CN102220495B - Method for purifying vanadium-precipitating mother liquor - Google Patents
Method for purifying vanadium-precipitating mother liquor Download PDFInfo
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Abstract
The invention discloses a method for purifying vanadium-precipitating mother liquor, wherein the vanadium-precipitating mother liquor comprises hexavalent chromium, sodium sulfate, ammonium sulfate and pentavalent vanadium. The method comprises the following steps of: adding sulfur dioxide into the vanadium-precipitating mother liquor to obtain the hexavalent chromium; reducing the hexavalent chromium into mixed liquid of trivalent chromium, neutralizing the mixed liquid to be alkaline to generate a post-precipitation liquid containing chromium hydroxide precipitate; and filtering the post-precipitation liquid containing the chromium hydroxide precipitate to obtain the chromium hydroxide precipitate and filtrate containing sodium sulfate, ammonium sulfate and pentavalent vanadium. The purifying method disclosed by the invention has at least one of the advantages of high efficiency, low cost, low energy consumption, safety and environment friendliness.
Description
Technical field
The present invention relates to field of metallurgy.More specifically, the present invention relates to prepare the purifying method of deposition vanadium mother liquid.
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, 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 purifying method of deposition vanadium mother liquid, and it has one of advantage at least: efficient, low-cost, energy consumption is low, safety, environmental protection.
According to embodiments of the invention; A kind of purifying method of deposition vanadium mother liquid is provided; Wherein said deposition vanadium mother liquid contains sexavalent chrome, sodium sulfate, ammonium sulfate and pentavalent vanadium; Said method comprising the steps of: in said deposition vanadium mother liquid, add sulfurous gas acquisition 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 being filtered, the said post precipitation liquid that contains chromium hydroxide precipitation obtains chromium hydroxide precipitation and the filtrating of containing sodium sulfate, ammonium sulfate and pentavalent vanadium.
According to embodiments of the invention, the purifying method of deposition vanadium mother liquid can also have following additional technical feature:
According to one embodiment of present invention, the addition through control sulfurous gas only makes sexavalent chrome be reduced to trivalent chromium and the pentavalent vanadium is not reduced.
According to one embodiment of present invention, under 100-120 degree centigrade temperature, the said filtrating of containing sodium sulfate, ammonium sulfate and vanadic acid sodium is evaporated to obtain sodium sulfate crystal and to contain the solution of ammonium sulfate, pentavalent vanadium and remaining sodium sulfate.
According to one embodiment of present invention, said deposition vanadium mother liquid obtains through the following step: the leach liquor that contains vanadic acid sodium is provided; In the said 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 sedimentary mixed solution of ammonium poly-vanadate with generation; The said sedimentary mixed solution of ammonium poly-vanadate that contains is carried out filtration washing acquisition ammonium poly-vanadate deposition and deposition vanadium mother liquid; Said ammonium poly-vanadate is deposited in thermal degradation generates Vanadium Pentoxide in FLAKES under 400-500 degree centigrade the temperature.
According to one embodiment of present invention, the said leach liquor that contains vanadic acid sodium obtains through the following step: meticulous vanadium slag is provided; In said meticulous vanadium slag, add yellow soda ash and obtain the roasting mixture; Said roasting mixture is carried out the roasting material that roasting obtains to contain vanadic acid sodium under the 700-850 degree celsius temperature; Said roasting material is carried out below the shrend to 100 degree centigrade; The roasting material that will pass through shrend carries out calcining matter pellet mill and obtains slurry; Said slurry is carried out water logging obtain to leach slurry; And the leaching slurry that is obtained filtered obtain filter residue and the leach liquor that contains vanadic acid sodium.
According to one embodiment of present invention, said meticulous vanadium slag obtains through the following step: 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 said, once select powder to obtain meal then and as a fine powder of meticulous vanadium slag;
A said meal sieved obtain plus sieve and minus sieve; Said 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 through practice of the present invention.
Description of drawings
Above-mentioned and/or additional aspect of the present invention and advantage obviously with are easily understood becoming the description of embodiment from combining figs, wherein:
Fig. 1 is the preparing method's of meticulous vanadium slag a 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 handled according to further embodiment of this invention.
Fig. 4 is according to the schematic flow sheet that meal is further handled 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 of equipment that is used to prepare meticulous vanadium slag according to the embodiment of the invention.
Figure 13 is the synoptic diagram of equipment that is used to prepare meticulous vanadium slag according to further embodiment of this invention.
Figure 14 is the synoptic diagram of equipment that is used to prepare meticulous vanadium slag according to further embodiment of this invention.
Figure 15 is the synoptic diagram of equipment that is used to prepare meticulous vanadium slag according to further embodiment of this invention.
Figure 16 is the synoptic diagram of equipment that is used to prepare meticulous vanadium slag according to further embodiment of this invention.
Embodiment
Describe embodiments of the invention below in detail, the example of said embodiment is shown in the drawings, and wherein identical from start to finish or similar label is represented identical or similar elements or the element with identical or similar functions.Be exemplary through the embodiment that is described with reference to the drawings below, only be used to explain the present invention, and can not be interpreted as limitation of the present invention.
In description of the invention; Term " vertically ", " laterally ", " on ", the orientation of indications such as D score, " preceding ", " back ", " left side ", " right side ", " vertically ", " level ", " top ", " end " or position relation be for based on orientation shown in the drawings or position relation; Only be for the ease of describing the present invention rather than requiring the present invention therefore can not be interpreted as limitation of the present invention with specific azimuth configuration 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 is adopted is to utilize meticulous vanadium slag to prepare the deposition vanadium mother liquid that is produced 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, through 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 through 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.
Describe for ease, technical scheme of the present invention is described according to above-mentioned flow process.
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 is adopted does not in the present invention receive special restriction, can be any material that contains vanadium.According to a concrete example of the present invention; Said raw material vanadium slag is " slag " after the steel-making of vanadium titano-magnetite process, 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 quicklime 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, can carry out tertiary crushing-magnetic separation and handle for the raw material vanadium slag of granularity greater than 500mm.For granularity is the raw material vanadium slag below the 200mm, 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 the 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,, further reduce the granularity of vanadium slag, obtain the vanadium slag after the secondary breaking once selecting the vanadium slag behind the iron to carry out secondary breaking; At last, the vanadium slag after the secondary breaking is carried out the secondary magnetic separation obtain the 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 to carry out ball-milling processing one time.Need to prove that similar terms such as the term of being mentioned in this article " once ", " secondary " are just distinguished for ease and used, rather than expression sequencing relation.According to embodiments of the invention,, can further handle for resulting scum in fragmentation-magnetic separation treating processes.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, thereby can obtain iron and deironing vanadium slag so that vanadium slag can physically separate with iron; 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, and the amount that contains vanadium in the resulting iron can be delivered to steel mill and smelt less than 4 weight %.Thus, can fully reclaim vanadium, thereby improve the production efficiency of Vanadium Pentoxide in FLAKES, and obtain iron.
Next; To through the vanadium slag that choosing behind the iron and carry out ball milling one time, same, 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, thereby make the finally uniform component of the meticulous vanadium slag of acquisition carrying out preparatory homogenizing through the vanadium slag that selects iron.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,, can a said meal be sieved and obtain plus sieve and minus sieve according to embodiments of the invention; Said 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.Handle to access through above-mentioned ball milling-select powder and can be used for follow-up roasting and leach the meticulous vanadium slag of handling.According to embodiments of the invention, can plus sieve 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,, can the minus sieve that secondary selects the resulting secondary meal of powder to return after selecting iron be carried out the operation of secondary choosing branch with reference to figure 4 and Fig. 5.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, promptly; Resulting meticulous vanadium slag is mixed according to the stoichiometric ratio of sodium method roasting with yellow soda ash and water; Obtain being used to carry out the roasting mixture of roasting reaction, also can be called raw material, 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,, can carry out rerolling, realize good homogeneous property thus, be convenient to subsequent disposal according to specific examples of the present invention.
According to embodiments of the invention, the present invention also provides a kind of equipment that is used to prepare meticulous vanadium slag.Next, the applicant describes the equipment that is used to prepare meticulous vanadium slag.In description of the invention, need to prove that unless otherwise prescribed and limit, term " installations ", " linking to each other ", " connection " should be done broad understanding, for example, can be fixed connections, also can be to removably connect; Can be directly to link to each other, also can link to each other indirectly, for those of ordinary skill in the art, can understand the concrete implication of above-mentioned term as the case may be through intermediary.
With reference to figure 12-16, describe down in the face of the equipment that is used to prepare meticulous vanadium slag according to the embodiment of the invention.According to embodiments of the invention, the equipment that is used to prepare meticulous vanadium slag comprises first crusher, first magnetic separator, first ball mill, first powder separating machine, first sieve apparatus, second ball mill and second powder separating machine.Wherein, first crusher is used for that the raw material vanadium slag is carried out primary fragmentation and obtains the primary fragmentation vanadium slag; First magnetic separator links to each other with first crusher and is used for the primary fragmentation vanadium slag is carried out the vanadium slag 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 a ball milling to obtain the 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 to be used for a meal sieved and obtains plus sieve and minus sieve; Second ball mill links to each other with first sieve apparatus and is used for plus sieve is carried out the plus sieve that secondary ball milling obtains the process secondary ball milling; Link to each other with second ball mill with second powder separating machine and to be used for selecting powder to obtain the secondary meal and as the secondary fine powder of meticulous vanadium slag carry out secondary through the minus sieve of secondary ball milling.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 scum is carried out the scum that autogenous grinding obtains the process 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 obtaining iron and the first deironing vanadium slag and the first deironing vanadium slag is inputed to said first ball mill carrying out ball milling one time with selecting the vanadium slag behind the iron to carry out magnetic separation through the scum of autogenous grinding.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 is used for that plus sieve is carried out magnetic separation and obtains iron and the 3rd deironing vanadium slag and said the 3rd deironing vanadium slag is inputed to said second ball mill carrying out secondary ball milling with said minus sieve.According to embodiments of the invention, the equipment for preparing meticulous vanadium slag can further include the secondary meal and is back to said 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 and second crusher link to each other with first ball mill and are used for that the secondary breaking vanadium slag is carried out magnetic separation and obtain scum and the 4th deironing vanadium slag.The advantage of the characteristic of this equipment is described in the introduction of preceding method, repeats no more at this.
Roasting is leached
Behind the meticulous vanadium slag of preparation, generate vanadic acid sodium through 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 is comprised that at first in the meticulous vanadium slag of aforementioned acquisition, adding the yellow soda ash mixing obtains the roasting mixture, and according to embodiments of the invention, yellow soda ash adds with the particulate form.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 does not receive special restriction, and according to concrete example of the present invention, the time of roasting is 3-6 hour, can under cost-effective situation, react more thoroughly thus.
Next, said 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 help improving the organic efficiency of vanadium.
Then, the calcining matter that will pass through shrend carries out calcining matter pellet mill and obtains slurry, and slurry is 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, the roasting material that will pass through shrend carries out calcining matter pellet mill, 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, in a plurality of successive leachings chamber, leaches continuously, can improve the efficient of leaching thus, and then improve 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, can filter residue 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 said 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 used to prepare 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 deposition thus, can make that thus the phosphorus content in the leach liquor is reduced.Do not receive any restriction on the addition manner of sal epsom and opportunity.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,, can also add Tai-Ace S 150, thereby generate the pure aluminium silicate deposition to remove the silicon in the leach liquor according to embodiments of the invention.Do not receive any restriction on the addition manner of Tai-Ace S 150 and opportunity.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, add at least a of ammonium sulfate and Tai-Ace S 150 alternatively with the aqueous solution that contains sal epsom.According to other embodiments of the invention, can also sal epsom, ammonium sulfate and Tai-Ace S 150 be added in the leach liquor, filter the leach liquor that is purified.Here the ammonium sulfate that is added, sal epsom and Tai-Ace S 150 be with respect to the quantification metering of the phosphorus that will remove and/or silicon go up excessively, can improve purification effects thus.
The preparation Vanadium Pentoxide in FLAKES
After obtaining to contain the leach liquor of vanadic acid sodium, the reaction through 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,, in the said leach liquor that contains vanadic acid sodium, add ammonium sulfate, and regulate pH to pH value and be 1.5-2 with reference to figure 8, under 90-100 degree centigrade temperature, heat afterwards, contain the sedimentary mixed solution of ammonium poly-vanadate with generation; The sedimentary mixed solution of ammonium poly-vanadate be will contain and filtration washing acquisition ammonium poly-vanadate deposition and deposition vanadium mother liquid carried out; 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 and to contain the sedimentary mixed solution of ammonium poly-vanadate 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, add ammonium sulfate, under 80-90 degree centigrade temperature, heat afterwards, form the mixed solution that contains ammonium vanadate through a pH regulator; The mixed solution that will contain ammonium vanadate carries out the secondary pH regulator, to the pH value be 1.5-2; The mixed solution that contains ammonium vanadate that will pass through the secondary pH regulator heats under 90-100 degree centigrade temperature, contains the sedimentary mixed solution of ammonium poly-vanadate with generation.Thus, can improve the formation efficiency of ammonium poly-vanadate greatly.In the present invention, the means of regulating pH do not receive any restriction, according to embodiments of the invention, utilize sulfuric acid to carry out a said pH regulator and/or said secondary pH regulator.In the present invention; Carry out filtering method and do not receive special restriction, according to embodiments of the invention, the sedimentary water cut of said ammonium poly-vanadate is lower than 40 weight %; Be preferably 10-40 weight %; Be convenient to subsequent disposal thus, and, cut down the consumption of energy because water cut is low thereby in follow-up thermal degradation oxidising process, can save mass 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 exsiccant equipment and method does not receive special restriction, 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 accomplish 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 sedimentary water cut of ammonium poly-vanadate of filtration treatment relatively low; Can once accomplish the step of dry decomposing oxidation in the rotary kiln the inside, save and carried out the exsiccant step separately, thereby saved mass 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 is obtained.The tablet Vanadium Pentoxide in FLAKES that obtains like this can directly be used for the smelting iron and steel industry.
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 deleterious, 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; In deposition vanadium mother liquid, add sulfurous gas acquisition 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 filtrating 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 is adopted prepares through burning sulphur, can save cost like this, and sulphur is convenient to preserve.According to embodiments of the invention, through 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.Can the pentavalent vanadium 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 filtrating of containing sodium sulfate, ammonium sulfate and vanadic acid sodium is evaporated to obtain sodium sulfate crystal and to 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, can obtain highly purified saltcake (purity is 99.5-99.9%) through resulting sodium sulfate crystal being made with extra care filter according to concrete example of the present invention.In addition, can the solution that contain ammonium sulfate, pentavalent vanadium and remaining sodium sulfate 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 be brought, and improved economic benefit.
In the description of this specification sheets, the description of reference term " embodiment ", " some embodiment ", " example ", " concrete example " or " some examples " etc. means the concrete characteristic, structure, material or the characteristics that combine this embodiment or example to describe and is 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 characteristic, structure, material or the characteristics of description can combine with suitable manner 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: under the situation that does not break away from principle of the present invention and aim, can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited claim and equivalent thereof.
Claims (6)
1. the purifying method of a deposition vanadium mother liquid, wherein said deposition vanadium mother liquid contains sexavalent chrome, sodium sulfate, ammonium sulfate and pentavalent vanadium, said method comprising the steps of:
In said deposition vanadium mother liquid, add sulfurous gas acquisition 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 said post precipitation liquid that contains chromium hydroxide precipitation is filtered the filtrating that obtains chromium hydroxide precipitation and contain sodium sulfate, ammonium sulfate and pentavalent vanadium.
2. the purifying method of deposition vanadium mother liquid according to claim 1 is characterized in that, the addition through control sulfurous gas only makes sexavalent chrome be reduced to trivalent chromium and the pentavalent vanadium is not reduced.
3. the purifying method of deposition vanadium mother liquid according to claim 1; It is characterized in that, under 100-120 degree centigrade temperature, the said filtrating of containing sodium sulfate, ammonium sulfate and pentavalent vanadium is evaporated to obtain sodium sulfate crystal and to contain the solution of ammonium sulfate, pentavalent vanadium and remaining sodium sulfate.
4. the purifying method of deposition vanadium mother liquid according to claim 1 is characterized in that, said deposition vanadium mother liquid obtains through the following step:
The leach liquor that contains vanadic acid sodium is provided;
In the said 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 sedimentary mixed solution of ammonium poly-vanadate with generation;
The said sedimentary mixed solution of ammonium poly-vanadate that contains is carried out filtration washing acquisition ammonium poly-vanadate deposition and deposition vanadium mother liquid;
Said ammonium poly-vanadate is deposited in thermal degradation generates Vanadium Pentoxide in FLAKES under 400-500 degree centigrade the temperature.
5. the purifying method of deposition vanadium mother liquid according to claim 4 is characterized in that, the said leach liquor that contains vanadic acid sodium obtains through the following step:
Meticulous vanadium slag is provided;
In said meticulous vanadium slag, add yellow soda ash and obtain the roasting mixture;
Said roasting mixture is carried out the roasting material that roasting obtains to contain vanadic acid sodium under the 700-850 degree celsius temperature;
Said roasting material is carried out below the shrend to 100 degree centigrade;
The roasting material that will pass through shrend carries out calcining matter pellet mill and obtains slurry;
Said slurry is carried out water logging obtain to leach slurry; And
The leaching slurry that is obtained is filtered the leach liquor that obtains filter residue and contain vanadic acid sodium.
6. the purifying method of deposition vanadium mother liquid according to claim 5 is characterized in that, said meticulous vanadium slag obtains through the following step:
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 said, once select powder to obtain meal then and as a fine powder of meticulous vanadium slag;
A said meal sieved obtain plus sieve and minus sieve;
Said 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.
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| CN106521154B (en) * | 2016-12-01 | 2018-08-21 | 中信锦州金属股份有限公司 | A kind of method of Upper-liquor of Precipitating Vanadate Process production low silicon-hydrogen chromium oxide |
| CN106978542A (en) * | 2017-03-31 | 2017-07-25 | 江苏省冶金设计院有限公司 | The system and method for handling converter vanadium chromium slag |
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| CN101538652B (en) * | 2009-04-14 | 2011-01-12 | 杨秋良 | Method for separating and recovering vanadium and chrome from vanadium and chrome-containing waste |
| CN101709376B (en) * | 2009-12-10 | 2011-01-26 | 攀钢集团攀枝花钢钒有限公司 | Method for purifying alkaline vanadium leachate |
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