtains vanadium chromium mixing pregnant solution；Parsing
Ion-exchange fibre uses as adsorbing medium again afterwards；Parsing agent is 1mol/l naoh aqueous solution.
3) precipitation: add calcium oxide slurry in vanadium chromium mixing pregnant solution, by the amount of v element material in desorbed solution: calcium oxide
In slurry, the amount of calcium constituent material=1.1:1 adds, after stirring, under the conditions of 100 DEG C of temperature, response time 0.5h, and filter,
Obtain liquid after vanadic acid calcium product and precipitation；
4) heavy chromium: add sulphuric acid to adjust ph value to 6 in liquid after precipitation, add reducing agent, hexavalent chromium is reduced into three
Valency chromium ion, adds naoh, adjusts ph value between 9, obtains liquid after chromic oxide gel product and heavy chromium；After heavy chromium, liquid can
Mix with tail washings after absorption and carry out deamination, four-effect evaporation process.
Reducing agent is sodium thiosulfate；Amount by chromium material in liquid after precipitation: the amount=2:1 of reducing agent material adds
Enter, 10 DEG C of reaction temperature, response time 4h.
Separating the calcium vanadate product purity obtaining is 96.36%, can be directly used for the raw material as smelting ferrovanadium；Hydroxide
Chromium product purity, up to 98.25%, can use directly as steel-making additive.
After table 7 vanadium chrome waste water before processing, main chemical compositions compare
| v5+(mg/l) | cr6+(mg/l) | ph | |
| Before processing | 50 | 653 | 1.9 |
| After process | 0.3 | 0.2 | 2.1 |
Table 8 vanadium chromium mixing pregnant solution main chemical compositions
| v5+(mg/l) | cr6+(mg/l) | ph |
| 632 | 15550 | 14 |
Embodiment 5:
Take the vanadium extraction tail washings 2l of Chengde iron and steel enterprise, after its before processing, main chemical compositions are shown in Table 9, according to vanadium chrome waste water
Stepwise adsorption technological process, carries out the process of vanadium chrome waste water, after process, is fully achieved discharging standards and requires, processing method
As follows:
1) adsorb: using strongly basic anion ion exchange fibre as adsorbing medium, to the pentavalent vanadium ion in vanadium chrome waste water
And hexavalent chromium carries out selectivity stepwise adsorption.Add sulphuric acid in waste water, adjust waste water ph value to 1, fine by exchanging
Dimension post, until absorption after tail washings contain chromium be higher than 0.5mg/l, after adsorb ion-exchange fibre and adsorb after tail washings；
Add naoh in tail washings to after absorption, adjust its ph value to 2.5, by exchange fiber column, until tail washings contains vanadium after absorption
Higher than 0.5mg/l, tail washings after ion-exchange fibre and absorption after being adsorbed, tail washings deamination after absorption, quadruple effect steam
After forwarding method is processed, recycle.
2) parse: after above-mentioned absorption, ion-exchange fibre adds parsing agent to be parsed, and obtains chromium pregnant solution；Ion is handed over
Changing fiber adds parsing agent to be parsed, and obtains vanadium enrichment liquid；Ion-exchange fibre, again conduct absorption Jie after parsing
Matter uses.
Described parsing agent, first using parsing agent for 2mol/l naoh aqueous solution, is obtained using previous flow process afterwards
Liquid after heavy chromium.
3) precipitation: add alkaline matter calcium hydroxide powder in vanadium enrichment liquid, by the amount of v element material in desorbed solution: hydrogen
In lime powder, the amount of calcium constituent material=1.1:1 adds, 60 DEG C of reaction temperature, response time 1h, after stirring, mistake
Filter, obtains liquid after vanadic acid calcium product and precipitation.
4) heavy chromium: add barium hydroxide powder in chromium pregnant solution, by the amount of chromium material in liquid after precipitation: baric material
The amount of barium elemental substance=1:1 adds, and under the conditions of 40 DEG C of temperature, response time 1h obtains liquid after barium chromate product and heavy chromium,
After heavy chromium, liquid recycles as parsing agent.
Separate the calcium vanadate product purity obtaining up to 96.93%, can be directly used for the raw material as smelting ferrovanadium；Chromic acid
Barium product purity, up to 96.17%, can use directly as high-grade dyestuff.After heavy chromium, liquid can recycle as desorbed solution.
After table 9 vanadium chrome waste water before processing, main chemical compositions compare
| v5+(mg/l) | cr6+(mg/l) | ph | |
| Before processing | 50 | 703 | 1.9 |
| After process | 0.1 | Do not detect | 2.1 |
Table 10 chromium pregnant solution main chemical compositions
| cr6+(mg/l) | ph |
| 18500 | 14 |
Table 11 vanadium enrichment liquid main chemical compositions
| v5+(mg/l) | ph |
| 6500 | 14 |
Embodiment 6:
Take the vanadium extraction tail washings 2l of Chengde iron and steel enterprise, after its before processing, main chemical compositions are shown in Table 12, give up according to vanadium chromium
Moisture walks absorbing process flow process, carries out the process of vanadium chrome waste water, after process, is fully achieved discharging standards and requires, process side
Method is as follows:
1) adsorb: using strongly basic anion ion exchange fibre as adsorbing medium, to the pentavalent vanadium ion in vanadium chrome waste water
And hexavalent chromium carries out selectivity stepwise adsorption.Add sulphuric acid in waste water, adjust waste water ph value to 1.5, by exchanging
Fibre columns, until absorption after tail washings contain chromium be higher than 0.5mg/l, after adsorb ion-exchange fibre and adsorb after tail washings
ⅱ；Add naoh in tail washings to after absorption, adjust its ph value to 3, by exchange fiber column, until tail washings contains vanadium after absorption
Higher than 0.5mg/l, tail washings after ion-exchange fibre and absorption after being adsorbed, tail washings deamination after absorption, quadruple effect steam
After forwarding method is processed, recycle.
2) parse: after above-mentioned absorption, ion-exchange fibre adds parsing agent to be parsed, and obtains chromium pregnant solution；Ion is handed over
Changing fiber adds parsing agent to be parsed, and obtains vanadium enrichment liquid；Ion-exchange fibre, again conduct absorption Jie after parsing
Matter uses；Parsing agent is 2.7mol/l naoh aqueous solution.
3) precipitation: add alkaline matter lime powder in vanadium enrichment liquid, by the amount of v element material in desorbed solution: oxidation
In calcium powder, the amount of calcium constituent material=1:1 adds, 48 DEG C of reaction temperature, response time 4h, after stirring, filters, obtains
Liquid after vanadic acid calcium product and precipitation.
4) heavy chromium: add sulphuric acid to adjust ph value to 5 in chromium pregnant solution, add reducing agent, hexavalent chromium is reduced into three
Valency chromium ion, adds naoh, adjusts ph value to 8, obtains liquid after chromic oxide gel product and heavy chromium, after heavy chromium, liquid can be with suction
Attached tail washings mixing carries out deamination, four-effect evaporation is processed.
Reducing agent is the mixture of sodium thiosulfate and sodium sulfite mass ratio 1:1；Reducing agent is by chromium unit in liquid after precipitation
The amount of plain material: the amount of reducing agent material=1:1 adds, 100 DEG C of reaction temperature, response time 0.5h.
Separate the calcium vanadate product purity obtaining up to 96.64%, can be directly used for the raw material as smelting ferrovanadium；Chromic acid
Barium product purity, up to 96.31%, can use directly as high-grade dyestuff.After heavy chromium, liquid can recycle as desorbed solution.
After table 12 vanadium chrome waste water before processing, main chemical compositions compare
| v5+(mg/l) | cr6+(mg/l) | ph | |
| Before processing | 50 | 703 | 1.9 |
| After process | 0.1 | Do not detect | 2.1 |
Table 13 chromium pregnant solution main chemical compositions
| cr6+(mg/l) | ph |
| 18560 | 14 |
Table 14 vanadium enrichment liquid main chemical compositions
| v5+(mg/l) | ph |
| 6580 | 14 |
Embodiment 7:
Take the vanadium extraction tail washings 2l of Chengde iron and steel enterprise, after its before processing, main chemical compositions are shown in Table 15, give up according to vanadium chromium
Moisture walks absorbing process flow process, carries out the process of vanadium chrome waste water, after process, is fully achieved discharging standards and requires, process side
Method is as follows:
1) adsorb: using strongly basic anion ion exchange fibre as adsorbing medium, to the pentavalent vanadium ion in vanadium chrome waste water
And hexavalent chromium carries out selectivity stepwise adsorption.Add sulphuric acid in waste water, adjust waste water ph value to 1.2, by exchanging
Fibre columns, until absorption after tail washings contain chromium be higher than 0.5mg/l, after adsorb ion-exchange fibre and adsorb after tail washings
ⅱ；Add naoh in tail washings to after absorption, adjust its ph value to 2, by exchange fiber column, until tail washings contains vanadium after absorption
Higher than 0.5mg/l, tail washings after ion-exchange fibre and absorption after being adsorbed, tail washings deamination after absorption, quadruple effect steam
After forwarding method is processed, recycle.
2) parse: after above-mentioned absorption, ion-exchange fibre adds parsing agent to be parsed, and obtains chromium pregnant solution；Ion is handed over
Changing fiber adds parsing agent to be parsed, and obtains vanadium enrichment liquid；Ion-exchange fibre, again conduct absorption Jie after parsing
Matter uses.
Described parsing agent, first using parsing agent for 3.5mol/l naoh aqueous solution, is obtained using previous flow process afterwards
Heavy chromium after liquid.
3) precipitation: add alkaline matter calcium oxide slurry in vanadium enrichment liquid, by the amount of v element material in desorbed solution: oxidation
In calcium slurry, the amount of calcium constituent material=1.2:1 adds, 78 DEG C of reaction temperature, response time 2.5h, after stirring, filters,
Obtain liquid after vanadic acid calcium product and precipitation.
4) heavy chromium: add barium chloride solution in chromium pregnant solution, by the amount of chromium material in liquid after precipitation: barium chloride solution
The amount of middle barium elemental substance=0.9:1 adds, under the conditions of 10 DEG C of temperature, after response time 4h obtains barium chromate product and heavy chromium
Liquid, after heavy chromium, liquid can recycle as parsing agent.
Separate the calcium vanadate product purity obtaining up to 97.03%, can be directly used for the raw material as smelting ferrovanadium；Chromic acid
Barium product purity, up to 97.97%, can use directly as high-grade dyestuff.After heavy chromium, liquid can recycle as desorbed solution.
After table 15 vanadium chrome waste water before processing, main chemical compositions compare
| v5+(mg/l) | cr6+(mg/l) | ph | |
| Before processing | 50 | 703 | 1.9 |
| After process | 0.1 | Do not detect | 2.1 |
Table 16 chromium pregnant solution main chemical compositions
| cr6+(mg/l) | ph |
| 18540 | 14 |
Table 17 vanadium enrichment liquid main chemical compositions
| v5+(mg/l) | ph |
| 6580 | 14 |
Embodiment 8:
Take the vanadium extraction tail washings 2l of Chengde iron and steel enterprise, after its before processing, main chemical compositions are shown in Table 18, give up according to vanadium chromium
Moisture walks absorbing process flow process, carries out the process of vanadium chrome waste water, after process, is fully achieved discharging standards and requires, process side
Method is as follows:
1) adsorb: using strongly basic anion ion exchange fibre as adsorbing medium, to the pentavalent vanadium ion in vanadium chrome waste water
And hexavalent chromium carries out selectivity stepwise adsorption.Add sulphuric acid in waste water, adjust waste water ph value to 1.4, by exchanging
Fibre columns, until absorption after tail washings contain chromium be higher than 0.5mg/l, after adsorb ion-exchange fibre and adsorb after tail washings
ⅱ；Add naoh in tail washings to after absorption, adjust its ph value to 2.8, by exchange fiber column, until tail washings contains after absorption
Vanadium be higher than 0.5mg/l, after adsorb ion-exchange fibre and adsorb after tail washings, tail washings deamination, quadruple effect after absorption
After method of evaporating is processed, recycle.
2) parse: after above-mentioned absorption, ion-exchange fibre adds parsing agent to be parsed, and obtains chromium pregnant solution；Ion is handed over
Changing fiber adds parsing agent to be parsed, and obtains vanadium enrichment liquid；Ion-exchange fibre, again conduct absorption Jie after parsing
Matter uses；Parsing agent is 5mol/l naoh aqueous solution.
3) precipitation: add alkaline matter lime powder in vanadium enrichment liquid, by the amount of v element material in desorbed solution: oxidation
In calcium powder, the amount of calcium constituent material=0.85:1 adds, 92 DEG C of reaction temperature, response time 1.5h, after stirring, filters,
Obtain liquid after vanadic acid calcium product and precipitation.
4) heavy chromium: add sulphuric acid to adjust ph value to 4.5 in chromium pregnant solution, add reducing agent, hexavalent chromium is reduced into
Trivalent chromic ion, adds naoh, adjusts ph value to 7.5, obtains liquid after chromic oxide gel product and heavy chromium, after heavy chromium, liquid can
Mix with tail washings after absorption and carry out deamination, four-effect evaporation process.
Reducing agent is sulfur dioxide；Reducing agent is by the amount of chromium material in liquid after precipitation: the amount=2:1 of reducing agent material
Add, 67 DEG C of reaction temperature, response time 3.5h.
Separate the calcium vanadate product purity obtaining up to 96.77%, can be directly used for the raw material as smelting ferrovanadium；Chromic acid
Barium product purity, up to 97.52%, can use directly as high-grade dyestuff.After heavy chromium, liquid can recycle as desorbed solution.
After table 18 vanadium chrome waste water before processing, main chemical compositions compare
| v5+(mg/l) | cr6+(mg/l) | ph | |
| Before processing | 50 | 703 | 1.9 |
| After process | 0.2 | Do not detect | 2.1 |
Table 19 chromium pregnant solution main chemical compositions
| cr6+(mg/l) | ph |
| 18510 | 14 |
Table 20 vanadium enrichment liquid main chemical compositions
| v5+(mg/l) | ph |
| 6570 | 14 |
Claims (9)
1. a kind of utilization strong basic ion exchange fiber process vanadium chrome waste water method it is characterised in that using strong basicity cloudy from
Sub- exchange fiber, as adsorbing medium, adsorbs to the pentavalent vanadium ion in vanadium chrome waste water and hexavalent chromium, reclaims five
Valency vanadium ion and hexavalent chromium；After absorption, ion-exchange fibre adds parsing agent to be parsed, and obtains desorbed solution, adds alkali
Property material carry out precipitation, heavy chromium, reclaim v element and chromium；Described strongly basic anion ion exchange fibre, is polypropylene
After graft phenylethene, grafting quaternary ammonium obtains product, and functional group is :-n+(ch3)3cl-；
The method that a kind of described utilization strong basic ion exchange fiber processes vanadium chrome waste water, comprises the following steps:
1) adsorb: using strongly basic anion ion exchange fibre as adsorbing medium, to the pentavalent vanadium ion in vanadium chrome waste water and
Hexavalent chromium carries out selectivity stepwise adsorption；
Described selectivity stepwise adsorption is directed to add sulphuric acid in waste water, adjusts waste water ph value to 1-1.5, by exchange fiber column
, until absorption after tail washings contain chromium be higher than 0.5mg/l, after adsorb ion-exchange fibre and adsorb after tail washings；To suction
Add naoh in attached tail washings, adjust its ph value to 2.5-3, by exchange fiber column, until tail washings contains vanadium height after absorption
In 0.5mg/l, after being adsorbed ion-exchange fibre and absorption after tail washings；
2) parse: after above-mentioned absorption, ion-exchange fibre adds parsing agent to be parsed, and obtains chromium pregnant solution；Ion exchange is fine
Dimension adds parsing agent to be parsed, and obtains vanadium enrichment liquid；Ion-exchange fibre after parsing, again make as adsorbing medium
With；
3) precipitation: add alkaline matter in vanadium enrichment liquid, after stirring, filter, obtain liquid after vanadic acid calcium product and precipitation；Institute
State alkaline matter be calcium oxide, any one or a few in calcium hydroxide powder or calcium hydroxide slurry；
4) sink chromium: select one and precipitate chromium from following two modes:
Method one: add in chromium pregnant solution barium hydroxide or barium chloride any one powder or solution, obtain barium chromate product
With liquid after heavy chromium, after heavy chromium, liquid can recycle as parsing agent；
Method two: add sulphuric acid to adjust ph value to 4-6 in chromium pregnant solution, add reducing agent, hexavalent chromium is reduced into
Trivalent chromic ion, adds naoh, adjusts ph value to 7-9, obtains liquid after chromic oxide gel product and heavy chromium；
Described parsing agent is 1-5mol/l naoh aqueous solution.
2. the method that a kind of utilization strong basic ion exchange fiber according to claim 1 processes vanadium chrome waste water, its feature
It is, comprise the following steps:
1) adsorb: using strongly basic anion ion exchange fibre as adsorbing medium, to the pentavalent vanadium ion in vanadium chrome waste water and
Hexavalent chromium is adsorbed completely；
Described completely absorption refer to by vanadium chrome waste water directly pass through exchange fiber column, which by the pentavalent vanadium ion in waste water,
Hexavalent chromium adsorbs simultaneously, and up to after absorption, tail washings contains vanadium and is higher than 0.5mg/l or contains chromium higher than after 0.5mg/l, stops absorption,
After being adsorbed ion-exchange fibre and absorption after tail washings；
2) parse: after above-mentioned absorption, ion-exchange fibre adds parsing agent to be parsed, and obtains vanadium chromium mixing pregnant solution；Parsing
Ion-exchange fibre uses as adsorbing medium again afterwards；
3) precipitation: add alkaline matter in vanadium chromium mixing pregnant solution, after stirring, filter, obtain vanadic acid calcium product and precipitation
Liquid afterwards；Described alkaline matter is any one or a few in calcium oxide, calcium hydroxide powder or calcium hydroxide slurry；
4) sink chromium: select one and precipitate chromium from following two modes:
Method one: add in liquid after precipitation barium hydroxide or barium chloride any one powder or solution, obtain barium chromate product
With liquid after heavy chromium；After heavy chromium, liquid can recycle as parsing agent；
Method two: add sulphuric acid to adjust ph value to 4-6 in liquid after precipitation, add reducing agent, hexavalent chromium is reduced into
Trivalent chromic ion, adds naoh, adjusts ph value to 7-9, obtains liquid after chromic oxide gel product and heavy chromium.
3. the method that a kind of utilization strong basic ion exchange fiber according to claim 2 processes vanadium chrome waste water, its feature
Be, after described heavy chromium liquid with absorption after tail washings mix or carries out respectively deamination, four-effect evaporation process after, recycle.
4. the method that a kind of utilization strong basic ion exchange fiber according to claim 1 processes vanadium chrome waste water, its feature
It is, after after described heavy chromium, liquid can mix or carry out respectively deamination with tail washings after absorption, four-effect evaporation processes, circulation is sharp
With.
5. a kind of utilization strong basic ion exchange fiber according to claim 1-4 any one processes the side of vanadium chrome waste water
Method is it is characterised in that described parsing agent is liquid after heavy chromium.
6. a kind of utilization strong basic ion exchange fiber according to claim 1-4 any one processes the side of vanadium chrome waste water
Method is it is characterised in that during described precipitation, the addition of alkaline matter is: by the amount of v element material in desorbed solution: alkali
Property material in the amount=0.8:1-1.2:1 of calcium constituent material add, reaction temperature 40-100 DEG C, response time 0.5-4h.
7. a kind of utilization strong basic ion exchange fiber according to claim 1-4 any one processes the side of vanadium chrome waste water
Method it is characterised in that during described heavy chromium, barium hydroxide or barium chloride any one powder or after its solution presses precipitation
The amount of chromium material in liquid or chromium pregnant solution: in baric material, the amount of barium elemental substance=0.8:1-1.2:1 adds, reaction temperature
10-100 DEG C of degree, response time 0.5-4h.
8. a kind of utilization strong basic ion exchange fiber according to claim 1-4 any one processes the side of vanadium chrome waste water
Method it is characterised in that during described heavy chromium, reducing agent is sulfur dioxide, sodium thiosulfate, sodium sulfite any one
Or it is several；Reducing agent is by the amount of chromium material in liquid after precipitation or chromium pregnant solution: the amount of reducing agent material=2:1-1:2 adds,
Reaction temperature 10-100 DEG C, response time 0.5-4h.
9. a kind of utilization strong basic ion exchange fiber according to claim 1-4 any one processes the side of vanadium chrome waste water
Method, it is characterised in that described strongly basic anion ion exchange fibre, has extremely strong absorbability to high price vanadium chromium ion, can make suction
Attached tail washings contains vanadium and is less than 0.5mg/l, vanadium recovery more than 99.9%, and after absorption, tail washings contains chromium less than 0.5mg/l, chromium recovery ratio
More than 99.9%.
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