CN102219257B - Method for preparing vanadium pentoxide - Google Patents

Method for preparing vanadium pentoxide Download PDF

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Publication number
CN102219257B
CN102219257B CN2011100824440A CN201110082444A CN102219257B CN 102219257 B CN102219257 B CN 102219257B CN 2011100824440 A CN2011100824440 A CN 2011100824440A CN 201110082444 A CN201110082444 A CN 201110082444A CN 102219257 B CN102219257 B CN 102219257B
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China
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vanadium
vanadate
vanadium slag
roasting
ammonium
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CN2011100824440A
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Chinese (zh)
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CN102219257A (en
Inventor
甘炤坤
杜国山
周文龙
徐月和
吕东
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中国恩菲工程技术有限公司
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Abstract

The invention provides a method for preparing vanadium pentoxide from leachate containing sodium vanadate. The method comprises the following steps of: providing the leachate containing sodium vanadate; adding ammonium sulfate to the leachate containing sodium vanadate, and adjusting the pH value to 1.5-2, and heating at the temperature of 90-100 DEG C to generate a mixed liquid containing an ammonium poly-vanadate precipitate; filtering and washing the mixed liquid containing the ammonium poly-vanadate precipitate to obtain the ammonium poly-vanadate precipitate and vanadium precipitation mother liquor; and heating for decomposing and oxidizing the ammonium poly-vanadate precipitate at the temperature of 400-500 DEG C to generate vanadium pentoxide. The method for preparing vanadium pentoxide has at least one of the following advantages: high efficiency, low cost, low energy consumption, safety and environmental protection.

Description

The method for preparing Vanadium Pentoxide in FLAKES
Technical field
The present invention relates to field of metallurgy.More specifically, the present invention relates to prepare the method for Vanadium Pentoxide in FLAKES.
Background technology
Vanadium has many good physicochemical property, is widely used in industries such as metallurgy, electronics and chemical industry, and wherein about 85% the smelting ferrovanadium that is used for is used as alloy addition, mainly is to use with the form of Vanadium Pentoxide in FLAKES.At present the raw material of preparation Vanadium Pentoxide in FLAKES is mainly vanadium slag, technologies such as main method comprises that sodium roasting, pressurization alkali soak, calcification baking acidleach and the leaching of calcification baking alkali lye carbonating.Produce the method for Vanadium Pentoxide in FLAKES at present, the safety and sanitation that the ubiquity process is long, energy consumption is high, efficient is low and serious and environmental pollution problems.Along with country is more and more stricter to environmental requirement, the preparation method of traditional Vanadium Pentoxide in FLAKES can not satisfy environmental protection requirement.
Summary of the invention
The present invention is intended to solve at least one of technical problem that exists in the prior art.For this reason, one object of the present invention is to propose a kind of method for preparing Vanadium Pentoxide in FLAKES, and it has one of following advantage at least: efficient, low-cost, energy consumption is low, safety, environmental protection.
According to embodiments of the invention, provide a kind of and prepared the method for Vanadium Pentoxide in FLAKES from the leach liquor that contains vanadic acid sodium, it is characterized in that, may further comprise the steps: the described leach liquor that contains vanadic acid sodium is provided; In the described leach liquor that contains vanadic acid sodium, add ammonium sulfate, and regulate pH to pH value and be 1.5-2, under 90-100 degree centigrade temperature, heat afterwards, contain the mixed solution of ammonium poly-vanadate precipitation with generation; The described mixed solution that contains the ammonium poly-vanadate precipitation is carried out filtration washing obtain ammonium poly-vanadate precipitation and deposition vanadium mother liquid; Described ammonium poly-vanadate is deposited in the thermal degradation oxidation generates Vanadium Pentoxide in FLAKES under 400-500 degree centigrade the temperature.
According to embodiments of the invention, the method for preparing Vanadium Pentoxide in FLAKES from the leach liquor that contains vanadic acid sodium can also have following additional technical feature:
According to one embodiment of present invention, in the described leach liquor that contains vanadic acid sodium, add ammonium sulfate, and adjusting pH to pH value is 1.5-2, heat under 90-100 degree centigrade temperature afterwards, the mixed solution that contains the ammonium poly-vanadate precipitation with generation may further comprise the steps: it is 6-7 that the described leach liquor that contains vanadic acid sodium is carried out pH regulator to a pH value; In the solution that contains vanadic acid sodium through a pH regulator described, add ammonium sulfate, under 80-90 degree centigrade temperature, heat afterwards, form the mixed solution that contains ammonium vanadate; The described mixed solution that contains ammonium vanadate is carried out secondary pH regulator to pH value be 1.5-2; The described mixed solution that contains ammonium vanadate through the secondary pH regulator is heated under 90-100 degree centigrade temperature, contain the mixed solution of ammonium poly-vanadate precipitation with generation.Thus, can improve the preparation efficiency of ammonium poly-vanadate, and then improve the production efficiency of Vanadium Pentoxide in FLAKES.
According to one embodiment of present invention, utilize sulfuric acid to carry out a described pH regulator and/or described secondary pH regulator.According to one embodiment of present invention, thus, can improve the preparation efficiency of ammonium poly-vanadate, and then improve the production efficiency of Vanadium Pentoxide in FLAKES.Can improve the efficient of pH regulator thus, and can not introduce impurity component, be convenient to subsequent disposal, improve the production efficiency of Vanadium Pentoxide in FLAKES.
According to one embodiment of present invention, the water content of described ammonium poly-vanadate precipitation is lower than 25 weight %.Thus, can improve the efficient of follow-up thermal degradation oxidation, save the energy, cut down the consumption of energy.
According to one embodiment of present invention, further comprise: after 800 degrees centigrade of following heat fused, the cooling crushing obtains the tablet Vanadium Pentoxide in FLAKES with the Vanadium Pentoxide in FLAKES that obtains.Thus, be convenient to Vanadium Pentoxide in FLAKES is applied in the smelting of iron and steel.
According to one embodiment of present invention, the described leach liquor that contains vanadic acid sodium is to leach to handle by the roasting of meticulous vanadium slag to obtain, and the roasting of wherein said meticulous vanadium slag is leached to handle and be may further comprise the steps: described meticulous vanadium slag is provided; In described meticulous vanadium slag, add yellow soda ash acquisition roasting mixture; Described roasting mixture is carried out the roasting material that roasting obtains to contain vanadic acid sodium under the 700-850 degree celsius temperature; Described roasting material is carried out below the shrend to 100 degree centigrade; To carry out calcining matter pellet mill through the roasting material of shrend and obtain slurry; Described slurry is carried out water logging obtain to leach slurry; And the leaching slurry that obtains filtered the leach liquor that obtains filter residue and contain vanadic acid sodium.
According to one embodiment of present invention, described meticulous vanadium slag obtains through the following steps: the raw material vanadium slag is carried out fragmentation, carry out the vanadium slag after magnetic separation iron obtains scum and selects iron then; Select the vanadium slag behind the iron to carry out ball milling one time with described, once select powder to obtain meal then and as a fine powder of meticulous vanadium slag;
A described meal sieved obtain plus sieve and minus sieve; Described minus sieve is carried out secondary ball milling, carry out secondary then and select powder to obtain the secondary meal and as the secondary fine powder of meticulous vanadium slag.
Additional aspect of the present invention and advantage part in the following description provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Description of drawings
Above-mentioned and/or additional aspect of the present invention and advantage are from obviously and easily understanding becoming the description of embodiment in conjunction with following accompanying drawing, wherein:
Fig. 1 is the preparation method's of meticulous vanadium slag schematic flow sheet according to an embodiment of the invention.
Fig. 2 is the schematic flow sheet that according to another embodiment of the present invention vanadium slag is carried out twice fragmentation and twice magnetic separation.
Fig. 3 is the schematic flow sheet that scum is further processed according to further embodiment of this invention.
Fig. 4 is according to the schematic flow sheet that meal is further processed with the another embodiment of invention.
Fig. 5 is the schematic flow sheet according to the preparation method of the meticulous vanadium slag of following the another embodiment of invention.
Fig. 6 is the schematic flow sheet according to the meticulous vanadium slag roasting leaching method of the embodiment of the invention.
Fig. 7 is the schematic flow sheet according to the meticulous vanadium slag roasting leaching method of further embodiment of this invention.
Fig. 8 prepares the schematic flow sheet of Vanadium Pentoxide in FLAKES according to the embodiment of the invention from vanadic acid sodium.
Fig. 9 prepares the schematic flow sheet of Vanadium Pentoxide in FLAKES according to further embodiment of this invention from vanadic acid sodium.
Figure 10 is the schematic flow sheet according to the purification deposition vanadium mother liquid of the roasting leaching of the embodiment of the invention.
Figure 11 is the schematic flow sheet according to the purification deposition vanadium mother liquid of the roasting leaching of the embodiment of the invention.
Figure 12 is the synoptic diagram for the preparation of the equipment of meticulous vanadium slag according to the embodiment of the invention.
Figure 13 is the synoptic diagram for the preparation of the equipment of meticulous vanadium slag according to further embodiment of this invention.
Figure 14 is the synoptic diagram for the preparation of the equipment of meticulous vanadium slag according to further embodiment of this invention.
Figure 15 is the synoptic diagram for the preparation of the equipment of meticulous vanadium slag according to further embodiment of this invention.
Figure 16 is the synoptic diagram for the preparation of the equipment of meticulous vanadium slag according to further embodiment of this invention.
Embodiment
Describe embodiments of the invention below in detail, the example of described embodiment is shown in the drawings, and wherein identical or similar label is represented identical or similar elements or the element with identical or similar functions from start to finish.Be exemplary below by the embodiment that is described with reference to the drawings, only be used for explaining the present invention, and can not be interpreted as limitation of the present invention.
In description of the invention, term " vertically ", " laterally ", " on ", close the orientation of indications such as D score, " preceding ", " back ", " left side ", " right side ", " vertically ", " level ", " top ", " end " or position is based on orientation shown in the drawings or position relation, only be the present invention for convenience of description rather than require the present invention therefore can not be interpreted as limitation of the present invention with specific orientation structure and operation.
According to embodiments of the invention, the invention provides a kind of purifying method to deposition vanadium mother liquid.In an embodiment of the present invention, the implication of deposition vanadium mother liquid should be made broad understanding, can be any the easy of sexavalent chrome, sodium sulfate, ammonium sulfate and pentavalent vanadium that contain.In a preferred embodiment of the invention, the deposition vanadium mother liquid that adopts is to utilize meticulous vanadium slag to prepare the deposition vanadium mother liquid that produces in the process of Vanadium Pentoxide in FLAKES.According to the method for the embodiment of the invention, can be used as a part for preparing the Vanadium Pentoxide in FLAKES overall process from vanadium slag.Particularly, the technology for preparing Vanadium Pentoxide in FLAKES from vanadium slag comprises following components:
At first, from the meticulous vanadium slag of vanadium slag feedstock production;
The second, by meticulous vanadium slag is prepared burden, carry out roasting then and leach, obtain containing the roasting leach liquor of ammonium vanadate;
The 3rd, prepare ammonium poly-vanadate from the roasting leach liquor that contains ammonium vanadate, and then prepare Vanadium Pentoxide in FLAKES by ammonium poly-vanadate is carried out dry oxygenolysis, produce deposition vanadium mother liquid simultaneously; And
The 4th, resulting deposition vanadium mother liquid is carried out purifying treatment.
For convenience of description, according to above-mentioned flow process technical scheme of the present invention is described.
The preparation of meticulous vanadium slag
With reference to figure 1, according to embodiments of the invention, the method for preparing meticulous vanadium slag from the raw material vanadium slag may further comprise the steps:
As shown in Figure 1, at first, the raw material vanadium slag is carried out fragmentation, carry out the vanadium slag after magnetic separation iron obtains scum and selects iron then.According to embodiments of the invention, the raw material vanadium slag that adopts in the present invention is not particularly limited, and can be any material that contains vanadium.According to a concrete example of the present invention, described raw material vanadium slag is that vanadium titano-magnetite is through " slag " after making steel, thus, can from waste material, reclaim vanadium, reduce industrial cost, the applicant finds that vanadium titano-magnetite is through the calcium contents low (content of calcium oxide is for being lower than 3.5 weight %) of " slag " after making steel, thereby resulting meticulous vanadium slag will be applicable to sodium method roasting lixiviation process treatment process.
According to embodiments of the invention, can adopt any known crusher that the raw material vanadium slag is carried out fragmentation, and can adopt any known magnetic separator to carry out magnetic separation.According to embodiments of the invention, depend on the kind of raw material vanadium slag, can carry out multiple stage crushing-magnetic separation to the raw material vanadium slag and handle.For example for the raw material vanadium slag of granularity greater than 500mm, can carry out tertiary crushing-magnetic separation and handle.Be raw material vanadium slag below the 200mm for granularity, can carry out twice fragmentation-magnetic separation and handle.The synoptic diagram that carries out twice broken and twice magnetic separation has been shown among Fig. 2, concrete, at first the raw material vanadium slag is carried out primary fragmentation, the granularity of reduction raw material vanadium slag obtains the vanadium slag behind the primary fragmentation; Then, the vanadium slag behind the primary fragmentation is carried out vanadium slag after a magnetic separation obtains a scum and once selects iron, obviously, select once that iron level is significantly reduced in the vanadium slag behind the iron; Then, with once selecting the vanadium slag behind the iron to carry out secondary breaking, further reduce the granularity of vanadium slag, obtain the vanadium slag after the secondary breaking; At last, the vanadium slag after the secondary breaking is carried out the secondary magnetic separation obtain vanadium slag after secondary scum and secondary select iron, further reduce the iron level in the vanadium slag.Thus, can further improve the organic efficiency of vanadium, and then improve the production efficiency of Vanadium Pentoxide in FLAKES.Granularity through the vanadium slag after fragmentation-magnetic separation processing is less than 20mm, can be used for carrying out one time ball-milling processing.Need to prove that similar terms such as the term of mentioning in this article " once ", " secondary " are just used for convenience of distinguishing, rather than expression sequencing relation.According to embodiments of the invention, for resulting scum in fragmentation-magnetic separation treating processes, can further handle.Concrete, for example with reference to figure 5, at first in autogenous mill, scum is carried out autogenous grinding, thereby can carry out magnetic separation then so that vanadium slag can separate physically with iron, thereby can obtain iron and deironing vanadium slag; The deironing vanadium slag can obtain in other steps selects vanadium slag behind the iron to merge to carry out a follow-up ball-milling processing, contain the amount of vanadium in the resulting iron less than 4 weight %, can be delivered to steel mill and smelt.Thus, can fully reclaim vanadium, thereby improve the production efficiency of Vanadium Pentoxide in FLAKES, and obtain iron.
Next, to carry out ball milling one time through selecting the vanadium slag behind the iron, equally, also can use any ball mill as known in the art to carry out, according to embodiments of the invention, can before carrying out ball milling, handle carrying out pre-homogenizing through the vanadium slag that selects iron, thereby make the finally uniform component of the meticulous vanadium slag of acquisition.Then to once selecting powder to obtain meal through the vanadium slag of ball milling and as a fine powder of meticulous vanadium slag, those skilled in the art can understand can use that any known powder separating machine selects the powder operation in this area.With reference to figure 4, according to embodiments of the invention, a described meal can be sieved and obtain plus sieve and minus sieve; Described minus sieve is carried out secondary ball milling, carry out secondary then and select powder to obtain the secondary meal and as the secondary fine powder of meticulous vanadium slag.By above-mentioned ball milling-selecting the powder processing to access can be for the meticulous vanadium slag of follow-up roasting leaching processing.According to embodiments of the invention, plus sieve can be carried out the plus sieve after magnetic separation obtains iron and selects iron, and will select the plus sieve behind the iron to carry out secondary ball milling with minus sieve.Thus, can further reclaim vanadium, and improve the production efficiency of Vanadium Pentoxide in FLAKES.In addition, according to embodiments of the invention, with reference to figure 4 and Fig. 5, the minus sieve that secondary can be selected the resulting secondary meal of powder to return after selecting iron carries out the operation of secondary choosing branch.Thus, can further improve the organic efficiency of vanadium.
More than described the method according to the meticulous vanadium slag of preparation of the embodiment of the invention, according to embodiments of the invention, the iron level of resulting meticulous vanadium slag is below the 5 weight %.Thus, can improve follow-up roasting and leach the efficient of handling.In addition, according to another concrete example of the present invention, thin vanadium slag granularity is less than 150 microns.Thus, can further improve follow-up roasting and leach the efficient of handling.In addition, according to embodiments of the invention, also further comprise the step that resulting meticulous vanadium slag is prepared burden, namely, resulting meticulous vanadium slag is mixed according to the stoichiometric ratio of sodium method roasting with yellow soda ash and water, obtain also can being called raw material be used to the roasting mixture that carries out the roasting reaction, leach reaction thereby be convenient to follow-up roasting.According to another embodiment of the invention, the addition of yellow soda ash can be excessive on the stoichiometry, thereby can carry out roasting and leaching to resulting meticulous vanadium slag fully, thereby can improve the organic efficiency of vanadium.According to other embodiments of the invention, can also in the process of batching, add roasting and leach the resulting leached mud of reaction, thereby can improve the organic efficiency of vanadium.In addition, according to specific examples of the present invention, can carry out rerolling, realize good homogeneous thus, be convenient to subsequent disposal.
According to embodiments of the invention, the present invention also provides a kind of equipment for the preparation of meticulous vanadium slag.Next, the applicant is described the equipment for the preparation of meticulous vanadium slag.In description of the invention, need to prove that unless otherwise prescribed and limit, term " installation ", " linking to each other ", " connection " should be done broad understanding, for example, can be fixedly connected, also can be to removably connect; Can be directly to link to each other, also can link to each other indirectly by intermediary, for the ordinary skill in the art, can understand the concrete implication of above-mentioned term as the case may be.
With reference to figure 12-16, below the equipment for the preparation of meticulous vanadium slag according to the embodiment of the invention is described.According to embodiments of the invention, comprise first crusher, first magnetic separator, first ball mill, first powder separating machine, first sieve apparatus, second ball mill and second powder separating machine for the preparation of the equipment of meticulous vanadium slag.Wherein, first crusher obtains the primary fragmentation vanadium slag for the raw material vanadium slag is carried out primary fragmentation; First magnetic separator links to each other with first crusher for the vanadium slag that the primary fragmentation vanadium slag is carried out after a magnetic separation obtains scum and selects iron; First ball mill links to each other with first magnetic separator and will select vanadium slag behind the iron to carry out ball milling to obtain vanadium slag through a ball milling; First powder separating machine links to each other with first ball mill and is used for once selecting powder to obtain meal and as a fine powder of meticulous vanadium slag to the vanadium slag through a ball milling; First sieve apparatus links to each other with first powder separating machine and obtains plus sieve and minus sieve for a meal is sieved; Second ball mill links to each other with first sieve apparatus and is used for that plus sieve is carried out secondary ball milling and obtains plus sieve through secondary ball milling; Link to each other with second ball mill with second powder separating machine and to be used for that the minus sieve through secondary ball milling is carried out secondary and to select powder to obtain the secondary meal and as the secondary fine powder of meticulous vanadium slag.Thus, utilize aforesaid device, can prepare meticulous vanadium slag.
According to embodiments of the invention, the iron level of resulting meticulous vanadium slag is below the 5 weight %.Thus, can improve follow-up roasting and leach the efficient of handling.In addition, according to another concrete example of the present invention, thin vanadium slag granularity is less than 150 microns.Thus, can further improve follow-up roasting and leach the efficient of handling.
According to embodiments of the invention, the equipment for preparing meticulous vanadium slag can further include autogenous mill, and this autogenous mill is connected with first magnetic separator and is used for that scum is carried out autogenous grinding and obtains scum through autogenous grinding; With second magnetic separator, this second magnetic separator links to each other with first ball mill with autogenous mill respectively and is used for that the scum through autogenous grinding is carried out magnetic separation and obtains iron and the first deironing vanadium slag and the first deironing vanadium slag is inputed to described first ball mill carrying out ball milling one time with selecting the vanadium slag behind the iron.According to embodiments of the invention, the equipment for preparing meticulous vanadium slag can further include the 3rd magnetic separator, and the 3rd magnetic separator links to each other with second ball mill with first sieve apparatus respectively and obtains iron and the 3rd deironing vanadium slag and described the 3rd deironing vanadium slag is inputed to described second ball mill carrying out secondary ball milling with described minus sieve for plus sieve being carried out magnetic separation.According to embodiments of the invention, the equipment for preparing meticulous vanadium slag can further include the secondary meal and is back to described second ball mill so that this secondary meal is carried out secondary ball milling.According to embodiments of the invention, the equipment for preparing meticulous vanadium slag can further include second crusher, and this second crusher links to each other with first magnetic separator and is used for obtaining the secondary breaking vanadium slag to selecting vanadium slag behind the iron to carry out secondary breaking; With the 4th magnetic separator, the 4th magnetic separator links to each other with first ball mill with second crusher and obtains scum and the 4th deironing vanadium slag for the secondary breaking vanadium slag is carried out magnetic separation.The advantage of the feature of this equipment is described in the introduction of preceding method, does not repeat them here.
Roasting is leached
Behind the meticulous vanadium slag of preparation, generate vanadic acid sodium by meticulous vanadium slag being mixed with yellow soda ash and carrying out roasting, because the vanadic acid sodium water soluble, thereby can carry out water logging, and vanadic acid sodium is dissolved in the water, obtain to contain the leach liquor of vanadic acid sodium.
Particularly, with reference to figure 6, according to embodiments of the invention, roasting is leached and to be comprised that at first adding yellow soda ash in the meticulous vanadium slag of aforementioned acquisition mixes and obtain the roasting mixture, and according to embodiments of the invention, yellow soda ash is that the form with particle adds.Then, above-mentioned roasting mixture is carried out roasting under the 700-850 degree celsius temperature, trivalent or tetravalence vanadium are oxidized to the pentavalent barium oxide, and the Na that comes out with the yellow soda ash pyrolytic decomposition 2The O effect generates vanadic acid sodium soluble in water, obtains to contain the roasting material of vanadic acid sodium, so that carry out water logging.The time of roasting also is not particularly limited, and according to concrete example of the present invention, the time of roasting is 3-6 hour, can react more thoroughly under cost-effective situation thus.
Next, described roasting material is carried out shrend, be quickly cooled to below 100 degrees centigrade.The applicant finds when the roasting material slowly cools off, and is low thereby vanadic acid sodium can form the organic efficiency of water-fast material vanadium.And when adopting Water Quenching to be quickly cooled to below 100 degrees centigrade, can avoid this situation, and then be conducive to improve the organic efficiency of vanadium.
Then, will carry out calcining matter pellet mill through the calcining matter of shrend and obtain slurry, and slurry be carried out the water logging acquisition leach slurry.Because the vanadic acid sodium water soluble, thereby in the process of water logging, vanadic acid sodium is dissolved in the water, forms the leach liquor that contains vanadic acid sodium.Because, before carrying out water logging, will carry out calcining matter pellet mill through the roasting material of shrend, thereby can improve the efficient of water logging greatly.Adding the amount of water in the water logging process here, is excessive based on the solubleness of vanadic acid sodium.In addition, according to embodiments of the invention, leaching is carried out continuously, for example, leaches continuously in a plurality of continuous leaching chambers, can improve the efficient of leaching thus, and then improves the production efficiency of Vanadium Pentoxide in FLAKES.
At last, resulting leaching slurry is filtered, obtain filter residue and the leach liquor that contains vanadic acid sodium.With reference to figure 7, according to embodiments of the invention, filter residue can be returned and carry out water logging, can improve the organic efficiency of vanadium thus.Concrete, according to one embodiment of present invention, at first filter residue is washed, and will wash back liquid and carry out ball milling with described roasting material through shrend.Thus, can further improve the organic efficiency of vanadium, and then improve the production efficiency of Vanadium Pentoxide in FLAKES.In addition, the applicant finds can be for the preparation of black ceramic and solar absorber plate etc. according to the resulting filter residue of meticulous vanadium slag roasting leaching method of the embodiment of the invention, thereby has improved the utility value of refuse.According to embodiments of the invention, can after with meticulous vanadium slag and sodium carbonate roasting, add sal epsom, can generate the trimagnesium phosphate precipitation thus, can make that thus the phosphorus content in the leach liquor is reduced.Addition manner and the opportunity of sal epsom are unrestricted.With reference to figure 7, can be after shrend, add magnesium sulfate solution in the process of ball milling.In addition, can also further add ammonium sulfate, thereby generate the lower magnesium ammonium phosphate of solubleness, thus the better effects if of dephosphorization.In addition, according to embodiments of the invention, can also add Tai-Ace S 150, thereby the generation pure aluminium silicate precipitates to remove the silicon in the leach liquor.Addition manner and the opportunity of Tai-Ace S 150 are unrestricted.With reference to figure 7, can be after shrend, add aluminum sulfate aqueous solution in the process of ball milling.Thus, can improve the purity of leach liquor, and then improve the purity of prepared Vanadium Pentoxide in FLAKES.Can also in washing process, directly wash with the aqueous solution that contains sal epsom, add at least a of ammonium sulfate and Tai-Ace S 150 alternatively.According to other embodiments of the invention, sal epsom, ammonium sulfate and Tai-Ace S 150 can also be added in the leach liquor, filter the leach liquor that is purified.Here the ammonium sulfate that adds, sal epsom and Tai-Ace S 150 are upward excessive with respect to the quantification metering of the phosphorus that will remove and/or silicon, can improve purification effects thus.
The preparation Vanadium Pentoxide in FLAKES
After obtaining to contain the leach liquor of vanadic acid sodium, the reaction by vanadic acid sodium and ammonium sulfate can obtain ammonium poly-vanadate, further with the oxidation of ammonium poly-vanadate thermal degradation, can obtain Vanadium Pentoxide in FLAKES.
Concrete, according to embodiments of the invention, with reference to figure 8, in the described leach liquor that contains vanadic acid sodium, add ammonium sulfate, and regulate pH to pH value and be 1.5-2, under 90-100 degree centigrade temperature, heat afterwards, contain the mixed solution of ammonium poly-vanadate precipitation with generation; The mixed solution that will contain the ammonium poly-vanadate precipitation carries out filtration washing and obtains ammonium poly-vanadate precipitation and deposition vanadium mother liquid; Ammonium poly-vanadate is deposited in the thermal degradation oxidation generates Vanadium Pentoxide in FLAKES under 400-500 degree centigrade the temperature.According to embodiments of the invention, with reference to figure 9, generate the mixed solution contain the ammonium poly-vanadate precipitation and may further comprise the steps: the leach liquor that will contain vanadic acid sodium carries out pH regulator one time, to pH be 6-7; In the solution that contains vanadic acid sodium through a pH regulator, add ammonium sulfate, under 80-90 degree centigrade temperature, heat afterwards, form the mixed solution that contains ammonium vanadate; The mixed solution that will contain ammonium vanadate carries out the secondary pH regulator, to the pH value be 1.5-2; To under 90-100 degree centigrade temperature, heat through the mixed solution that contains ammonium vanadate of secondary pH regulator, contain the mixed solution of ammonium poly-vanadate precipitation with generation.Thus, can improve the formation efficiency of ammonium poly-vanadate greatly.In the present invention, the means of regulating pH are unrestricted, according to embodiments of the invention, utilize sulfuric acid to carry out a described pH regulator and/or described secondary pH regulator.In the present invention, the method of filtering is not particularly limited, according to embodiments of the invention, the water content of described ammonium poly-vanadate precipitation is lower than 40 weight %, be preferably 10-40 weight %, be convenient to subsequent disposal thus, and because water content is low thereby can save a large amount of energy in follow-up thermal degradation oxidising process, cut down the consumption of energy.Can earlier ammonium poly-vanadate be carried out drying earlier, and then in rotary kiln, carry out decomposing oxidation.According to embodiments of the invention, ammonium poly-vanadate is carried out dry equipment and method be not particularly limited, can use that any known equipment carries out in this area.According to concrete example of the present invention, can adopt flash drying equipment as known in the art, also can adopt the vacuum drying treatment method and apparatus.Certainly, also can once finish the step of dry decomposing oxidation in the rotary kiln the inside.The further embodiment according to the present invention, the applicant finds through the water content of the ammonium poly-vanadate precipitation of filtration treatment relatively low, can once finish the step of dry decomposing oxidation in the rotary kiln the inside, saved and carried out dry step separately, thereby save a large amount of energy, cut down the consumption of energy, realize the effect of environment-friendly and energy-saving emission-reduction.According to embodiments of the invention, after generating Vanadium Pentoxide in FLAKES, after 800 degrees centigrade of following heat fused, cooling press particle degree obtains the tablet Vanadium Pentoxide in FLAKES less than 10mm with the Vanadium Pentoxide in FLAKES that obtains.The tablet Vanadium Pentoxide in FLAKES of Huo Deing can be directly used in the smelting iron and steel industry like this.
The purification of deposition vanadium mother liquid
Prepare in the process of Vanadium Pentoxide in FLAKES in precipitation, obtained deposition vanadium mother liquid, this deposition vanadium mother liquid contains sexavalent chrome, sodium sulfate, ammonium sulfate and pentavalent vanadium.Wherein sexavalent chrome and pentavalent vanadium are poisonous, if thereby directly with deposition vanadium mother liquid discharging, will cause serious pollution.
According to embodiments of the invention, with reference to Figure 10 and 11, the purification of deposition vanadium mother liquid is comprised: deposition vanadium mother liquid is provided, and wherein deposition vanadium mother liquid contains sexavalent chrome, sodium sulfate, ammonium sulfate and pentavalent vanadium; Add sulfurous gas in the deposition vanadium mother liquid and obtain sexavalent chrome and be reduced to chromic mixed solution and be neutralized to alkalescence, contain the post precipitation liquid of chromium hydroxide precipitation with generation; Filter the filtrate that obtains chromium hydroxide precipitation and contain sodium sulfate, ammonium sulfate and pentavalent vanadium with the post precipitation liquid that will contain chromium hydroxide precipitation.According to embodiments of the invention, the sulfurous gas that adopts prepares by burning sulphur, can save cost like this, and sulphur is convenient to preserve.According to embodiments of the invention, by the addition of control sulfurous gas, thereby and then the control reduction potential only make sexavalent chrome be reduced to trivalent chromium and the pentavalent vanadium is not reduced.The pentavalent vanadium can be returned the preparation of carrying out Vanadium Pentoxide in FLAKES like this.Concrete, according to an example of the present invention, under 100-120 degree centigrade temperature, the filtrate evaporation of containing sodium sulfate, ammonium sulfate and vanadic acid sodium obtained sodium sulfate crystal and contain the solution of ammonium sulfate, pentavalent vanadium and remaining sodium sulfate.The applicant finds that the sodium sulfate crystal that crystallization obtains under 100-120 degree centigrade temperature does not contain crystal water, and according to concrete example of the present invention, can obtain highly purified saltcake (purity is 99.5-99.9%) by resulting sodium sulfate crystal being made with extra care filter.In addition, the solution that contains ammonium sulfate, pentavalent vanadium and remaining sodium sulfate can be returned the preparation Vanadium Pentoxide in FLAKES.Thereby make the best use of everything, the problem of environmental pollution of avoiding directly discharging to bring, and improved economic benefit.
In the description of this specification sheets, concrete feature, structure, material or characteristics that the description of reference term " embodiment ", " some embodiment ", " example ", " concrete example " or " some examples " etc. means in conjunction with this embodiment or example description are contained at least one embodiment of the present invention or the example.In this manual, the schematic statement to above-mentioned term not necessarily refers to identical embodiment or example.And concrete feature, structure, material or the characteristics of description can be with the suitable manner combination in any one or more embodiment or example.
Although illustrated and described embodiments of the invention, those having ordinary skill in the art will appreciate that: can carry out multiple variation, modification, replacement and modification to these embodiment under the situation that does not break away from principle of the present invention and aim, scope of the present invention is limited by claim and equivalent thereof.

Claims (1)

1. one kind prepares the method for Vanadium Pentoxide in FLAKES from the leach liquor that contains vanadic acid sodium, it is characterized in that, may further comprise the steps:
The described leach liquor that contains vanadic acid sodium is provided;
In the described leach liquor that contains vanadic acid sodium, add ammonium sulfate, and regulate pH to pH value and be 1.5-2, under 90-100 degree centigrade temperature, heat afterwards, contain the mixed solution of ammonium poly-vanadate precipitation with generation;
The described mixed solution that contains the ammonium poly-vanadate precipitation is carried out filtration washing obtain ammonium poly-vanadate precipitation and deposition vanadium mother liquid;
Described ammonium poly-vanadate is deposited in the thermal degradation oxidation generates Vanadium Pentoxide in FLAKES under 400-500 degree centigrade the temperature; And
Resulting deposition vanadium mother liquid is carried out purifying treatment,
Wherein,
Purification to described deposition vanadium mother liquid comprises:
Described deposition vanadium mother liquid is provided, and wherein said deposition vanadium mother liquid contains sexavalent chrome, sodium sulfate, ammonium sulfate and pentavalent vanadium;
Add sulfurous gas in the described deposition vanadium mother liquid and obtain sexavalent chrome and be reduced to chromic mixed solution and be neutralized to alkalescence, contain the post precipitation liquid of chromium hydroxide precipitation with generation; With
The described post precipitation liquid that contains chromium hydroxide precipitation is filtered the filtrate that obtains described chromium hydroxide precipitation and contain sodium sulfate, ammonium sulfate and pentavalent vanadium,
Add ammonium sulfate in the described leach liquor that contains vanadic acid sodium, and regulate pH to pH value and be 1.5-2, heat under 90-100 degree centigrade temperature afterwards, the mixed solution that contains the ammonium poly-vanadate precipitation with generation may further comprise the steps:
The described leach liquor that contains vanadic acid sodium is carried out pH regulator to a pH value be 6-7;
In the solution that contains vanadic acid sodium through a pH regulator described, add ammonium sulfate, under 80-90 degree centigrade temperature, heat afterwards, form the mixed solution that contains ammonium vanadate;
The described mixed solution that contains ammonium vanadate is carried out secondary pH regulator to pH value be 1.5-2;
The described mixed solution that contains ammonium vanadate through the secondary pH regulator is heated under 90-100 degree centigrade temperature, contains the mixed solution that ammonium poly-vanadate precipitates with generation,
Utilize sulfuric acid to carry out a described pH regulator and/or described secondary pH regulator,
The water content of described ammonium poly-vanadate precipitation is lower than 25 weight %,
Further comprise:
After 800 degrees centigrade of following heat fused, the cooling crushing obtains the tablet Vanadium Pentoxide in FLAKES with the Vanadium Pentoxide in FLAKES that obtains,
The described leach liquor that contains vanadic acid sodium is to leach to handle by the roasting of meticulous vanadium slag to obtain, and the roasting of wherein said meticulous vanadium slag is leached to handle and be may further comprise the steps:
Described meticulous vanadium slag is provided;
In described meticulous vanadium slag, add yellow soda ash acquisition roasting mixture;
Described roasting mixture is carried out the roasting material that roasting obtains to contain vanadic acid sodium under the 700-850 degree celsius temperature;
Described roasting material is carried out below the shrend to 100 degree centigrade;
To carry out calcining matter pellet mill through the roasting material of shrend and obtain slurry;
Described slurry is carried out water logging obtain to leach slurry; And
The leaching slurry that obtains is filtered the leach liquor that obtains filter residue and contain vanadic acid sodium,
Described meticulous vanadium slag obtains through the following steps:
The raw material vanadium slag is carried out fragmentation, carry out the vanadium slag after magnetic separation iron obtains scum and selects iron then;
Select the vanadium slag behind the iron to carry out ball milling one time with described, once select powder to obtain meal then and as a fine powder of meticulous vanadium slag;
A described meal sieved obtain plus sieve and minus sieve;
Described minus sieve is carried out secondary ball milling, carry out secondary then and select powder to obtain the secondary meal and as the secondary fine powder of meticulous vanadium slag.
CN2011100824440A 2011-04-01 2011-04-01 Method for preparing vanadium pentoxide CN102219257B (en)

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