CN107055612A - A kind of method that utilization vanadium chromium reducing slag prepares vanadium trioxide and chrome green - Google Patents
A kind of method that utilization vanadium chromium reducing slag prepares vanadium trioxide and chrome green Download PDFInfo
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- CN107055612A CN107055612A CN201710306634.3A CN201710306634A CN107055612A CN 107055612 A CN107055612 A CN 107055612A CN 201710306634 A CN201710306634 A CN 201710306634A CN 107055612 A CN107055612 A CN 107055612A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
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Abstract
The invention discloses a kind of method that utilization vanadium chromium reducing slag prepares vanadium trioxide and chrome green, vanadium chromium reducing slag after water slurry with adding reducing agent, the oxidation-reduction potential of adjustment system, V (III) is reduced into by the V (IV) in system；Alkali is added into reduction reaction system, alkali leaching process is carried out, the Cr (III) in system is changed into Cr (OH)4 ‑, separation of solid and liquid is then carried out, leachate containing chromium and vanadium trioxide filter cake is obtained；Vanadium trioxide filtration cakes torrefaction obtains vanadium trioxide product；The acid adding Precipitation hydrated chromium oxide into leachate containing chromium；Hydrated chromium oxide must calcine material through calcining；Chrome green product is obtained after the pickling of calcining material, drying.The inventive method reducing agent consumption is few, and production process will not produce the content for containing V in hexavalent chromium wastewater and waste residue, obtained vanadium trioxide of severe toxicity more than 65.8%；The purity of chrome green is more than 98.2%；Vanadium chromium recovery ratio is high, and the rate of recovery of vanadium is more than 99.1%, and the rate of recovery of chromium is more than 96.1%.
Description
Technical field
The present invention relates to comprehensive utilization of resources and technical field of material, and in particular to one kind utilizes vanadium chromium reducing slag system
The method of standby vanadium trioxide and chrome green.
Background technology
Vanadium trioxide is the important source material for producing high vanadium ferroalloy and VN alloy.Vanadic anhydride is substituted with vanadium trioxide
High vanadium ferroalloy is produced, the rate of recovery of vanadium can be both improved or the consumption of reducing agent can be saved；And during vanadium nitride is prepared, with three
V 2 O replaces vanadic anhydride, and not only greatling save cost can also avoid what is be also easy to produce from being adhered problem.In addition, three oxidations two
Vanadium can also be directly used in the electronic products such as production thermal element.The raw material for preparing vanadium trioxide at present is mainly five oxidations two
Vanadium, ammonium metavanadate and poly ammonium vanadate, at certain temperature and reducing atmosphere obtained by reaction, reaction temperature is generally higher than 500
DEG C, energy consumption is big, and production cost is high.Chrome green is also important industrial chemicals, is widely used in national defence, electrical alloy, face
In terms of material, hard alloy；Current chrome green is generally thermally decomposed using sodium dichromate with ammonium sulfate or chromic anhybride is thermally decomposed
Prepared by method, production process is both needed to use the hexavalent chromium compound of severe toxicity for raw material.
Vanadium chromium reducing slag is Leaching of Vanadium from Vanadium slag deposition vanadium mother liquid through reducing a kind of solid waste that neutralisation treatment is obtained, except containing
Have outside vanadium and chromium also containing materials such as sodium, silicon, ammonium salts.Vanadium more than 85% in vanadium chromium reducing slag exists in V (IV) form, remaining
With V (III) form exist；Chromium is all with Cr (OH)3Form exist.The research on utilization of current vanadium chromium reducing slag mainly has two
Class：(1) selective oxidation extracts vanadium.Hydrogen peroxide is that oxidant is selected vanadium chromium reducing slag middle or low price vanadium using sodium hydroxide solution
Property is oxidized to pentavalent vanadium and realizes the leaching of vanadium, but part Cr (III) can also be oxidized leaching, vanadium chromium inferior separating effect；Vanadium chromium
Alkaline-leaching and vanadium extraction after reducing slag oxidizing roasting, this method needs are baked above at 850 DEG C, and equipment is complicated, and obtained after vanadium extraction
Phase structure containing chromium is complicated in containing chromium slag, and chromium is difficult again extraction and application；Under stress can be by vanadium by adding high price vanadic salts
V (III) selective oxidation in chromium reducing slag is V (IV), then utilizes V (IV) and Cr (OH)3With pH needed for alkali reaction not
With the leaching V (IV) of selectivity, but due to Cr (OH)3It can also be reacted with alkali and V (IV) reacts the HV generated with alkali2O5 -Advantage
Interval is narrow so needs strictly control leaching condition and leaching process needs operation with high pressure, and cost is high.(2) at the same extract vanadium and
Chromium.Patent CN104357671A is disclosed first using acid Leaching Vanadium and chromium, then oxidizing lower vanadium and chromium in the basic conditions simultaneously,
Then melamine precipitation, evaporative crystallization extracts the technology of sodium chromate, but because the presence of silicon in vanadium chromium reducing slag causes acidleach
Filtering exudate is difficult, and can also be produced largely containing V (V) and Cr (VI) waste water after separation and recovery vanadium chromium from Oxidation Leaching liquid.Specially
Sharp CN106048240A discloses a kind of method of vanadium chromium reducing slag separation and Extraction vanadium chromium, and this method is also first to be leached simultaneously with acid
The vanadium and chromium of vanadium chromium reducing slag, then again by being selectively oxidized leachate middle or low price vanadium come separation and Extraction vanadium, the party
Method there is also acid leaching liquor separation of solid and liquid it is difficult the problem of, and flow growth process is complicated.In summary as can be seen that vanadium chromium is also at present
The separation and Extraction of vanadium chromium is all that make use of V (IV) and V (III) to be easier oxidized characteristic than Cr (III) in former slag, either
Selective oxidation Low Valent Vanadium is V (V) to leaching process selective oxidation Low Valent Vanadium either in leachate, so as to expand vanadium chromium
The difference of matter reaches the purpose of vanadium chromium separation and Extraction, and final products are all the low vanadic anhydride of added value, whole process flow
Complicated, cost is high.
The content of the invention
Prepared for above-mentioned existing various treatment technologies and vanadium trioxide and chrome green to vanadium chromium reducing slag
The defect that technology is present, vanadium trioxide and three oxidations two are prepared it is an object of the invention to provide one kind using vanadium chromium reducing slag
A kind of method of chromium, it is intended to utilize the vanadium trioxide and chrome green product of solid slag coproduction high added value.
A kind of method that utilization vanadium chromium reducing slag prepares vanadium trioxide and chrome green, comprises the following steps：
Step (1)：Selective reduction V (IV)：
Vanadium chromium reducing slag is with adding reducing agent after water slurry, the oxidation-reduction potential of adjustment system is 0.2V~-0.8V, will
V (IV) in system is reduced into V (III)；
Step (2)：Alkali leaches Cr (III)：
Alkali is added into the reduction reaction system of step (1), alkali leaching process is carried out, the Cr (III) in system is converted
Into Cr (OH)4 -, separation of solid and liquid is then carried out, leachate containing chromium and vanadium trioxide filter cake is obtained；
Step (3)：It is prepared by vanadium trioxide：
Vanadium trioxide filtration cakes torrefaction obtains vanadium trioxide product；
Step (4)：It is prepared by chrome green：
Into leachate containing chromium, the pH of acid adding regulation and control leachate containing chromium is 9.0~12.0；Precipitation hydrated chromium oxide；Water
Material must be calcined through calcining by closing chromium oxide；Chrome green product is obtained after the pickling of calcining material, drying.
The inventive method, innovatively leaches Cr (III) collaboration technique, with vanadium chromium using selective reduction V (IV) and alkali
Reducing slag is raw material coproduction vanadium trioxide and chrome green.Using the inventive method, realize first with solid slag system
For the vanadium trioxide and chrome green product for going out high added value and high-quality；Aoxidized compared to existing vanadium trioxide and three
The preparation technology of two chromium and the utilization technique of vanadium chromium reducing slag, the present invention have technique is simple, cost is low, good product quality,
And vanadium and chromium in vanadium chromium reducing slag can be comprehensively utilized, vanadium chromium recovery ratio is high, and will not produce severe toxicity contains hexavalent chromium wastewater and waste residue,
The characteristics of disclosure satisfy that industrialization production requirements.
Preferably, in step (1), in slurrying process, the solid-to-liquid ratio of vanadium chromium reducing slag and water is 1: 1.5~10g/mL；
More preferably 1: 3~4g/mL.
Preferably, in step (1), the reducing agent is selected from Na252O5、Na252O3、Na252O4、Na2SO3In one kind or
It is several.
Preferably, in step (1), reduction reaction temperature is 20-110 DEG C, the time is 1~8 hour.
The inventors discovered that, under described reducing agent, regulation and control pulp after system oxidation-reduction potential 0.2V~-
In 0.8V, and stirring reaction 1~8 hour at 20-110 DEG C；V (IV) in alternative reduction system is V (III)；Have
Good synergy, for example, can cooperate with the yield of lifting vanadium trioxide.
Further preferably, the oxidation-reduction potential for adding reducing agent adjustment and control system is 0.1V~-0.7V.Research discovery,
Under the preferred parameter, the recovering effect of separating effect and vanadium chromium is more excellent.
Further preferably, in step (1), reduction reaction temperature is 60-100 DEG C, and the time is 4~6 hours.
In the present invention, the alkali that alkali leaching process is used is alkali metal hydroxide.
Preferably, the alkali is NaOH and/or KOH.
Preferably, in step (2), the dosage of alkali is that Cr (III) is changed into Cr (OH)4 -The 1~6.0 of theoretical amount
Times.
In reaction temperature it is stirring reaction 0.5~6 hour at 20-110 DEG C under described alkali in the present invention；Selectivity
Leach Cr (III).
Further preferably, in step (2), the dosage of alkali is that Cr (III) is changed into Cr (OH)4 -The 3~4.5 of theoretical amount
Times；Alkali extraction temperature is 70-100 DEG C；Stirring reaction 3~5 hours.Research finds that the treatment effect under the preferred scope is more
It is excellent.
The vanadium in vanadium chromium reducing slag is originally set preferentially to be separated out with vanadium trioxide precipitation form by the present invention program；
The rate of recovery of vanadium can be so ensure that, is reclaimed while additionally aiding the high selectivity of chromium, high-purity.
Preferably, in step (3), vanadium trioxide filter cake prepares vanadium trioxide production using vacuum drying mode
Product.
Preferably, in step (4), during sour Precipitation, the pH of acid adding regulation and control leachate containing chromium for 9.0~
12.0.The temperature of sour Precipitation process is preferably 25-100 DEG C, the preferred pH and at a temperature of, mixing time preferably
For 0.5~10 hour.
Further preferably, in step (4), acid out goes out in precipitation process, the pH of acid adding regulation and control leachate containing chromium for 10.0~
11.0.Adjust and stirred 1.5~2.5 hours at 25-70 DEG C again after pH.Research discovery, the treatment effect under the preferred scope
It is more excellent.
Preferably, the acid is sulfuric acid, hydrochloric acid, the one or more of phosphoric acid.
Preferably, in step (4), calcining heat is 800-1300 DEG C, calcination time is 0.5-6 hours.
Further preferably, in step (4), calcining heat is 900-1300 DEG C, and calcination time is 3-6 hours.Research discovery,
Treatment effect under the preferred scope is more excellent；For example, helping further to avoid Cr in roasting material (VI) washing losses, cause
Handle water pollution.
Most preferably, in step (4), calcining heat is 1100-1300 DEG C.At the preferred temperature, during preferred calcining
Between be 3-4 hours.
Preferably, in step (4), in acid cleaning process, calcining material is placed in acid solution, the stirring to pulp at 20-100 DEG C
Separation of solid and liquid after 0.5~4h；Described acid solution is H+Concentration is 0.01~2mol/L sulfuric acid or/and hydrochloric acid solution；Calcining material
Solid-to-liquid ratio with acid solution is 1: 1.5~4g/mL.Under the preferred pickling parameter, treatment effect is more excellent.
The solid that separation of solid and liquid after pickling is obtained is dried, that is, obtains high-quality chrome green product.
The method that a kind of preferred utilization vanadium chromium reducing slag of the present invention prepares vanadium trioxide and chrome green, including
Following steps：
Step (a)：By solid-to-liquid ratio it is that 1: 1.5~10g/mL adds water after pulp by vanadium chromium reducing slag, adds reducing agent adjustment
V (IV) in the oxidation-reduction potential selective reduction vanadium chromium reducing slag of solution is V (III)；Then according in vanadium chromium reducing slag
Chromium by Cr (III) generate Cr (OH)4 -1~6.0 times of addition alkali of theoretical amount, Selectively leaching chromium therein, subsequent solid-liquid point
From obtaining leachate containing chromium and vanadium trioxide filter cake；Vanadium trioxide filter cake is vacuum dried, obtains vanadium trioxide product；
V (IV) in the selective reduction vanadium chromium reducing slag is that V (III) refers to that the oxidation-reduction potential of adjustment system is 0.2V
~-0.8V, and stirring reaction 1~8 hour at 20-110 DEG C；
Step (b)：The acid adding Precipitation hydrated chromium oxide into leachate containing chromium；The Precipitation hydrated chromium oxide refers to
Be control pH of leaching solution containing chromium for 9.0~12.0 at 25-100 DEG C stirring reaction 0.5~10 hour；
Step (c)：800-1300 DEG C of calcining of hydrated chromium oxide must calcine material in 0.5-6 hours；After calcining material pickling drying
To chrome green product；The calcining material pickling refers to using H+Concentration is 0.01~2mol/L sulfuric acid or/and hydrochloric acid
Solution agitator treating 0.5~4 hour at 20~100 DEG C under conditions of solid-to-liquid ratio is 1: 1.5~4g/mL, then separation of solid and liquid.
Beneficial effect：
In the present invention, the technique created by the present invention can be achieved to prepare high added value using vanadium chromium reducing slag as raw material
With the vanadium trioxide and chrome green product of high-quality.
Traditional preparation V2O3Required raw material is all pure pentavalent vanadium compound, and vanadium reverts to trivalent process by pentavalent and needed
Substantial amounts of reducing agent is wanted, and is required for high temperature reduction process, causes V2O3Preparation cost it is high, process is complicated.Same Cr2O3's
Preparation is also required to high price chromic salts, and cost is high, and production process can produce severe toxicity contain hexavalent chromium wastewater and waste residue.Vanadium chromium reducing slag
Belong to dangerous solid waste, but contain vanadium and chromium valuable element again simultaneously.The present invention changes traditional selective oxidation at a low price
Vanadium handles the mode of thinking of vanadium chromium reducing slag, the principle of reduction is more difficult to than V (IV) using Cr (III), by controlling appropriate oxygen
It is V (III) to change the V (IV) in reduction potential selective reduction vanadium chromium reducing slag.Then V is utilized2O3Do not reacted and Cr with alkali
(OH)3Alkaline bleach liquor soluble nature difference realizes the separation of vanadium chromium, and combine water and chromium oxide it is different with impurity precipitation pH's and
Hydrated chromium oxide roasting process valence state and composition variation characteristic, impurity is realized by Selective separation-out hydrated chromium oxide and pickling
Remove, so that the vanadium trioxide product and chrome green of preparing high added value as raw material with vanadium chromium reducing slag are produced
Product.
This method reducing agent consumption is few, and what production process will not produce severe toxicity contains hexavalent chromium wastewater and waste residue, and technique is simple,
Cost is low, and good product quality added value is high, and V content is more than 65.8% in vanadium trioxide；The purity of chrome green exceedes
98.2%, it disclosure satisfy that industrialization production requirements.Whole process vanadium chromium recovery ratio is high, the rate of recovery of vanadium more than 99.1%, chromium
The rate of recovery is more than 96.1%.
Embodiment
Following examples are intended to illustrate invention, rather than the further restriction to protection scope of the present invention.
Embodiment 1
The vanadium chromium reducing slag 500g containing 5.2% vanadium and 13.5% chromium is taken to be added water pulp, addition by solid-to-liquid ratio 1: 4g/mL
Na2S2O4It is -0.5V stirring reaction 5 hours at 60 DEG C to control solution oxide reduction potential, then according in vanadium chromium reducing slag
Chromium generates Cr (OH) by Cr (III)4 -3.0 times of theoretical amount add stirring reaction 5 hours at NaOH, 70 DEG C, and separation of solid and liquid must contain
Chromium leachate and vanadium trioxide filter cake.Vanadium trioxide filter cake is scrubbed, vacuum drying, obtains three oxidations containing 65.9%V
Two vanadium products.Sulfuric acid is added into leachate containing chromium controls solution ph to be stirred at room temperature 2.5 hours for 10.0, the water being filtrated to get
Close 1300 DEG C of calcinings of chromium oxide and obtain within 3 hours calcining material.Calcining material is using containing H+Bar of the 1mol/L sulfuric acid solutions in solid-to-liquid ratio 1: 3
The lower 50 DEG C of agitator treatings of part 1 hour, the Cr that purity is 98.5% is obtained after the solid drying that separation of solid and liquid is obtained2O3Product, pickling
Cr (VI) is can't detect in liquid.The rate of recovery of whole technical process vanadium is 99.5%, and the rate of recovery of chromium is 97.5%.
Comparative example 1
The vanadium chromium reducing slag 500g containing 5.2% vanadium and 13.5% chromium is taken to be added water pulp, addition by solid-to-liquid ratio 1: 4g/mL
Na2S2O4Solution oxide reduction potential is controlled to add stirring reaction at 60 DEG C 5 hours for 0.25V, then according to vanadium chromium reducing slag
In chromium by Cr (III) generate Cr (OH)4 -3.0 times of theoretical amount add stirring reaction 5 hours, separation of solid and liquid at NaOH, 70 DEG C
Chromium leachate and filter cake containing vanadium must be contained.Filter cake containing vanadium is scrubbed, vacuum drying, obtains containing barium oxide containing 38.1%V.Xiang Han
Sulfuric acid is added in chromium leachate controls solution ph to be stirred at room temperature 2.5 hours for 10.0, the hydrated chromium oxide 1300 being filtrated to get
DEG C calcining obtain within 3 hours calcining material.Calcining material is using containing H+The 50 DEG C of stirrings under conditions of solid-to-liquid ratio 1: 3 of 1mol/L sulfuric acid solutions
Washing 1 hour, the Cr that purity is 98.0% is obtained after the solid drying that separation of solid and liquid is obtained2O3It can't detect in product, pickle
Cr(VI).The rate of recovery of whole technical process vanadium is 21.6%, and the rate of recovery of chromium is 80.3%.
By comparative example 1 it can be seen that when scope of the solution oxide reduction potential not in application claims, it is impossible to obtain
Qualified vanadium trioxide product, the rate of recovery of vanadium also only has 21.6%；For chromium, product quality slightly has attenuating, still
The rate of recovery is but reduced substantially.
Embodiment 2
The vanadium chromium reducing slag 1000g containing 2.8% vanadium and 9.4% chromium is taken to be added water pulp, addition by solid-to-liquid ratio 1: 3g/mL
Na2SO3It is 0.1V stirring reaction 6 hours at 100 DEG C to control solution oxide reduction potential, then according in vanadium chromium reducing slag
Chromium generates Cr (OH) by Cr (III)4 -3.5 times of theoretical amount add stirring reaction 4 hours at KOH, 100 DEG C, and separation of solid and liquid is obtained
Leachate containing chromium and vanadium trioxide filter cake.Vanadium trioxide filter cake is scrubbed, vacuum drying, obtains three oxygen containing 65.8%V
Change two vanadium products.Added into leachate containing chromium hydrochloric acid control solution pH value be 11.0 at 70 DEG C stirring reaction 1.5 hours, mistake
Filter obtained 1100 DEG C of calcinings of hydrated chromium oxide to obtain within 4 hours calcining material, calcining material is using containing H+0.5mol/L hydrochloric acid solutions exist
Washing 1 hour is stirred at room temperature under conditions of solid-to-liquid ratio 1: 2, it is 98.2% to obtain purity after the solid drying obtained after separation of solid and liquid
Cr2O3Cr (VI) is can't detect in product, pickle.The rate of recovery of whole technical process vanadium is 99.1%, and the rate of recovery of chromium is
96.1%.
Comparative example 2
The vanadium chromium reducing slag 1000g containing 2.8% vanadium and 9.4% chromium is taken to be added water pulp, addition by solid-to-liquid ratio 1: 3g/mL
Na2SO3It is 0.1V stirring reaction 6 hours at 100 DEG C to control solution oxide reduction potential, then according in vanadium chromium reducing slag
Chromium generates Cr (OH) by Cr (III)4 -3.5 times of theoretical amount add stirring reaction 4 hours at KOH, 100 DEG C, and separation of solid and liquid is obtained
Leachate containing chromium and vanadium trioxide filter cake.Vanadium trioxide filter cake is scrubbed, vacuum drying, obtains three oxygen containing 65.7%V
Change two vanadium products.Added into leachate containing chromium hydrochloric acid control solution pH value be 8.0 at 70 DEG C stirring reaction 1.5 hours, mistake
Filter obtained 1100 DEG C of calcinings of hydrated chromium oxide to obtain within 4 hours calcining material, calcining material is using containing H+0.5mol/L hydrochloric acid solutions exist
Washing 1 hour is stirred at room temperature under conditions of solid-to-liquid ratio 1: 2, it is 79.5% to obtain purity after the solid drying obtained after separation of solid and liquid
Cr2O3Cr (VI) is can't detect in product, pickle.The rate of recovery of whole technical process vanadium is 99.2%, and the rate of recovery of chromium is
96.2%.
By comparative example 2 it can be seen that controlling solution ph not in the scope of application claims when containing acid adding in chromium leachate
When, it is impossible to obtain qualified Cr2O3Product.
Embodiment 3
The vanadium chromium reducing slag 500g containing 5.2% vanadium and 13.5% chromium is taken to be added water pulp, addition by solid-to-liquid ratio 1: 4g/mL
Na2S2O4It is -0.7V stirring reaction 4 hours at 100 DEG C to control solution oxide reduction potential, then according in vanadium chromium reducing slag
Chromium by Cr (III) generate Cr (OH)4 -4.5 times of theoretical amount add stirring reaction 3 hours at NaOH, 100 DEG C, and separation of solid and liquid is obtained
Leachate containing chromium and vanadium trioxide filter cake.Vanadium trioxide filter cake is scrubbed, vacuum drying, obtains three oxygen containing 66.3%V
Change two vanadium products.Sulfuric acid is added into leachate containing chromium controls solution ph to be stirred at room temperature 2.5 hours for 10.0, is filtrated to get
900 DEG C of calcinings of hydrated chromium oxide obtain calcining material for 6 hours.Calcining material is using containing H+2mol/L hydrochloric acid solutions are in solid-to-liquid ratio 1: 4
Under the conditions of 50 DEG C of agitator treatings 1 hour, obtain the Cr that purity is 98.3% after the solid drying that separation of solid and liquid is obtained2O3Product, acid
Cr (VI) is can't detect in washing lotion.The rate of recovery of whole technical process vanadium is 99.7%, and the rate of recovery of chromium is 97.8%.
Comparative example 3
The vanadium chromium reducing slag 500g containing 5.2% vanadium and 13.5% chromium is taken to be added water pulp, addition by solid-to-liquid ratio 1: 4g/mL
Na2S2O4It is -0.7V stirring reaction 4 hours at 100 DEG C to control solution oxide reduction potential, then according in vanadium chromium reducing slag
Chromium by Cr (III) generate Cr (OH)4 -4.5 times of theoretical amount add stirring reaction 3 hours at NaOH, 100 DEG C, and separation of solid and liquid is obtained
Leachate containing chromium and vanadium trioxide filter cake.Vanadium trioxide filter cake is scrubbed, vacuum drying, obtains three oxygen containing 66.2%V
Change two vanadium products.Sulfuric acid is added into leachate containing chromium controls solution ph to be stirred at room temperature 2.5 hours for 10.0, is filtrated to get
700 DEG C of calcinings of hydrated chromium oxide obtain calcining material for 6 hours.Calcining material is using containing H+2mol/L hydrochloric acid solutions are in solid-to-liquid ratio 1: 4
Under the conditions of 50 DEG C of agitator treatings 1 hour, obtain the Cr that purity is 98.3% after the solid drying that separation of solid and liquid is obtained2O3Product, acid
Cr (VI) content is 0.12g/L in washing lotion.The rate of recovery of whole technical process vanadium is 99.8%, and the rate of recovery of chromium is 96.5%.
By comparative example 3 it can be seen that when scope of the hydrated chromium oxide calcining heat not in application claims, pickle
In just have Cr (VI), that is to say, that whole process just have containing Cr (VI) waste water produce.
Claims (10)
1. a kind of method that utilization vanadium chromium reducing slag prepares vanadium trioxide and chrome green, it is characterised in that including following
Step：
Step (1)：Selective reduction V (IV)：
Vanadium chromium reducing slag is with adding reducing agent after water slurry, the oxidation-reduction potential of adjustment system is 0.2V~-0.8V, by system
In V (IV) be reduced into V (III)；
Step (2)：Alkali leaches Cr (III)：
Alkali is added into the reduction reaction system of step (1), alkali leaching process is carried out, the Cr (III) in system is changed into Cr
(OH)4 -, separation of solid and liquid is then carried out, leachate containing chromium and vanadium trioxide filter cake is obtained；
Step (3)：It is prepared by vanadium trioxide：
Vanadium trioxide filtration cakes torrefaction obtains vanadium trioxide product；
Step (4)：It is prepared by chrome green：
Into leachate containing chromium, the pH of acid adding regulation and control leachate containing chromium is 9.0~12.0；Precipitation hydrated chromium oxide；It is hydrated oxygen
Material must be calcined through calcining by changing chromium；Chrome green product is obtained after the pickling of calcining material, drying.
2. the method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag as claimed in claim 1, its feature
It is, in step (1), the oxidation-reduction potential for adding reducing agent adjustment and control system is 0.1V~-0.7V.
3. the method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag as claimed in claim 1, its feature
It is, in step (1), the reducing agent is selected from Na2S2O5、Na2S2O3、Na2S2O4、Na2SO3In one or more.
4. the method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag as claimed in claim 1, its feature
It is, in step (1), in slurrying process, the solid-to-liquid ratio of vanadium chromium reducing slag and water is 1: 1.5~10g/mL；Reduction reaction temperature
For 20-110 DEG C, the time is 1~8 hour.
5. the method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag as claimed in claim 1, its feature
It is, in step (2), the dosage of alkali is that Cr (III) is changed into Cr (OH)4 -1~6.0 times of theoretical amount；Alkali leaching process
Temperature be 20-110 DEG C, the leaching time be 0.5~6 hour.
6. the method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag as claimed in claim 1, its feature
It is, in step (4), in sour precipitation process, the pH of acid adding regulation and control leachate containing chromium is 10~11.
7. the method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag as claimed in claim 1, its feature
It is, in step (4), the acid is sulfuric acid, hydrochloric acid, the one or more of phosphoric acid；The temperature of acid out process is 25-100 DEG C, acid
It is 0.5~10 hour to analyse mixing time.
8. the method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag as claimed in claim 7, its feature
It is, in step (4), calcining heat is 800-1300 DEG C, and calcination time is 0.5-6 hours.
9. the method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag as claimed in claim 1, its feature
It is, in step (4), calcining heat is 1100-1300 DEG C.
10. the method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag as claimed in claim 9, its feature
It is, in step (4), in acid cleaning process, calcining material is placed in acid solution, it is solid after 0.5~4h of stirring to pulp at 20-100 DEG C
Liquid is separated；Described acid solution is the sulfuric acid or/and hydrochloric acid solution that H+ concentration is 0.01~2mol/L；Calcining material and the solid-liquid of acid solution
Than for 1: 1.5~4g/mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710306634.3A CN107055612B (en) | 2017-05-04 | 2017-05-04 | A kind of method for preparing vanadium trioxide and chrome green using vanadium chromium reducing slag |
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Cited By (3)
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| CN108892171A (en) * | 2018-07-11 | 2018-11-27 | 首都师范大学 | A kind of thermodynamics restoring method synthesizing vanadium oxide nano material |
| CN113213537A (en) * | 2021-06-03 | 2021-08-06 | 清华大学 | Method for separating and preparing vanadium trioxide from mixed solution of vanadium and chromium |
| CN113337715A (en) * | 2021-06-03 | 2021-09-03 | 清华大学 | Method for recycling vanadium and chromium from vanadium and chromium-containing wastewater |
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| CN103602819A (en) * | 2013-11-29 | 2014-02-26 | 中南大学 | Comprehensive recovery method of vanadate-chromate-containing solution |
| CN103773956A (en) * | 2012-10-28 | 2014-05-07 | 孙刚 | Method for separating and recycling vanadium and chromium |
| CN106048240A (en) * | 2016-07-15 | 2016-10-26 | 中南大学 | Method for separating and extracting vanadium and chromium from vanadium and chromium reduction slag |
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| CN108892171A (en) * | 2018-07-11 | 2018-11-27 | 首都师范大学 | A kind of thermodynamics restoring method synthesizing vanadium oxide nano material |
| CN113213537A (en) * | 2021-06-03 | 2021-08-06 | 清华大学 | Method for separating and preparing vanadium trioxide from mixed solution of vanadium and chromium |
| CN113337715A (en) * | 2021-06-03 | 2021-09-03 | 清华大学 | Method for recycling vanadium and chromium from vanadium and chromium-containing wastewater |
| CN113337715B (en) * | 2021-06-03 | 2022-07-22 | 清华大学 | Method for recycling vanadium and chromium from vanadium and chromium-containing wastewater |
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