CN106277420B - A kind of dechromium method of organic reducing Cr VI alkaline waste liquor - Google Patents
A kind of dechromium method of organic reducing Cr VI alkaline waste liquor Download PDFInfo
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- CN106277420B CN106277420B CN201510297243.0A CN201510297243A CN106277420B CN 106277420 B CN106277420 B CN 106277420B CN 201510297243 A CN201510297243 A CN 201510297243A CN 106277420 B CN106277420 B CN 106277420B
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Abstract
The invention belongs to chromaking works and chromic salts clearer production technology field, and in particular to a kind of dechromium method of organic reducing sexavalence chromium waste liquid.The present invention is that the alkaline feed liquid after organic reducing Cr VI is adjusted to pH between 10-14 first, then in room temperature at 90 DEG C, a certain amount of reducing agent is added, it is to be restored complete, a certain amount of flocculant is added into feed liquid again, it after the completion of flocculating, is separated by solid-liquid separation and obtains the feed liquid that chrome content is less than 3mg/L, the feed liquid after taking off chromium can be used for making carbonate products that meet national standards.The dechromium method is without being added acidulant, and method is simple, the implementation of technique, can expand the production range of liquid phase organic reducing Cr VI, improves overall economic efficiency.
Description
Technical field
The invention belongs to chromaking works and chromic salts clearer production technology field, in particular it relates to a kind of organic reducing
The dechromium method of Cr VI alkaline waste liquor is gone back particular for caused by Cr VI organic reducing production chromium oxide under alkaline condition
The de- chromium of original nut liquid.
Background technique
Chromic salts is important inorganic chemical product, occupies an important position in national economy, and existing chromium oxide produces work
Skill production energy consumption is high, and product quality is poor, and more promising is organic liquid phase also original production chromium oxide new process, but by
Then organic matter Liquid reduction reaction process can generate a large amount of oxidation operation derivative, a large amount of carbonate, bicarbonate, pH value
Height, complicated composition, and due to technological reason, it is difficult to Cr VI is all restored, causes to contain one in the by-product material liquid generated
Quantitative Cr VI, conventional method are difficult to effectively remove chromium therein.The non-main product of chromium salt factory is strictly limited additionally, due to Chinese Ministry of Environmental Protection
The factory calibration of product is, it is specified that Leaching < 3mg/L just can be used as the factory of general industry solid waste.Therefore, the carbon of prior art production
Hydrochlorate byproduct can not use it for anything else as common product factory, return system or can only utilize on the spot in chromium salt factory, serious to make
The about exploitativeness of technique.
De- chromium processing for chromium-containing solution, existing precipitate reduction method be essentially all by solution be adjusted to it is acid into
Row reduction, then in meta-alkalescence, i.e. pH is removed chromium in 8 or so solution in the form of chromium hydroxide.This method needs big
The acid of amount, alkali adjust pH, and high production cost introduces impurity, be not particularly suited for the de- of the meta-alkalescence feed liquid of liquid-phase reduction generation
Chromium.
Patent CN101456588A is using starch or derivatives thereof hydrothermal reduction sodium chromate or sodium dichromate, chromium conversion ratio
98%, obtained mother-liquor is evaporated concentration, crystallisation by cooling, is separated by filtration, and obtains solid mixed base and crystalline mother solution,
As can be seen that acquired mixed base contains the Cr VI of high level, local chromium salt factory can only be returned and used.
Patent CN1410357A is equally by mother-liquor, evaporation, crystallization, separation, and mother liquor returns, and obtained crystal does not have
Illustrate what is used as, but contain Cr VI certainly, cannot directly as commercial articles vending, can only directly or indirectly reuse, energy consumption,
Process certainly will greatly increase.
HCO in patent CN100999335A after organic liquid phase Reduced separating chromium hydroxide in mother-liquor3-、CO3 2-Crystallization
As by-product containing chromium, it is difficult to utilize, remaining liquid phase Returning utilization.
In conclusion the above-mentioned processing about organic reducing Cr VI alkaline waste liquor technique does not account for the de- of Cr VI
It removes, causes the crystal content of 6-valence Cr ions of by-product high, it is difficult to as product utilization, seriously affect the usability of technique.Therefore, it opens
Send out a kind of alkaline feed liquid of effective, thorough organic reducing Cr VI depth dechromium method under the conditions of high alkalinity have it is very heavy
The realistic meaning wanted.
Summary of the invention
The object of the present invention is to provide a kind of organic reducing Cr VI alkaline waste liquor for deficiency existing for above-mentioned technique
The method of processing, solution is existing to be difficult to handle the height of processing cost existing for organic reducing Cr VI alkalies wet reducing, removing toxic substances
Halfway problem.The technique has process simple, and reducing agent dosage is few, at low cost, and chromium removing is thoroughly, reduction reaction temperature
It is low, it is suitable for industrialized production, there is preferable popularization and application foreground.
To achieve the above object, the present invention uses following design scheme:
The dechromium method of organic reducing Cr VI alkaline waste liquor of the invention, comprising the following steps:
1) pH value of organic reducing Cr VI alkaline waste liquor is adjusted between 10-14；
It 2) is room temperature at 90 DEG C in temperature, whipping step 1) gained waste liquid, while reducing agent is added, restore anti-
It answers；
3) it is reduced to Cr (III) completely to the Cr (VI) in step 2), flocculant is added into feed liquid, is preferably in temperature
It at 20-90 DEG C, flocculates after 30min-24h, is separated by solid-liquid separation, complete de- chromium.
Dechromium method according to the present invention, wherein the organic reducing Cr VI alkaline waste liquor is by organic reducing agent
The slurry that reduction obtains after feed liquid containing Cr VI, alternatively, being further separated by solid-liquid separation obtained liquid feed liquid by the slurry.Institute
The organic reducing agent stated includes formaldehyde and its derivative, methanol and its derivative, grape carbohydrates and their derivative, fructose and its derivative
Object or one or more of starch and its derivative.The slurry obtained after other organic reducing agent reduction feed liquids containing Cr VI
It is applicable in dechromium method of the invention, but the feed liquid after preferably above-mentioned organic reducing agent reduction.
The present invention is applicable in the organic reducing Cr VI alkaline waste liquor of all concentration, it is preferable that the present invention is in high alkalinity condition
Under remove low concentration organic reducing Cr VI alkaline waste liquor so that meeting national standard.The low concentration organic reducing Cr VI alkalinity is useless
Cr (VI) concentration of liquid is 10mg/L-50g/L, preferably 10mg/L-5g/L.
Dechromium method according to the present invention, wherein alkali used in the adjusting pH value described in step 1) can be hydrogen-oxygen
Change one of sodium, sodium hydroxide, sodium carbonate, potassium carbonate or other alkaline matters or a variety of.
Dechromium method according to the present invention, wherein the amount that reducing agent is added in step 2) is to restore in feed liquid needed for Cr VI
Reducing agent Cr (VI) is wanted to be reduced to 1.2-3 times of the theoretical amount of Cr (III) completely.The reducing agent is preferably hydrazine hydrate.
Dechromium method according to the present invention, wherein as long as step 2) guarantees uniformly, if locating the stirring of waste liquid
Reason waste liquid is that the slurry without separation of solid and liquid then needs stirring to solid to be completely dispersed.
Dechromium method according to the present invention, wherein step 3), the flocculant can be anionic, cationic,
Non-ionic or hydrolysis-type polyacrylamide, wherein preferably anion-polyacrylamide.The addition of the polyacrylamide
Measure the concentration 1-50mg/L for generally making it after addition according to the determination of the volume of feed liquid in the solution.
The prior art is usually to adjust the pH of chrome waste liquid to slant acidity condition first to restore Cr VI completely, then by pH
The meta-alkalescence to 8 or so is adjusted, is completely removed in the form that trivalent chromium precipitates, needs to expend a large amount of bronsted lowry acids and bases bronsted lowry, is introduced a large amount of
Impurity, and the present invention then completely do not have the above disadvantage.
Compared with prior art, the present invention having the advantage that the technique can remove organic reducing Cr VI completely
Cr VI in alkaline feed liquid avoids accumulation, the stockpiling of by-product, and expanding production range increases overall economic efficiency, and final
Power-assisted is provided for the clean manufacturing of Chrome Salt Industry.
Specific embodiment
Any feature is disclosed to obtain in this specification, it unless specifically stated, can be equivalent or with similar purpose by other
Alternative features are replaced.Unless specifically stated, each feature is an example in a series of equivalent or similar characteristics
?.It is described to understand the present invention just for the sake of help, it should not be considered as to concrete restriction of the invention.
Embodiment 1
The slurry for selecting the molten brilliant liquid obtained from the liquid phase oxidation of potassium system to obtain after starch restores, wherein (VI) containing Cr is
The theoretical amount that Cr (VI) is reduced to Cr (III) completely is added in 2.34g/L, pH 10.00, complete pulp at 40 DEG C of temperature
1.2 times of hydrazine hydrate is added a certain amount of cationic polyacrylamide flocculant agent, makes it in solution after insulated and stirred 30 minutes
In concentration be 10mg/L, keep when flocculation feed liquid to be in the state that is slowly stirred, temperature is 40 DEG C, flocculation time 3h, flocculation
It is separated by solid-liquid separation after completely, the obtained total chrome content in feed liquid is 0.48mg/L.
Embodiment 2
The filtrate for selecting the molten brilliant liquid obtained from the liquid phase oxidation of potassium system to be separated by solid-liquid separation after starch restores, wherein containing
Cr (VI) is 3.76g/L, and potassium hydroxide is added and adjusts pH to 11.79, and complete pulp, is added under temperature 60 C by Cr (VI)
It is reduced to 1.8 times of theoretical amount of the hydrazine hydrate of Cr (III) completely, after twenty minutes, it is poly- that a certain amount of anion is added in insulated and stirred
Acrylamide flocculating agent, makes its concentration 8mg/L in the solution, and when flocculation keeps feed liquid to be in and is slowly stirred state, temperature
It is 60 DEG C, flocculation time 4h, is separated by solid-liquid separation after flocculation completely, the obtained total chrome content in feed liquid is 0.32mg/L.
Embodiment 3
The slurry for selecting the molten brilliant liquid obtained from the liquid phase oxidation of sodium system to obtain after sucrose restores, wherein (VI) containing Cr is
1.44g/L is added sodium carbonate and adjusts pH to 10.50, and complete pulp, is added at 25 DEG C of room temperature and is reduced to Cr (VI) completely
After insulated and stirred 30 minutes, a certain amount of hydrolyzed polyacrylamide flocculation is added in 2.0 times of theoretical amount of the hydrazine hydrate of Cr (III)
Agent, makes its concentration 6mg/L in the solution, and when flocculation keeps feed liquid to be in the state that is slowly stirred, and temperature is 40 DEG C, when flocculation
Between be 5h, flocculation completely after be separated by solid-liquid separation, the obtained total chrome content in feed liquid be 0.41mg/L.
Embodiment 4
The filtrate for selecting the molten brilliant liquid obtained from the liquid phase oxidation of sodium system to be separated by solid-liquid separation after Reduction of methanol, wherein containing
Cr (VI) is 1.49g/L, and sodium hydroxide is added and adjusts pH to 13.72, and complete pulp, is added under temperature 60 C by Cr (VI)
It is reduced to 3 times of theoretical amount of the hydrazine hydrate of Cr (III) completely, after twenty minutes, a certain amount of anion poly- third is added in insulated and stirred
Acrylamide flocculant, makes its concentration 4mg/L in the solution, and when flocculation keeps feed liquid to be in and is slowly stirred state, and temperature is
It 60 DEG C, flocculation time 3h, is separated by solid-liquid separation after flocculation completely, the obtained total chrome content in feed liquid is 0.25mg/L.
Embodiment 5
It selects and carrys out the filtrate that the molten brilliant liquid that calcium-free roasting obtains is separated by solid-liquid separation after glucose restores, wherein containing Cr
(VI) it is 1.07g/L, sodium hydroxide is added and adjusts pH to 13.5, and complete pulp, is added under temperature 60 C Cr (VI) is complete
It is reduced to 1.8 times of theoretical amount of the hydrazine hydrate of Cr (III) entirely, after insulated and stirred 30 minutes, a certain amount of cation poly- third is added
Acrylamide flocculant, makes its concentration 6mg/L in the solution, and when flocculation keeps feed liquid to be in and is slowly stirred state, and temperature is
It 40 DEG C, flocculation time 2h, is separated by solid-liquid separation after flocculation completely, the obtained total chrome content in feed liquid is 0.45mg/L.
Embodiment 6
The filtrate for selecting the mixed solution for coming sodium dichromate and sodium chromate to be separated by solid-liquid separation after starch restores, wherein containing
Cr (VI) is 0.87g/L, and sodium hydroxide is added and adjusts pH to 14.00, and complete pulp, is added at 80 DEG C of temperature by Cr (VI)
It is reduced to 1.6 times of theoretical amount of the hydrazine hydrate of Cr (III) completely, after twenty minutes, it is poly- that a certain amount of anion is added in insulated and stirred
Acrylamide flocculating agent, makes its concentration 2mg/L in the solution, and when flocculation keeps feed liquid to be in and is slowly stirred state, temperature
It is 60 DEG C, flocculation time 3h, is separated by solid-liquid separation after flocculation completely, the obtained total chrome content in feed liquid is 0.36mg/L.
Certainly, the present invention can also there are many embodiments, without deviating from the spirit and substance of the present invention, are familiar with
Those skilled in the art can disclosure according to the present invention make various corresponding changes and modifications, but these it is corresponding change and
Deformation all should belong to scope of protection of the claims of the invention.
Claims (6)
1. a kind of dechromium method of organic reducing Cr VI alkaline waste liquor, comprising the following steps:
1) pH value of organic reducing Cr VI alkaline waste liquor is adjusted between 10-14；The organic reducing Cr VI alkalinity
Waste liquid is to restore the slurry obtained after feed liquid containing Cr VI by organic reducing agent, alternatively, by the slurry through further solid-liquid point
From obtained liquid feed liquid；Wherein, the organic reducing agent includes formaldehyde and its derivative, methanol and its derivative, grape
Carbohydrates and their derivative, fruit carbohydrates and their derivative or one or more of starch and its derivative；
It 2) is room temperature at 90 DEG C in temperature, whipping step 1) gained waste liquid, while reducing agent is added, carry out reduction reaction；Its
In, the reducing agent is hydrazine hydrate；
3) it is reduced to Cr (III) completely to the Cr (VI) in step 2, flocculant is added into feed liquid, carried out after the completion of flocculating
It is separated by solid-liquid separation, completes de- chromium.
2. dechromium method as described in claim 1, which is characterized in that it includes hydroxide that step 1), which adjusts alkali used in pH value,
One or more of sodium, potassium hydroxide, sodium carbonate and potassium carbonate.
3. dechromium method as described in claim 1, which is characterized in that the additional amount of the reducing agent is reduction organic reducing six
Cr VI needs 1.2-3 times of the theoretical amount of reducing agent in valence chromium alkaline waste liquor.
4. dechromium method as described in claim 1, which is characterized in that flocculant described in step 3) be anionic, sun from
Subtype, non-ionic or hydrolysis-type polyacrylamide.
5. dechromium method as claimed in claim 4, which is characterized in that the flocculant is anion-polyacrylamide.
6. claim 1,4 or 5 it is any as described in dechromium method, which is characterized in that step 3) is flocculated under the conditions of 20-90 DEG C
30min-24h。
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| CN108017136A (en) * | 2017-12-14 | 2018-05-11 | 广州市香港科大霍英东研究院 | A kind of method that poisonous Cr VI is changed into trivalent chromium using organic matter |
| CN109437384B (en) * | 2018-11-28 | 2021-10-15 | 大连理工大学 | Copper ion accelerated fructose-K2HPO4Method for treating chromium-containing wastewater by using product |
| CN110339731B (en) * | 2019-07-02 | 2021-11-12 | 昆明理工大学 | Preparation method and application of chromium (VI) ion imprinting composite membrane |
| CN110395815A (en) * | 2019-07-13 | 2019-11-01 | 河南大学 | A kind of processing method of acidity electroplating wastewater of chromium |
| CN112326874A (en) * | 2020-11-30 | 2021-02-05 | 宁夏日盛高新产业股份有限公司 | Method for analyzing mixed alkali in hydrazine hydrate by hydrogen peroxide oxidation method |
| CN115385483A (en) * | 2022-09-16 | 2022-11-25 | 嘉兴学院 | Environment-friendly treatment method for fur processing wastewater |
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| CN101875520A (en) * | 2010-08-10 | 2010-11-03 | 南京师范大学 | Processing method of electroplating wastewater containing cyanogens and chrome |
| CN102101732A (en) * | 2011-01-14 | 2011-06-22 | 南京大学 | Method for recovering hydrazine sulfate and chromium hydroxide from chromium-containing waste acid |
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| RU2433961C2 (en) * | 2010-02-04 | 2011-11-20 | Тураев Дмитрий Юрьевич | Method of decontaminating aqueous solutions containing hexavalent chromium compounds |
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