CN102424913B - Method for separating vanadium and chromium from mixing solution containing vanadium (V) and chromium (VI) - Google Patents
Method for separating vanadium and chromium from mixing solution containing vanadium (V) and chromium (VI) Download PDFInfo
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- CN102424913B CN102424913B CN2011104138182A CN201110413818A CN102424913B CN 102424913 B CN102424913 B CN 102424913B CN 2011104138182 A CN2011104138182 A CN 2011104138182A CN 201110413818 A CN201110413818 A CN 201110413818A CN 102424913 B CN102424913 B CN 102424913B
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Abstract
The present invention provides a method for separating vanadium and chromium from a mixing solution containing vanadium (V) and chromium (VI). The method comprises the following steps: adjusting the pH value of the mixing solution to 10.4-10.5; adding a calcium salt to the mixing solution; adjusting the pH value of the resulting mixing solution to 10.4-10.5; filtering the mixing solution to obtain a first vanadium-containing filter cake and a chromium-containing filtrate; soaking the first vanadium-containing filter cake by an alkaline solution with the pH value of 11-11.1, and filtering to obtain a second vanadium-containing filter cake; cleaning the second vanadium-containing filter cake by clear water, and drying to obtain calcium vanadate; treating the chromium-containing filtrate to obtain the chromium product. With the method of the present invention, the vanadium and the chromium can be effectively separated and recovered from the mixing solution containing the vanadium (V) and the chromium (VI) so as to contribute to the recovery and the utilization of the vanadium resources and the chromium resources. In addition, the method of the present invention has advantages of simpleness and easy operation.
Description
Technical field
The present invention relates to recycle the technical field of vanadium (V) chromium (VI), more particularly, relate to a kind of method that contains vanadium, chromium in vanadium (V) chromium (VI) mixed solution with precipitator method separation and recovery.
Background technology
At present, when producing ammonium poly-vanadate (APV), can produce a large amount of contain vanadium (V) (, the pentavalent vanadium) chromium (VI) (namely, sexavalent chrome) trade effluent, because these two kinds of materials have very strong toxicity, so must high valence chrome and high price vanadium be reduced into trivalent chromium and low price vanadium through reducing to handle, again by transferring pH to make vanadium, chromium precipitation just can reach environmental requirement.But vanadium chromium is as the important strategic resource, and so processing certainly will cause the wasting of resources, and if the vanadium chromium filter cake that contains that produces arbitrarily stack, still have bigger environment hidden danger.
At the problems referred to above, a kind of method that adopts brothers varies extracting and separating vanadium chromium has been invented by Chinese Academy Of Sciences Process Engineering Research Institute, its patent publication No. is CN101121962A, though this technology is conducive to the recycling of vanadium chromium resource, but the technological process relative complex, and be difficult to accurate operation, energy consumption is higher.Chinese patent CN1073414A discloses a kind of method that adopts chemical process to separate vanadium chromium in the waste water, and this method adopts FeCl
3With the vanadium precipitation, reclaim chromium with reduction precipitation method again, this method is because of Fe (OH)
3Deng the existence of impurity, be difficult to obtain the high vanadium chromium product of purity, and the technology relative complex, cost is also higher.
Summary of the invention
At the above-mentioned deficiency of prior art, one of purpose of the present invention is to provide a kind of and can effectively separates and reclaim the vanadium that contains in vanadium (V) chromium (VI) mixed solution, the method for chromium element.
The invention provides a kind of method of from contain vanadium (V) chromium (VI) mixed solution, separating vanadium, chromium.Described method comprises the steps: to regulate pH to 10.4～10.5 of mixed solution; In mixed solution, add calcium salt; Then, regulate pH to 10.4～10.5 of mixed solution; Filter mixed solution, obtain first and contain the vanadium filter cake and contain chromium filtrate; To contain vanadium filter cake pH and be 11～11.1 aqueous slkali soaking after-filtration, and obtain second and contain the vanadium filter cake; Water cleans described second and contains the vanadium filter cake, obtains vanadic acid calcium after the oven dry; Handle the described chromium filtrate that contains, obtain the chromium product.
According to method of separating vanadium, chromium from contain vanadium (V) chromium (VI) mixed solution of the present invention, wherein, the add-on of described calcium salt can make that adding calcium ion mass concentration in the mixed solution behind the calcium salt is 2～5 times of vanadium ion mass concentration.
Method of separating vanadium, chromium from contain vanadium (V) chromium (VI) mixed solution according to the present invention can be regulated the pH value by adding alkali or alkaline solution in mixed solution.
According to method of separating vanadium, chromium from contain vanadium (V) chromium (VI) mixed solution of the present invention, wherein, described calcium salt can be soluble calcium salt.
Method of separating vanadium, chromium from contain vanadium (V) chromium (VI) mixed solution according to the present invention can also be included in and add calcium salt and contain in the process of vanadium filter cake to obtain first to filtering mixed solution, the step that mixed solution is stirred.
According to method of separating vanadium, chromium from contain vanadium (V) chromium (VI) mixed solution of the present invention, wherein, the time of described stirring is preferably more than the 10min.
According to method of from contain vanadium (V) chromium (VI) mixed solution, separating vanadium, chromium of the present invention, wherein, the described step that contains chromium filtrate of described processing can use the S-WAT reduction to contain chromium filtrate, obtains chromium hydroxide precipitation, filter the back calcining then, obtain chromium trioxide.
Compared with prior art, method of the present invention provides a kind of and can separate effectively and reclaim the method that contains vanadium, chromium in vanadium (V) chromium (VI) mixed solution.The present invention adopts chemical precipitation method to separate vanadium, the chromium that contains in vanadium (V) chromium (VI) mixed solution, not only technology is simple, cost is low, and have advantages such as low for equipment requirements, easy to operate, quick, energy-conservation, be well suited for recovery and the utilization of vanadium chromium resource in the vanadium chromium trade effluent, have good social benefit and economic benefit.
Embodiment
Hereinafter, will describe method of from contain vanadium (V) chromium (VI) mixed solution, separating vanadium, chromium of the present invention in detail in conjunction with exemplary embodiment.
Method of separating vanadium, chromium from contain vanadium (V) chromium (VI) mixed solution according to the present invention comprises the steps: to regulate pH to 10.4～10.5 of mixed solution; In mixed solution, add calcium salt; Then, regulate pH to 10.4～10.5 of mixed solution; Filter mixed solution, obtain first and contain the vanadium filter cake and contain chromium filtrate; To contain vanadium filter cake pH and be 11～11.1 aqueous slkali soaking after-filtration, and obtain second and contain the vanadium filter cake; Water cleans described second and contains the vanadium filter cake, obtains vanadic acid calcium after the oven dry; Handle the described chromium filtrate that contains, obtain the chromium product.
In one exemplary embodiment, the add-on of described calcium salt can make that adding calcium ion mass concentration in the mixed solution behind the calcium salt is 2～5 times of vanadium ion mass concentration.
In one exemplary embodiment, described method of separating vanadium, chromium from contain vanadium (V) chromium (VI) mixed solution is regulated the pH value by adding alkali or alkaline solution in mixed solution.Described alkali or alkaline solution can be alkali or alkaline solution commonly used such as sodium hydroxide or sodium hydroxide solution.
In one exemplary embodiment, described calcium salt can be for such as soluble calcium salts such as calcium chloride, nitrocalcite.
In one exemplary embodiment, described method of separating vanadium, chromium from contain vanadium (V) chromium (VI) mixed solution can also be included in and add calcium salt and contain in the process of vanadium filter cake to obtain first to filtering mixed solution, the step that mixed solution is stirred.Preferably, the time of described stirring is more than the 10min.
In one exemplary embodiment, the described step that contains chromium filtrate of described processing can contain chromium filtrate for using the S-WAT reduction, obtains chromium hydroxide precipitation, filters the back calcining then, obtains chromium trioxide.
In addition, method of separating vanadium, chromium from contain vanadium (V) chromium (VI) mixed solution of the present invention can also realize by following steps:
A, adjusting contain pH to 10.4～10.5 of vanadium (V) chromium (VI) mixed solution;
B, stir and be metered into calcium salt;
The pH to 10.4 of c, conditioned reaction liquid～105;
D, stirring 10min after-filtration must contain the vanadium filter cake and contain chromium filtrate;
E, will to contain vanadium filter cake pH be 11～11.1 aqueous slkali soaking after-filtration;
F, water cleaning step e gained filter cake obtain vanadic acid calcium after the oven dry;
G, the steps d gained is contained chromium filtrate handle and produce the chromium product.
Wherein, the pH regulator among the above-mentioned steps a can be realized by sodium hydroxide solution.
Be metered into calcium salt among the above-mentioned steps b, should make calcium ion mass concentration in the solution is 2～5 times of vanadium ion mass concentration.
PH regulator among the above-mentioned steps c can be realized by sodium hydroxide solution.
Churning time among the above-mentioned steps d is 10min, obtains containing the vanadium filter cake after the filtration and contains chromium filtrate.
The alkaline solution pH that immersion among the above-mentioned steps e contains the vanadium filter cake is 11～11.1.
Processing among the above-mentioned steps g contain chromium filtrate method can for: add S-WAT and will contain the reduction of chromium filtrate and make chromium hydroxide precipitation, filter, calcining obtains chromium trioxide behind the washing leaching cake.
The present invention is further illustrated below in conjunction with concrete example.Example only is used for explanation the present invention, rather than limits the present invention by any way.
Example one
The mixed solution that contains pentavalent vanadium (3.8g/L) and sexavalent chrome (4.6g/L) of 200ml is regulated pH to 10.4 with sodium hydroxide solution.Stir also and be metered into Calcium Chloride Powder Anhydrous, making calcium ion mass concentration in the solution is 2.2 times of vanadium ion mass concentration.Then, with the pH to 10.4 of sodium hydroxide solution conditioned reaction liquid, stir the 10min after-filtration, obtain containing vanadium filter cake and chromium-containing solution.Next, will contain vanadium filter cake pH and be 11 aqueous slkali soaking after-filtration, obtain containing vanadium filter cake (also can be designated as second and contain the vanadium filter cake) again, clean that second of gained contains the vanadium filter cake and oven dry obtains vanadic acid calcium.Here, full vanadium (TV) content of vanadic acid calcium is 28.31wt%, and the vanadium yield is 92.15wt%.Calcine 1 hour at 1000 ℃ after will containing chromium filtrate precipitate reduction, calcination product obtains content greater than the chromium sesquioxide of 97wt% through washing and drying again.
Example two
The mixed solution that contains pentavalent vanadium (4.6g/L) and sexavalent chrome (8.8g/L) of 200ml is regulated pH to 10.4 with sodium hydroxide solution.Stir also and be metered into nitrocalcite, making calcium ion mass concentration in the solution is 2.8 times of vanadium ion mass concentration.Then, with the pH to 10.4 of sodium hydroxide solution conditioned reaction liquid, stir the 10min after-filtration, obtain containing vanadium filter cake and chromium-containing solution.Next, will contain vanadium filter cake pH and be 11.05 aqueous slkali soaking after-filtration, obtain containing vanadium filter cake (also can be designated as second and contain the vanadium filter cake) again, clean that second of gained contains the vanadium filter cake and oven dry obtains vanadic acid calcium.Here, the TV of vanadic acid calcium is 29.92wt%, and the vanadium yield is 94.74wt%.Calcine 1 hour at 1000 ℃ after will containing chromium filtrate precipitate reduction, calcination product obtains content greater than the chromium sesquioxide of 97wt% through washing and drying again.
Example three
The mixed solution that contains pentavalent vanadium (5.6g/L) and sexavalent chrome (10.9g/L) of 200ml is regulated pH to 10.5 with sodium hydroxide solution.Stir also and be metered into nitrocalcite, making calcium ion mass concentration in the solution is 3.3 times of vanadium ion mass concentration.Then, continue the pH to 10.5 with sodium hydroxide solution conditioned reaction liquid, stir the 10min after-filtration, obtain containing vanadium filter cake and chromium-containing solution.Next, will contain vanadium filter cake pH and be 11.08 aqueous slkali soaking after-filtration, obtain containing vanadium filter cake (also can be designated as second and contain the vanadium filter cake) again, clean that second of gained contains the vanadium filter cake and oven dry obtains vanadic acid calcium.Here, the TV of vanadic acid calcium is 30.13wt%, and the vanadium yield is greater than 95wt%.Calcine 1 hour at 1000 ℃ after will containing chromium filtrate precipitate reduction, calcination product obtains content greater than the chromium sesquioxide of 97wt% through washing and drying again.
Example four
The mixed solution that contains pentavalent vanadium (7.5g/L) and sexavalent chrome (10.8g/L) of 200ml is transferred pH to 10.5 with sodium hydroxide solution.Stir also and be metered into Calcium Chloride Powder Anhydrous, making calcium ion mass concentration in the solution is 4.9 times of vanadium ion mass concentration.Then, continue the pH to 10.5 with sodium hydroxide solution conditioned reaction liquid, stir the 10min after-filtration, obtain containing vanadium filter cake and chromium-containing solution.Next, will contain vanadium filter cake pH and be 11.05 aqueous slkali soaking after-filtration, obtain containing vanadium filter cake (also can be designated as second and contain the vanadium filter cake) again, clean that second of gained contains the vanadium filter cake and oven dry obtains vanadic acid calcium.Here, the TV of vanadic acid calcium is 31.35wt%, and the vanadium yield is greater than 95wt%.Calcine 1 hour at 1000 ℃ after will containing chromium filtrate precipitate reduction, calcination product obtains content greater than the chromium sesquioxide of 97wt% through washing and drying again.
In sum, vanadium, chromium can be separated and reclaim to method of separating vanadium, chromium from contain vanadium (V) chromium (VI) mixed solution of the present invention effectively from contain vanadium (V) chromium (VI) mixed solution, be conducive to the recycling of vanadium chromium resource, have good social benefit and economic benefit.In addition, method of the present invention also has simple, easy-operating advantage.
Although described method of the present invention in conjunction with exemplary embodiment above, yet, it will be understood by those skilled in the art that under the situation of the scope that does not break away from the claim protection, can carry out various changes to above-mentioned exemplary embodiment.
Claims (6)
1. a method of separating vanadium, chromium from contain vanadium (V) chromium (VI) mixed solution is characterized in that described method comprises the steps:
Regulate pH to 10.4～10.5 of mixed solution;
Add calcium salt in mixed solution, the add-on of described calcium salt can make that adding calcium ion mass concentration in the mixed solution behind the calcium salt is 2～5 times of vanadium ion mass concentration;
Further, regulate pH to 10.4～10.5 of mixed solution;
Filter mixed solution, obtain first and contain the vanadium filter cake and contain chromium filtrate;
To contain vanadium filter cake pH and be 11～11.1 aqueous slkali soaking after-filtration, and obtain second and contain the vanadium filter cake;
Water cleans described second and contains the vanadium filter cake, obtains vanadic acid calcium after the oven dry;
Handle the described chromium filtrate that contains, obtain the chromium product.
2. method of separating vanadium, chromium from contain vanadium (V) chromium (VI) mixed solution as claimed in claim 1 is characterized in that, described method is regulated the pH value by adding alkali or alkaline solution in mixed solution.
3. method of separating vanadium, chromium from contain vanadium (V) chromium (VI) mixed solution as claimed in claim 1 is characterized in that described calcium salt is soluble calcium salt.
4. method of from contain vanadium (V) chromium (VI) mixed solution, separating vanadium, chromium as claimed in claim 1, it is characterized in that, described method also is included in and adds calcium salt and contain in the process of vanadium filter cake to obtain first to filtering mixed solution, the step that mixed solution is stirred.
5. method of separating vanadium, chromium from contain vanadium (V) chromium (VI) mixed solution as claimed in claim 4 is characterized in that the time of described stirring is more than the 10min.
6. method of from contain vanadium (V) chromium (VI) mixed solution, separating vanadium, chromium as claimed in claim 1, it is characterized in that the described step that contains chromium filtrate of described processing comprises uses the S-WAT reduction to contain chromium filtrate, obtains chromium hydroxide precipitation, filter the back calcining then, obtain chromium trioxide.
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| CN102424913B true CN102424913B (en) | 2013-08-14 |
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| CN105420519B (en) * | 2015-12-21 | 2018-10-12 | 中南大学 | A method of extracting vanadium chromium from containing vanadium or/and chromium material |
| CN105861829B (en) * | 2016-04-18 | 2017-09-29 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of vanadium chromium solution separation, the method for reclaiming vanadium chromium |
| CN106186064B (en) * | 2016-07-26 | 2017-10-31 | 大连博融新材料股份有限公司 | A kind of method that depth produces high-purity ammonium metavanadate except chromium |
| CN108531718A (en) * | 2018-04-23 | 2018-09-14 | 东北大学 | A method of producing chrome green using tailings in vanadium extraction |
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