CN107954474A - A kind of method that vanadium product and chromium sulfate basic are produced using vanadium chromium solution - Google Patents
A kind of method that vanadium product and chromium sulfate basic are produced using vanadium chromium solution Download PDFInfo
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- CN107954474A CN107954474A CN201810002197.0A CN201810002197A CN107954474A CN 107954474 A CN107954474 A CN 107954474A CN 201810002197 A CN201810002197 A CN 201810002197A CN 107954474 A CN107954474 A CN 107954474A
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- C—CHEMISTRY; METALLURGY
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
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- C22B34/32—Obtaining chromium
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Abstract
The present invention relates to a kind of method that vanadium product and chromium sulfate basic are produced using vanadium chromium solution, by hydrolyze precipitation, calcification reaction, the enrichment of chromium, prepare chromium sulfate basic and etc. obtain high purity vanadium product and chromium sulfate basic product, the purity of gained vanadium product is up to more than 99.5%, Cr in chromium sulfate basic2O3Content can reach 24 26%, and the content of impurity F e is less than 0.1%, and the rate of recovery of vanadium chromium can reach more than 99.5%, realizes high efficiency extraction and separates the purpose of vanadium chromium.Production process of the present invention cleans, and the brine and NaOH mother liquors produced in preparation process can return to system use, and whole technological process is produced without ammonia nitrogen waste water.The technology of the present invention is feasible, equipment is simple, and production cost is low and easy to automate, with good economic efficiency and application prospect.
Description
Technical field
The invention belongs to vanadium field of chemical metallurgical technology, and in particular to one kind using vanadium chromium solution clean manufacturing vanadium product and
The method of chromium sulfate basic.
Background technology
Vanadium and chromium are important strategic resources, and since property is similar, there are in vanadium ishkulite usually in a manner of symbiosis.
Vanadium ishkulite obtains slag containing chrome alum through processes such as blast furnace process, vanadium extraction by converter blowing.Vanadium slag sodium roasting vanadium-extracting is domestic and international vanadium life
Mainstream process for extracting vanadium used by production, vanadium slag by sodium roasting, leaching, solution purification and etc. obtain the different vanadium chromium of concentration
Solution system, since the properties of Aqueous Solution of vanadium chromium is similar, how high-efficiency cleaning therefrom extracts and separates vanadium chromium, while avoids vanadium extraction
Tailings forms danger wastes and major source of pollutant, is the important directions of vanadium enterprise development, and the emphasis of current research.
The containing vanadium and chromium solution obtained for containing vanadium and chromium mineral (such as vanadium slag) after chemical transformation (roasting, extraction),
Existing vanadium chromium separation method mainly has：Extraction, chemical precipitation method, ion-exchange, crystallisation and electrochemical process etc..
CN102531056A discloses a kind of method of vanadium slag pressure leaching clean manufacturing sodium vanadate sodium chromate, this method bag
Include following steps：(1) dispensing：Vanadium slag is mixed with NaOH solution, obtains reaction mass；(2) react：Vanadium slag is in NaOH solution
Oxidation reaction is carried out under high pressure with oxidizing gas, obtains containing NaOH, Na after reaction3VO4、Na2CrO4And water-solubility impurity group
The solution and the Solid-liquid mixture slurry of iron-rich tailings divided；(3) separation of solid and liquid；(4) desiliconization agent removal of impurities is added；(5) sodium vanadate crystallizes；
(6) sodium chromate crystallizes.This method is easily operated and security is good；Operation temperature is significantly less than traditional process for extracting vanadium temperature, energy consumption
It is small, and realize that vanadium chromium efficiently carries altogether, vanadium chromium recovery rate is above 95%.But there is also following problem：(1) due to the use of high pressure and
Highly basic, requires equipment material high；(2) circulating mother liquor impurity element is constantly enriched with, and influences product quality, and need to clean process.
CN104556522 discloses a kind of separation vanadium, the method for chromium from vanadium, chromium mixed liquor, comprises the following steps：A, adjust
The pH value of section mixed liquor is 3.0-4.0, and spent ion exchange resin absorption method adsorbs the vanadium and chromium in mixed liquor, obtains containing vanadium, chromium
Resin；B, resin containing vanadium and chromium-containing solution are obtained containing vanadium, chromium resin with 3%-4% sulfuric acid-ethanol solution elution；C, desorption contains
Vanadium resin obtains stripping liquid containing vanadium, and precipitation processing is carried out to stripping liquid containing vanadium to obtain vanadate；D, vanadate is calcined
Processing, obtains vanadic anhydride；E, chromium-containing solution adjusts pH and is neutralized, and chromium is with hydrate deposition Cr (OH)3·nH2The form of O
Separate out, chrome green is produced by calcination processing.The technological process is simple, easily operated, cost is low, is conducive to vanadium chromium resource
Separation and recovery, but used ion exchange resin, one-time investment is big, and operating condition is harsh, and resin is easily poisoned shadow
Exchange efficiency is rung, need to be replaced in time.
CN103966438A provide in a kind of electrolytic separation containing vanadium and chromium solution the method for vanadium and chromium the described method includes：Adjust
The pH value of containing vanadium and chromium solution is saved to 0-1.0；Containing vanadium and chromium solution is placed in electrolytic cell and is electrolysed, wherein, the electrolytic cell quilt
Amberplex is divided into cathode chamber and anode chamber；After the vanadium in the containing vanadium and chromium solution and chromium complete electrolytic migration, by institute
State the indoor anolyte of anode to remove out of anode chamber, the indoor catholyte of the cathode is moved out of cathode chamber
Go out, complete the separation of vanadium and chromium in containing vanadium and chromium solution.Although this method using electrochemical method in vanadium chromium solution by being realized
Vanadium chromium is directly separated, but electrolytic process energy consumption is excessive, and vanadium chromium separation rate is still too low, products obtained therefrom purity is not
Foot.
Although the above method can effectively extract vanadium chromium, in the prevalence of easily long-pending to equipment requirement height, impurity element
It is tired, the problems such as operating condition is harsh, and energy consumption is excessive and product purity is insufficient.Therefore, it is necessary to provide one by modified technique
Kind separates the new method of vanadium chromium using the extraction of vanadium chromium solution clean and effective.
The content of the invention
In view of problems of the prior art, the present invention provides one kind using vanadium chromium solution clean manufacturing vanadium product and
The method of chromium sulfate basic, by hydrolyze precipitation, calcification reaction, the enrichment of chromium, prepare chromium sulfate basic and etc. obtain it is high-purity
Two kinds of products of vanadium and chromium sulfate basic, the purity of vanadium product is up to more than 99.5%, Cr in chromium sulfate basic2O3Content is reachable
To 24-26%, Fe contents are less than 0.1%, and the rate of recovery of vanadium chromium reaches more than 99.5%；The brine that is produced in preparation process and
NaOH mother liquors can return to system reuse, and whole technological process is produced without ammonia nitrogen waste water, has achieveed the purpose that clean manufacturing, is had good
Good application prospect.
For this purpose, the present invention uses following technical scheme：
The present invention provides a kind of method that vanadium product and chromium sulfate basic are produced using vanadium chromium solution, the described method includes
Following steps：
(1) precipitation is hydrolyzed in the pH for adjusting vanadium chromium solution, then separation of solid and liquid, obtains the red cake of solid phase and containing vanadium, chromium
Liquid after precipitation；
(2) the red cake obtained step (1) and calcification agent mixing, which are added to the water, carries out calcification reaction, solid-liquid after the completion of reaction
Separation, obtains solid phase calcium vanadate；
(3) liquid carries out secondary precipitation and the heavy chromium of reduction after the precipitation obtained to step (1), obtains material containing chromium and sodium salt is molten
Liquid；
(4) material containing chromium that step (3) obtains is added in sulfuric acid and carries out the molten reaction of acid, oxidation is added after the completion of reaction
Agent, then adjusts pH, chromium sulfate solution is obtained after separation of solid and liquid, then adjusts basicity, then obtain alkali formula through evaporating, after drying
Chromium sulfate.
Step (1) the vanadium chromium solution of the present invention is the solution containing vanadium chromium, is preferably vanadium slag sodium roasting
The vanadium extraction scavenging solution that process for extracting vanadium obtains.
According to the present invention, it is 1.6-1.9 to adjust pH during step (1) the hydrolysis precipitation, such as can be 1.6,
1.7th, the specific point value between 1.8 or 1.9, and above-mentioned numerical value, it is as space is limited and no longer poor for concise consideration, the present invention
Enumerate to the greatest extent.
According to the present invention, salt acid for adjusting pH is utilized in step (1).
According to the present invention, step (2) the calcification agent is calcium oxide.
According to the present invention, it is (1-3) according to Ca/V in step (2):1 molar ratio addition calcification agent, such as can be 1:
1、3:2、2:1、5:2 or 3:Specific point value between 1, and above-mentioned numerical value, as space is limited and for concise consideration, the present invention
No longer exclusive list.
According to the present invention, the temperature of step (2) calcification reaction is 50-100 DEG C, for example, can be 50 DEG C, 60 DEG C, 70
DEG C, 80 DEG C, 90 DEG C or the specific point value between 100 DEG C, and above-mentioned numerical value, as space is limited and for concise consideration, this hair
Bright no longer exclusive list.
According to the present invention, the time of step (2) calcification reaction is 0.2-2h, for example, can be 0.2h, 0.4h,
Specific point value between 0.6h, 0.8h, 1h, 1.2h, 1.4h, 1.6h, 1.8h or 2h, and above-mentioned numerical value, as space is limited and goes out
In concise consideration, the present invention no longer exclusive list.
After obtaining calcium vanadate in step (2) of the present invention, the means of this area routine can be selected to prepare vanadium as raw material
Product, such as gained calcium vanadate can be prepared vanadic anhydride after ammoniumization turns molten, removal of impurities, crystallization, calcining, but non-only limit
In this.The above-mentioned operation that vanadic anhydride is prepared using calcium vanadate is the routine operation of this area, and the present invention is to its actual conditions
Do not do particular determination.
According to the present invention, precipitation agent used in step (3) the secondary precipitation is poly-ferric chloride, in order to avoid introducing newly
Impurity, without using bodied ferric sulfate.
Secondary precipitation described in step (3) of the present invention and the routine operation that the heavy chromium of reduction is this area, the present invention have it
Concrete conditions in the establishment of a specific crime does not do particular determination, exemplary, can be carried out according to following operation, but non-be only limitted to this.
Secondary precipitation and the operation of the heavy chromium of reduction can be：Precipitation agent tune is added after the precipitation obtained to step (1) in liquid
Save pH and carry out secondary precipitation reaction for 4.5-5.5, separation of solid and liquid after the completion of reaction, obtains liquid after secondary precipitation；It is secondary to gained
Reducing agent is added after precipitation in liquid and carries out chromium reduction reaction, it be 6.8-7.2 then to adjust pH, separation of solid and liquid obtain material containing chromium with
Sodium salt solution.
Above-mentioned reducing agent is reducing agent commonly used in the art, such as can be sulfur dioxide, sodium sulfite or thiosulfuric acid
Sodium etc., but it is non-be only limitted to this, as long as can realize to chromium reduction reducing agent be suitable for the present invention.
After the completion of above-mentioned chromium reduction reaction, Cr (OH) is generated by adjusting pH3Chromium is precipitated, trivalent chromium starts the pH value of precipitation
For 4.6, when pH is 6.8-7.2, it can be achieved that Cr (OH)3Precipitation completely.Contain high concentration in the liquid phase obtained after separation of solid and liquid
Sodium salt, gained brine can return to sodium roasting and leach process.
Chromium content is higher in the material containing chromium obtained in step (3) of the present invention, is chromium-rich material.
According to the present invention, the concentration of sulfuric acid used in step (4) is 10-98wt%, for example, can be 10wt%, 20wt%,
Tool between 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt%, 90wt% or 98wt%, and above-mentioned numerical value
Body point value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the liquid-solid ratio of step (4) sulfuric acid and the material containing chromium is (2-8):1, such as can be 2:1、
3:1、4:1、5:1、6:1、7:1 or 8:Specific point value between 1, and above-mentioned numerical value, as space is limited and for concise consideration,
The present invention no longer exclusive list.
The unit of liquid-solid ratio of the present invention is ml:g.
According to the present invention, the temperature of step (4) the molten reaction of acid is 30-90 DEG C, for example, can be 30 DEG C, 40 DEG C, 50
DEG C, 60 DEG C, 70 DEG C, 80 DEG C or the specific point value between 90 DEG C, and above-mentioned numerical value, as space is limited and for concise consideration,
The present invention no longer exclusive list.
According to the present invention, the time of step (4) the molten reaction of acid is 0.5-2h, for example, can be 0.5h, 0.8h,
Specific point value between 1.0h, 1.3h, 1.5h, 1.8h or 2h, and above-mentioned numerical value, as space is limited and for concise consideration,
The present invention no longer exclusive list.
According to the present invention, step (4) described oxidant is any one in air, ozone or hydrogen peroxide or at least two
Combination；Such as can be any one in air, ozone or hydrogen peroxide, typical but non-limiting is combined as：Air and
Ozone；Air and hydrogen peroxide；Ozone and hydrogen peroxide；Air, ozone and hydrogen peroxide.
, can be by the part ferric iron back in solution into ferrous iron due to introducing reducing agent in step (3), and divalence
Solubility is big in an acidic solution for iron, is not easy to remove, therefore present invention selection adds oxidant by solution in step (4)
It is ferrous oxidising into ferric iron.
According to the present invention, acid-base modifier is added in step (4) and adjusts pH, the acid-base modifier is sulfuric acid, NaOH or
Na2CO3In any one.
According to the present invention, step (4) is described adds after oxidant that to adjust pH be 2-4.6, for example, can be 2,2.3,2.5,
2.8th, the specific point value between 3,3.3,3.5,3.8,4,4.3 or 4.6, and above-mentioned numerical value, as space is limited and for simplicity
Consider, the present invention no longer exclusive list.
The present invention is after the completion of step (4) the molten reaction of acid, by adding oxidant oxidation of ferrous iron to ferric iron
After add acid-base modifier adjust pH carry out iron removaling.PH value when ferric iron starts precipitation is 2, and trivalent chromium starts the pH of precipitation
It is worth for 4.6, therefore, control ph between 2-4.6, chromium while iron precipitates in solution is not precipitated, and then realize to sulphur
The removal of iron in sour chromium solution.
Added in step (4) of the present invention after acid-base modifier iron removaling and obtain iron oxide red (main component three by separation of solid and liquid
Aoxidize two iron), gained iron oxide red can return in step (3) after acid is molten makees precipitation agent use.It is a small amount of due to that can be mingled with the iron oxide red
Chromium, therefore iron oxide red pigment use can not be done；But after dissolving with hydrochloric acid ferric sulfate can be prepared, and then return in it
Make precipitation agent use in step (3), while the chromium in iron oxide red also returns to preparation system.
According to the present invention, NaOH adjustment basicities are added in step (4).
According to the present invention, adjustment basicity be 32-36% in step (4), preferably 33%, such as can be 32%,
33%th, the specific point value between 34%, 35% or 36%, and above-mentioned numerical value, as space is limited and for concise consideration, this hair
Bright no longer exclusive list.
The present invention selects the routine operation of this area to carry out separation of solid and liquid, such as can be filtering, suction filtration, centrifugation etc., but
It is non-to be only limitted to this, it should be adjusted with actual conditions.For the present invention, the mode preferably using filtering carries out solid-liquid point
From.
As preferable technical solution, the method for the invention comprises the following steps：
(1) precipitation is hydrolyzed for 1.6-1.9 in the pH that vanadium chromium solution is adjusted using hydrochloric acid, then separation of solid and liquid, consolidate
Mutually red cake and containing vanadium, chromium precipitation after liquid；
(2) it is (1-3) according to Ca/V:1 molar ratio, red cake and calcium oxide that step (1) obtains are mixed and are added to the water,
Controlled at 50-100 DEG C of progress calcification reaction, reaction carries out separation of solid and liquid after 0.2-2h, obtains solid phase calcium vanadate；Gained vanadium
Sour calcium through ammoniumization turn it is molten, removal of impurities, crystallization, calcining after obtain vanadic anhydride；
(3) poly-ferric chloride is added after the precipitation obtained to step (1) in liquid and carries out secondary precipitation, it is heavy then to carry out reduction
Chromium, separation of solid and liquid obtains material containing chromium and brine after the completion of reaction；Gained brine may return to sodium roasting and leach process；
(4) material containing chromium for obtaining step (3) is according to (2-8):It is 10-98wt% sulphur that 1 liquid-solid ratio, which is added to concentration,
In acid, the molten reaction 0.5-2h of acid is carried out controlled at 30-90 DEG C, oxidant is added after the completion of reaction, then adds soda acid tune
It is 2-4.6 to save agent and adjust pH, and chromium sulfate solution is obtained after separation of solid and liquid, and it is 32-36% then to add NaOH adjustment basicities, then
Chromium sulfate basic is obtained through evaporating, after drying；Any one in the oxidant air, ozone or hydrogen peroxide or at least two
Combination, the acid-base modifier is sulfuric acid, NaOH or Na2CO3In any one.
Compared with prior art, the present invention at least has the advantages that：
(1) two kinds of products of high purity vanadium and chromium sulfate basic, vanadium product has been prepared using vanadium chromium solution in the present invention at the same time
Purity up to more than 99.5%, Cr in chromium sulfate basic2O3Content can reach 24-26%, Fe contents in chromium sulfate basic product
Less than 0.1%.
(2) valuable element that method provided by the invention can be in high efficiente callback vanadium chromium solution, the rate of recovery of vanadium chromium reach
More than 99.5%；And the brine and NaOH mother liquors produced in preparation process can return to system use, whole flow process is without ammonia nitrogen waste water
Produce, achieveed the purpose that clean manufacturing.
(3) the technology of the present invention is feasible, equipment is simple, and production cost is low and easy to automate, has good application
Prospect.
Brief description of the drawings
Fig. 1 is the process flow chart that a kind of embodiment of the present invention provides.
The present invention is described in more detail below.But following examples is only the simple example of the present invention, not generation
Table or limitation the scope of the present invention, protection scope of the present invention are subject to claims.
Embodiment
Further illustrate technical scheme below with reference to the accompanying drawings and specific embodiments.
As shown in Figure 1, a kind of embodiment offer of the present invention utilizes vanadium chromium solution production vanadium product and alkali formula sulphur
The technological process of sour chromium can be：It is normal by sodium roasting, clinker leaching, filtration washing and removal of impurities etc. using vanadium slag and sodium salt
The vanadium chromium solution that rule step obtains is raw material, and precipitation is hydrolyzed by adjusting pH, the red cake of solid phase is then obtained after separation of solid and liquid
With containing vanadium, chromium precipitation after liquid；It is added to the water after the red cake of gained and calcium oxide are mixed and carries out calcification reaction, it is solid after the completion of reaction
Liquid separates, and gained liquid phase is NaOH solution, available for the Leach reaction to roasting clinker；Gained solid phase calcium vanadate turns through ammoniumization
High purity vanadic anhydride (purity ＞ 99.5%) is obtained after the routine operations such as molten, removal of impurities, crystallization, calcining；Liquid after to gained precipitation
Middle addition precipitation agent, adjusts pH using NaOH and carries out secondary precipitation reaction, and solid phase vanadic acid iron cement and secondary is obtained after separation of solid and liquid
Liquid after precipitation；Gained vanadic acid iron cement can be back to sodium roasting step vanadium extraction as vanadium source；Add after to the secondary precipitation of gained in liquid
Enter reducing agent and carry out chromium reduction reaction to sink chromium, separation of solid and liquid obtains material containing chromium (chromium-rich material) and sodium salt solution after the completion of reaction；
Gained sodium salt solution can be back to sodium roasting as sodium source and leaching step carries out vanadium extraction；To material containing chromium add sulfuric acid in into
The molten reaction of row acid, adds oxidant and acid-base modifier after the completion of reaction, adjust pH and carry out iron removaling, sulfuric acid is obtained after separation of solid and liquid
Chromium solution and iron oxide red slag, gained iron oxide red slag can be used as precipitation agent to carry out secondary vanadium extraction after peracid is molten；Add NaOH adjustment sulfuric acid
The basicity of chromium solution, then chromium sulfate basic product is obtained after being dried by evaporation.
For the present invention is better described, technical scheme is readily appreciated, of the invention is typical but non-limiting
Embodiment is as follows：
Embodiment 1
(1) precipitation is hydrolyzed：To 24.5g/L containing vanadium, in the vanadium chromium solution of chromium 568.2mg/L plus hydrochloric acid tune pH is 1.8, hydrolysis
Filtered after precipitation, obtain the red cake of solid phase and containing vanadium, chromium precipitation after liquid；
(2) calcification is reacted：According to the molar ratio that Ca/V is 1.5, the red cake that step (1) obtains is mixed into addition with calcium oxide
Calcification reaction is carried out into water, controlling reaction temperature is 95 DEG C, and reaction time 1h, obtains solid phase calcium vanadate, gained after filtering
Calcium vanadate turns molten through ammoniumization, cleans, crystallizing, calcining obtains vanadic anhydride；
(3) enrichment of chromium：Poly-ferric chloride is added after the precipitation obtained to step (1) in liquid, it is secondary for 5 progress to adjust pH
Precipitation is reacted, and is filtered after the completion of reaction, and sulfur dioxide is passed through into gained filtrate and carries out chromium reduction reaction, it is 7 to adjust pH, is filtered
To material containing chromium and sodium salt solution；
(4) chromium sulfate basic is prepared：According to 3:Material containing chromium obtained by step (3) is added to concentration by 1 liquid-solid ratio
Progress acid is molten in the sulfuric acid solution of 98wt%, and controlling reaction temperature is 90 DEG C, and hydrogen peroxide is added after the completion of reaction and is aoxidized, so
It is 4 iron removalings to adjust pH afterwards, and chromium sulfate solution is obtained after filtering, and it is 33% that NaOH adjustment basicities are added into solution, then through steaming
Send out, be dried to obtain chromium sulfate basic product.
By detection, it is 95.9% that precipitation rate is hydrolyzed in the present embodiment, and the purity of gained vanadic anhydride is 99.52%,
Cr in gained chromium sulfate basic2O3Content is that 24.6%, Fe contents are 0.05%.
Embodiment 2
(1) precipitation is hydrolyzed：To 24.5g/L containing vanadium, in the vanadium chromium solution of chromium 568.2mg/L plus hydrochloric acid tune pH is 1.9, hydrolysis
Filtered after precipitation, obtain the red cake of solid phase and containing vanadium, chromium precipitation after liquid；
(2) calcification is reacted：According to the molar ratio that Ca/V is 1.9, the red cake that step (1) obtains is mixed into addition with calcium oxide
Calcification reaction is carried out into water, controlling reaction temperature is 85 DEG C, reaction time 1.5h, and solid phase calcium vanadate, institute are obtained after filtering
Calcium vanadate through ammoniumization turn it is molten, removal of impurities, crystallization, calcining obtain vanadic anhydride；
(3) enrichment of chromium：Poly-ferric chloride is added after the precipitation obtained to step (1) in liquid, pH is adjusted and carries out two for 4.5
Secondary precipitation reaction, is filtered after the completion of reaction, and sodium thiosulfate is added into gained filtrate and carries out chromium reduction reaction, and it is 7.1 to adjust pH,
Material containing chromium and sodium salt solution is obtained by filtration；
(4) chromium sulfate basic is prepared：According to 6:Material containing chromium obtained by step (3) is added to concentration by 1 liquid-solid ratio
Progress acid is molten in the sulfuric acid solution of 50wt%, and controlling reaction temperature is 80 DEG C, and hydrogen peroxide is added after the completion of reaction and is aoxidized, so
It is 3.5 iron removalings to adjust pH afterwards, and chromium sulfate solution is obtained after filtering, and it is 33% that NaOH adjustment basicities are added into solution, then is passed through
Evaporate, be dried to obtain chromium sulfate basic product.
By detection, it is 96.3% that precipitation rate is hydrolyzed in the present embodiment, and the purity of gained vanadic anhydride is 99.51%,
Cr in gained chromium sulfate basic2O3Content is that 24.3%, Fe contents are 0.08%.
Embodiment 3
(1) precipitation is hydrolyzed：To 24.5g/L containing vanadium, in the vanadium chromium solution of chromium 568.2mg/L plus hydrochloric acid tune pH is 1.6, hydrolysis
Filtered after precipitation, obtain the red cake of solid phase and containing vanadium, chromium precipitation after liquid；
(2) calcification is reacted：According to the molar ratio that Ca/V is 1.3, the red cake that step (1) obtains is mixed into addition with calcium oxide
Calcification reaction is carried out into water, controlling reaction temperature is 75 DEG C, and reaction time 2h, obtains solid phase calcium vanadate, gained after filtering
Calcium vanadate turns molten through ammoniumization, cleans, crystallizing, calcining obtains vanadic anhydride；
(3) enrichment of chromium：Poly-ferric chloride is added after the precipitation obtained to step (1) in liquid, pH is adjusted and carries out two for 5.2
Secondary precipitation reaction, is filtered after the completion of reaction, and sodium sulfite is added into gained filtrate and carries out chromium reduction reaction, and it is 7 to adjust pH, filtering
Obtain material containing chromium and sodium salt solution；
(4) chromium sulfate basic is prepared：According to 8:Material containing chromium obtained by step (3) is added to concentration by 1 liquid-solid ratio
Progress acid is molten in the sulfuric acid solution of 30wt%, and controlling reaction temperature is 60 DEG C, and hydrogen peroxide is added after the completion of reaction and is aoxidized, so
It is 4.5 iron removalings to adjust pH afterwards, and chromium sulfate solution is obtained after filtering, and it is 34% that NaOH adjustment basicities are added into solution, then is passed through
Evaporate, be dried to obtain chromium sulfate basic product.
By detection, it is 96.1% that precipitation rate is hydrolyzed in the present embodiment, and the purity of gained vanadic anhydride is 99.56%,
Cr in gained chromium sulfate basic2O3Content is that 24.9%, Fe contents are 0.04%.
Embodiment 4
(1) precipitation is hydrolyzed：To 24.5g/L containing vanadium, in the vanadium chromium solution of chromium 568.2mg/L plus hydrochloric acid tune pH is 1.7, hydrolysis
Filtered after precipitation, obtain the red cake of solid phase and containing vanadium, chromium precipitation after liquid；
(2) calcification is reacted：According to the molar ratio that Ca/V is 2.2, the red cake that step (1) obtains is mixed into addition with calcium oxide
Calcification reaction is carried out into water, controlling reaction temperature is 60 DEG C, reaction time 1.5h, and solid phase calcium vanadate, institute are obtained after filtering
Calcium vanadate through ammoniumization turn it is molten, removal of impurities, crystallization, calcining obtain vanadic anhydride；
(3) enrichment of chromium：Poly-ferric chloride is added after the precipitation obtained to step (1) in liquid, pH is adjusted and carries out two for 4.8
Secondary precipitation reaction, is filtered after the completion of reaction, and sulfur dioxide is passed through into gained filtrate and carries out chromium reduction reaction, and it is 7 to adjust pH, filtering
Obtain material containing chromium and sodium salt solution；
(4) chromium sulfate basic is prepared：According to 7:Material containing chromium obtained by step (3) is added to concentration by 1 liquid-solid ratio
Progress acid is molten in the sulfuric acid solution of 40wt%, and controlling reaction temperature is 70 DEG C, and ozone is passed through after the completion of reaction and is aoxidized, then
Adjusting pH is 4 iron removalings, and chromium sulfate solution is obtained after filtering, and it is 33% that NaOH adjustment basicities are added into solution, then through evaporating,
It is dried to obtain chromium sulfate basic product.
By detection, it is 96.5% that precipitation rate is hydrolyzed in the present embodiment, and the purity of gained vanadic anhydride is 99.52%,
Cr in gained chromium sulfate basic2O3Content is that 24.5%, Fe contents are 0.06%.
Embodiment 5
(1) precipitation is hydrolyzed：To 24.5g/L containing vanadium, in the vanadium chromium solution of chromium 568.2mg/L plus hydrochloric acid tune pH is 1.7, hydrolysis
Filtered after precipitation, obtain the red cake of solid phase and containing vanadium, chromium precipitation after liquid；
(2) calcification is reacted：According to the molar ratio that Ca/V is 3, the red cake that step (1) obtains is mixed to join with calcium oxide
Calcification reaction is carried out in water, controlling reaction temperature is 50 DEG C, reaction time 1h, and solid phase calcium vanadate, gained vanadium are obtained after filtering
Sour calcium turns molten through ammoniumization, cleans, crystallizing, calcining obtains vanadic anhydride；
(3) enrichment of chromium：Poly-ferric chloride is added after the precipitation obtained to step (1) in liquid, it is secondary for 5 progress to adjust pH
Precipitation is reacted, and is filtered after the completion of reaction, and sulfur dioxide is passed through into gained filtrate and carries out chromium reduction reaction, and it is 6.9 to adjust pH, filtering
Obtain material containing chromium and sodium salt solution；
(4) chromium sulfate basic is prepared：According to 4:Material containing chromium obtained by step (3) is added to concentration by 1 liquid-solid ratio
Progress acid is molten in the sulfuric acid solution of 60wt%, and controlling reaction temperature is 50 DEG C, and air is passed through after the completion of reaction and is aoxidized, then
Adjusting pH is 3 iron removalings, and chromium sulfate solution is obtained after filtering, and it is 33% that NaOH adjustment basicities are added into solution, then through evaporating,
It is dried to obtain chromium sulfate basic product.
By detection, it is 95.5% that precipitation rate is hydrolyzed in the present embodiment, and the purity of gained vanadic anhydride is 99.58%,
Cr in gained chromium sulfate basic2O3Content is that 24.8%, Fe contents are 0.09%.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
- A kind of 1. method that vanadium product and chromium sulfate basic are produced using vanadium chromium solution, it is characterised in that the described method includes with Lower step：(1) precipitation is hydrolyzed in the pH for adjusting vanadium chromium solution, and then separation of solid and liquid, obtains the red cake of solid phase and the precipitation containing vanadium, chromium Liquid afterwards；(2) the red cake obtained step (1) and calcification agent mixing, which are added to the water, carries out calcification reaction, solid-liquid point after the completion of reaction From obtaining solid phase calcium vanadate；(3) liquid carries out secondary precipitation and the heavy chromium of reduction after the precipitation obtained to step (1), obtains material containing chromium and sodium salt solution；(4) material containing chromium that step (3) obtains is added in sulfuric acid and carries out the molten reaction of acid, oxidant is added after the completion of reaction, Then pH is adjusted, chromium sulfate solution is obtained after separation of solid and liquid, then adjusts basicity, then alkali formula sulphur is obtained through evaporating, after drying Sour chromium.
- 2. the method as described in claim 1, it is characterised in that it is 1.6- to adjust pH during step (1) the hydrolysis precipitation 1.9。
- 3. method as claimed in claim 1 or 2, it is characterised in that salt acid for adjusting pH is utilized in step (1).
- 4. such as claim 1-3 any one of them methods, it is characterised in that step (2) the calcification agent is calcium oxide；Preferably, it is (1-3) according to Ca/V in step (2):1 molar ratio addition calcification agent.
- 5. such as claim 1-4 any one of them methods, it is characterised in that the temperature of step (2) the calcification reaction is 50- 100℃；Preferably, the time of step (2) the calcification reaction is 0.2-2h；Preferably, calcium vanadate obtained by step (2) obtains vanadic anhydride after ammoniumization turns molten, removal of impurities, crystallization, calcining.
- 6. such as claim 1-5 any one of them methods, it is characterised in that the precipitation agent of step (3) the secondary precipitation is Poly-ferric chloride；Preferably, the sodium salt solution that step (3) separation of solid and liquid obtains may return to sodium roasting and leach process.
- 7. such as claim 1-6 any one of them methods, it is characterised in that the concentration of sulfuric acid used in step (4) is 10- 98wt%；Preferably, the liquid-solid ratio of step (4) sulfuric acid and the material containing chromium is (2-8):1.
- 8. such as claim 1-7 any one of them methods, it is characterised in that the temperature of step (4) the molten reaction of acid is 30- 90 DEG C, reaction time 0.5-2h.
- 9. such as claim 1-8 any one of them methods, it is characterised in that step (4) described oxidant is air, ozone or In hydrogen peroxide any one or at least two combination；Preferably, acid-base modifier is added in step (4) and adjusts pH, the acid-base modifier is sulfuric acid, NaOH or Na2CO3In Any one；Preferably, it is 2-4.6 to adjust pH after step (4) the addition oxidant；Preferably, after step (4) the adjusting pH, solid phase iron oxide red is obtained by separation of solid and liquid, gained iron oxide red can after peracid is molten Make precipitation agent use in return to step (3)；Preferably, NaOH adjustment basicities are added in step (4)；Preferably, adjustment basicity is 32-36% in step (4), is preferably 33%.
- 10. such as claim 1-9 any one of them methods, it is characterised in that the described method comprises the following steps：(1) precipitation is hydrolyzed for 1.6-1.9 in the pH that vanadium chromium solution is adjusted using hydrochloric acid, and then separation of solid and liquid, it is red to obtain solid phase Cake and containing vanadium, chromium precipitation after liquid；(2) it is (1-3) according to Ca/V:1 molar ratio, red cake and calcium oxide that step (1) obtains are mixed and are added to the water, is controlled Temperature is 50-100 DEG C of progress calcification reaction, and reaction carries out separation of solid and liquid after 0.2-2h, obtains solid phase calcium vanadate；Gained calcium vanadate Through ammoniumization turn it is molten, removal of impurities, crystallization, calcining after obtain vanadic anhydride；(3) poly-ferric chloride is added after the precipitation obtained to step (1) in liquid and carries out secondary precipitation, then carry out reducing heavy chromium, Separation of solid and liquid after the completion of reaction, obtains material containing chromium and sodium salt solution；Gained sodium salt solution may return to sodium roasting process；(4) material containing chromium for obtaining step (3) is according to (2-8):1 liquid-solid ratio is added to concentration as in 10-98wt% sulfuric acid, The molten reaction 0.5-2h of acid is carried out controlled at 30-90 DEG C, oxidant is added after the completion of reaction, then adds acid-base modifier tune Section pH is 2-4.6, and chromium sulfate solution is obtained after separation of solid and liquid, and it is 32-36% then to add NaOH adjustment basicities, then through steaming Chromium sulfate basic is obtained after hair, drying；In the oxidant air, ozone or hydrogen peroxide any one or at least two group Close, the acid-base modifier is sulfuric acid, NaOH or Na2CO3In any one.
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| CN110343866A (en) * | 2019-08-15 | 2019-10-18 | 攀钢集团钒钛资源股份有限公司 | The method of vanadium chromium is separated from vanadium chromium reducing slag |
| CN111041205A (en) * | 2019-12-18 | 2020-04-21 | 昆明理工大学 | Method for separating vanadium and chromium from vanadium and chromium solution |
| CN113816847A (en) * | 2021-10-08 | 2021-12-21 | 上海良仁化工有限公司 | Method for preparing basic chromium acetate from chromium-containing sludge |
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| CN113957262A (en) * | 2021-10-29 | 2022-01-21 | 东北大学 | Method for precipitating vanadium from vanadium-chromium leaching solution without ammonium |
| CN113957262B (en) * | 2021-10-29 | 2022-09-23 | 东北大学 | Method for precipitating vanadium from vanadium-chromium leaching solution without ammonium |
| CN114058846A (en) * | 2021-11-12 | 2022-02-18 | 四川省绵阳市华意达化工有限公司 | Method for circularly separating vanadium and chromium in vanadium-chromium solution by calcium salt |
| CN114703363A (en) * | 2022-03-17 | 2022-07-05 | 四川省银河化学股份有限公司 | Method for separating vanadium and chromium in high-chromium system |
| CN114703363B (en) * | 2022-03-17 | 2023-10-20 | 四川省银河化学股份有限公司 | Method for separating vanadium from chromium in high-chromium system |
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