CN106277420A - 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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- CN106277420A CN106277420A CN201510297243.0A CN201510297243A CN106277420A CN 106277420 A CN106277420 A CN 106277420A CN 201510297243 A CN201510297243 A CN 201510297243A CN 106277420 A CN106277420 A CN 106277420A
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Abstract
The invention belongs to chromaking work and chromic salts clearer production technology field, be specifically related to the dechromium method of a kind of organic reducing Cr VI waste liquid.The present invention is first the alkaline feed liquid after organic reducing Cr VI to be adjusted to pH between 10-14, then at room temperature to 90 DEG C, add a certain amount of reducing agent, to be restored completely, a certain amount of flocculant is added again in feed liquid, after flocculation completes, solid-liquid separation obtains the chrome content feed liquid less than 3mg/L, and the feed liquid after de-chromium can be used for making the carbonate products meeting national standard.This dechromium method is without adding acidulant, and method is simple, the enforcement of technique, can expand the chromic production range of liquid phase organic reducing, improves overall economic efficiency.
Description
Technical field
The invention belongs to chromaking work and chromic salts clearer production technology field, in particular it relates to one is organic also
The dechromium method of former Cr VI alkaline waste liquor, produces chromium oxide institute particular for Cr VI organic reducing under the conditions of alkalescence
The de-chromium of the mother-liquor produced.
Background technology
Chromic salts is important inorganic chemical product, occupies an important position in national economy, and existing chromium oxide produces
Technique energy consumption is high, and product quality is poor, and more promising is the organic liquid phase also new work of original production chromium oxide
Skill, but owing to being Organic substance Liquid reduction reaction process, substantial amounts of oxidation operation derivant, a large amount of carbonic acid can be produced
Salt, bicarbonate, pH value is high, composition complexity, and due to technological reason, it is difficult to by Cr VI Restore All, lead
Causing containing a certain amount of Cr VI in the by-product feed liquid produced, conventional method is difficult to effectively remove chromium therein.Separately
The outer factory calibration strictly limiting the non-major product of chromium salt factory due to Chinese Ministry of Environmental Protection, it is stipulated that < 3mg/L just can conduct for Leaching
General industry solid waste is dispatched from the factory.Therefore, the carbonate side-product that existing technique produces cannot dispatch from the factory work as common product
For its use, system can only be returned or utilize in chromium salt factory on the spot, the serious exploitativeness restricting technique.
De-chromium for chromium-containing solution processes, and existing precipitate reduction method is essentially all and solution is adjusted to acidity
Reduce, then in the solution of about 8, chromium is removed with the form of chromic oxide gel at meta-alkalescence, i.e. pH.This
Method needs substantial amounts of acid, alkali to regulate pH, and production cost is high, introduces impurity, is not particularly suited for liquid-phase reduction and produces
The de-chromium of raw meta-alkalescence feed liquid.
Patent CN101456588A uses starch or derivatives thereof hydrothermal reduction sodium chromate or sodium dichromate, and chromium converts
Rate 98%, obtained mother-liquor is evaporated concentration, crystallisation by cooling, filtration separation, obtains solids mixing alkali
And crystalline mother solution, it can be seen that obtained mixed base contains the Cr VI of high level, can only return local chromic salts
Factory uses.
Patent CN1410357A is by mother-liquor equally, evaporates, crystallizes, separates, and mother solution returns, and obtains
What crystal do not illustrates to be used as, but certainly containing Cr VI, it is impossible to directly as commercial articles vending, can only be indirect
Or direct reuse, energy consumption, flow process certainly will be greatly increased.
HCO in mother-liquor after organic liquid phase Reduced separating chromic oxide gel in patent CN100999335A3-、
CO3 2-Crystallization becomes containing chromium by-product, it is difficult to utilize, remaining liquid phase Returning utilization.
In sum, the above-mentioned process about organic reducing Cr VI alkaline waste liquor technique does not all account for chromic
Removing, the crystal content of 6-valence Cr ions causing by-product is high, it is difficult to as product utilization, have a strong impact on the applicable of technique
Property.Therefore, exploitation one effectively, thoroughly organic reducing chromic alkalescence feed liquid degree of depth under the conditions of high alkalinity
Dechromium method has highly important realistic meaning.
Summary of the invention
It is an object of the invention to, the deficiency existed for above-mentioned technique, it is provided that a kind of organic reducing Cr VI alkalescence is given up
The method that liquid processes, solves existing being difficult to and processes the processing cost that organic reducing Cr VI alkalies wet reducing exists
Height, halfway problem of detoxifying.It is simple that this technique has flow process, and reducing agent consumption is few, low cost, and chromium removing
Thoroughly, reduction reaction temperature is low, is suitable for industrialized production, has preferable popularizing application prospect.
For achieving the above object, the present invention uses following design:
The dechromium method of the organic reducing Cr VI alkaline waste liquor of the present invention, comprises the following steps:
1) pH value of organic reducing Cr VI alkaline waste liquor is adjusted between 10-14；
2) temperature be room temperature to 90 DEG C at, whipping step 1) gained waste liquid, be simultaneously introduced reducing agent, carry out also
Former reaction；
3) treat step 2) in Cr (VI) be reduced to Cr (III) completely, in feed liquid, add flocculant, preferably in temperature
For at 20-90 DEG C, after flocculation 30min-24h, carry out solid-liquid separation, complete de-chromium.
According to the dechromium method of the present invention, wherein, described organic reducing Cr VI alkaline waste liquor is by organic reducing
The slurry that agent reduction obtains after containing Cr VI feed liquid, or, described slurry the liquid obtained through further solid-liquid separation
Body feed liquid.Described organic reducing agent includes formaldehyde and derivant, methanol and derivant thereof, glucose and spreads out
Biological, really one or more in carbohydrates and their derivative or starch and derivant thereof.The reduction of other organic reducing agent contains
The slurry obtained after Cr VI feed liquid is also suitable the dechromium method of the present invention, but after the reduction of preferred above-mentioned organic reducing agent
Feed liquid.
The present invention is suitable for the organic reducing Cr VI alkaline waste liquor of all concentration, it is preferable that the present invention is at high alkalinity bar
Low concentration organic reducing Cr VI alkaline waste liquor is removed so that meeting GB under part.Described low concentration organic reducing sexavalence
Cr (VI) concentration of chromium alkaline waste liquor is 10mg/L-50g/L, preferably 10mg/L-5g/L.
According to the dechromium method of the present invention, wherein, step 1) described in the alkali used by described regulation pH value can be
One or more in sodium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate or other alkaline matter.
According to the dechromium method of the present invention, wherein, step 2) add the amount of reducing agent for reducing Cr VI institute in feed liquid
Reducing agent Cr (VI) is needed to be reduced to 1.2-3 times of theoretical amount of Cr (III) completely.Described reducing agent is preferably hydration
Hydrazine.
According to the dechromium method of the present invention, wherein, step 2) as long as the stirring to waste liquid ensures uniformly, if
Handled waste liquid is that the slurry without solid-liquid separation then needs stirring to solid to be completely dispersed.
According to the dechromium method of the present invention, wherein, step 3), described flocculant can be anionic, sun from
Subtype, nonionic or hydrolysis-type polyacrylamide, the most preferably anion-polyacrylamide.Described poly-third
The addition of acrylamide determines according to the volume of feed liquid, and typically making its concentration in the solution after interpolation is 1-50
mg/L。
Prior art is usually and is first reduced completely by Cr VI to slant acidity condition by the pH regulator of chrome waste liquid, then will
PH regulator, to the meta-alkalescence of about 8, completely removes with the form of trivalent chromium precipitation, needs to expend substantial amounts of bronsted lowry acids and bases bronsted lowry,
Introducing substantial amounts of impurity, the present invention does not the most have the above shortcoming.
The present invention compared with prior art, has the advantage that this technique can remove organic reducing Cr VI completely
Alkaline feed liquid in Cr VI, it is to avoid the accumulation of by-product, store up, expanding production scope, increase mixed economy
Benefit, and finally for the cleaning production offer power-assisted of Chrome Salt Industry.
Detailed description of the invention
Disclosed in this specification any feature, unless specifically stated otherwise, all can by other equivalence or there is similar purpose
Alternative features replaced.Unless specifically stated otherwise, during each feature is a series of equivalence or similar characteristics
One example.Described it be only used to help and understand the present invention, should not be considered as the concrete restriction to the present invention.
Embodiment 1
Select the slurry that the molten brilliant liquid obtained from the liquid phase oxidation of potassium system obtains after starch reduces, wherein (VI) Han Cr
It is 10.00 for 2.34g/L, pH, complete pulp, add at temperature 40 DEG C and Cr (VI) is reduced to Cr (III) completely
The hydrazine hydrate of theoretical amount 1.2 times, insulated and stirred, after 30 minutes, adds a certain amount of PAMC wadding
Solidifying agent so that it is concentration in the solution is 10mg/L, keeps feed liquid to be in the state of being slowly stirred during flocculation, temperature is
40 DEG C, flocculation time is 3h, carries out solid-liquid separation after flocculation completely, and the total chrome content in the feed liquid obtained is
0.48mg/L。
Embodiment 2
Select the molten brilliant liquid filtrate that solid-liquid separation obtains after starch reduces obtained from the liquid phase oxidation of potassium system, wherein
(VI) containing Cr is 3.76g/L, adds potassium hydroxide regulation pH to 11.79, and pulp completely, at temperature 60 C
Cr (VI) is reduced to the hydrazine hydrate of the theoretical amount 1.8 times of Cr (III) by lower addition completely, and insulated and stirred is after 20 minutes,
Add a certain amount of PAMA flocculant so that it is concentration in the solution is 8mg/L, protect during flocculation
Holding feed liquid and be in the state of being slowly stirred, temperature is 60 DEG C, and flocculation time is 4h, carries out solid-liquid separation after flocculation completely,
Total chrome content in the feed liquid obtained is 0.32mg/L.
Embodiment 3
Select the slurry that the molten brilliant liquid obtained from the liquid phase oxidation of sodium system obtains after sucrose reduces, wherein (VI) Han Cr
For 1.44g/L, add sodium carbonate regulation pH to 10.50, and pulp completely, add Cr (VI) at room temperature 25 DEG C
Being reduced to the hydrazine hydrate of the theoretical amount 2.0 times of Cr (III) completely, insulated and stirred, after 30 minutes, adds a certain amount of water
Solve polyacrylamide flocculant so that it is concentration in the solution is 6mg/L, keep feed liquid to be in during flocculation and slowly stir
Mixing state, temperature is 40 DEG C, and flocculation time is 5h, carries out solid-liquid separation, in the feed liquid obtained after flocculation completely
Total chrome content is 0.41mg/L.
Embodiment 4
Select the filtrate that the molten brilliant liquid solid-liquid separation after Reduction of methanol obtained from the liquid phase oxidation of sodium system obtains, wherein
(VI) containing Cr is 1.49g/L, adds sodium hydroxide regulation pH to 13.72, and pulp completely, at temperature 60 C
Cr (VI) is reduced to the hydrazine hydrate of the theoretical amount 3 times of Cr (III) by lower addition completely, and insulated and stirred, after 20 minutes, adds
Enter a certain amount of PAMA flocculant so that it is concentration in the solution is 4mg/L, keep during flocculation
Feed liquid is in the state of being slowly stirred, and temperature is 60 DEG C, and flocculation time is 3h, carries out solid-liquid separation after flocculation completely,
Total chrome content in the feed liquid obtained is 0.25mg/L.
Embodiment 5
Select the molten brilliant liquid filtrate that solid-liquid separation obtains after glucose reduces that calcium-free roasting obtains, wherein containing Cr
(VI) it is 1.07g/L, adds sodium hydroxide regulation pH to 13.5, and pulp completely, add under temperature 60 C
Cr (VI) is reduced to the hydrazine hydrate of the theoretical amount 1.8 times of Cr (III) completely, and insulated and stirred, after 30 minutes, adds one
Quantitative cationic polyacrylamide flocculant agent so that it is concentration in the solution is 6mg/L, keeps feed liquid during flocculation
Being in the state of being slowly stirred, temperature is 40 DEG C, and flocculation time is 2h, carries out solid-liquid separation, obtain after flocculation completely
Feed liquid in total chrome content be 0.45mg/L.
Embodiment 6
Select the mixed solution filtrate that solid-liquid separation obtains after starch reduces of sodium dichromate and sodium chromate, wherein
(VI) containing Cr is 0.87g/L, adds sodium hydroxide regulation pH to 14.00, and pulp completely, temperature 80 DEG C
Cr (VI) is reduced to the hydrazine hydrate of the theoretical amount 1.6 times of Cr (III) by lower addition completely, and insulated and stirred is after 20 minutes,
Add a certain amount of PAMA flocculant so that it is concentration in the solution is 2mg/L, protect during flocculation
Holding feed liquid and be in the state of being slowly stirred, temperature is 60 DEG C, and flocculation time is 3h, carries out solid-liquid separation after flocculation completely,
Total chrome content in the feed liquid obtained is 0.36mg/L.
Certainly, the present invention can also have various embodiments, in the case of without departing substantially from present invention spirit and essence thereof,
Those of ordinary skill in the art can make various corresponding change and deformation according to disclosure of the invention, but these phases
The change answered and deformation all should belong to the scope of the claims of the present invention.
Claims (9)
1. a dechromium method for organic reducing Cr VI alkaline waste liquor, comprises the following steps:
1) pH value of organic reducing Cr VI alkaline waste liquor is adjusted between 10-14；
2) temperature be room temperature to 90 DEG C at, whipping step 1) gained waste liquid, be simultaneously introduced reducing agent, carry out also
Former reaction；
3) treat step 2) in Cr (VI) be reduced to Cr (III) completely, in feed liquid add flocculant, wait to have flocculated
Carry out solid-liquid separation after one-tenth, complete de-chromium.
2. dechromium method as claimed in claim 1, it is characterised in that described organic reducing Cr VI alkalescence is given up
Liquid is containing the slurry obtained after Cr VI feed liquid by organic reducing agent reduction, or, by described slurry through the most solid
The liquid feed liquid of liquid isolated.
3. dechromium method as claimed in claim 2, it is characterised in that described organic reducing agent include formaldehyde and
Its derivant, methanol and derivant thereof, Fructus Vitis viniferae carbohydrates and their derivative, really carbohydrates and their derivative or starch and derivative
One or more in thing.
4. dechromium method as claimed in claim 1, it is characterised in that step 1) regulation alkali bag used by pH value
Include one or more in sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
5. dechromium method as claimed in claim 1, it is characterised in that step 2) described in reducing agent be hydration
Hydrazine.
6. the dechromium method as described in claim 1 or 5, it is characterised in that the addition of described reducing agent is reduction
In organic reducing Cr VI alkaline waste liquor, Cr VI needs 1.2-3 times of the theoretical amount of reducing agent.
7. dechromium method as claimed in claim 1, it is characterised in that step 3) described in flocculant be cloudy from
Subtype, cationic, nonionic or hydrolysis-type polyacrylamide.
8. dechromium method as claimed in claim 7, it is characterised in that described flocculant is anionic polyacrylamide
Amine.
9. the dechromium method as described in as arbitrary in claim 1,7 or 8, it is characterised in that step 3) at 20-90 DEG C
Under the conditions of flocculate 30min-24h.
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Cited By (6)
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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 |
| CN109437384A (en) * | 2018-11-28 | 2019-03-08 | 大连理工大学 | Copper ion accelerates fructose-K2HPO4The method of product processing waste water containing chrome |
| CN110339731A (en) * | 2019-07-02 | 2019-10-18 | 昆明理工大学 | A kind of preparation method and applications of chromium (VI) ion blotting 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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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109437384A (en) * | 2018-11-28 | 2019-03-08 | 大连理工大学 | Copper ion accelerates fructose-K2HPO4The method of product processing waste water containing chrome |
| 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 |
| CN110339731A (en) * | 2019-07-02 | 2019-10-18 | 昆明理工大学 | A kind of preparation method and applications of chromium (VI) ion blotting 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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