CN106399694A - Method for synchronously extracting vanadium and aluminum from waste vanadium oxide smelter refractory brick - Google Patents
Method for synchronously extracting vanadium and aluminum from waste vanadium oxide smelter refractory brick Download PDFInfo
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- CN106399694A CN106399694A CN201610879207.XA CN201610879207A CN106399694A CN 106399694 A CN106399694 A CN 106399694A CN 201610879207 A CN201610879207 A CN 201610879207A CN 106399694 A CN106399694 A CN 106399694A
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
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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
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention relates to a method for synchronously extracting vanadium and aluminum from a waste vanadium oxide smelter refractory brick. The method includes the steps that the waste refractory brick is added into an inorganic acid solution, the mixture is heated, stirred and leached, and leachate is obtained after filtering is completed; ammonium salt is added into the prepared leachate, heating dissolution and cooling crystallization are carried out, and aluminum-ammonium complex salt crystals and crystallized liquid are obtained after solid-liquid separation is carried out; an oxidizing agent is added into the crystallized liquid, an alkaline solution is added, the mixture is stirred, and ammonium polyorthovanadate precipitates are obtained after filtering is completed; and the ammonium polyorthovanadate precipitates are calcined, and vanadium pentoxide is obtained. According to the vanadium and aluminum co-extraction method, the recovery rate of vanadium of the immersed refractory brick is high, the purity of obtained aluminum-ammonium complex salt and vanadium pentoxide products is high, waste of vanadium, aluminum and other valuable metals is reduced, and the production cost is reduced.
Description
Technical field
The invention belongs to field of metallurgical chemistry, especially a kind of recycling extracting vanadium in vanadium oxide smelting furnace refractory brick
Method.
Background technology
At present, vanadic anhydride tablet manufacturing, substantially adopts " three-step approach ", i.e. the dehydration of ammonium vanadate, deamination, fusing,
Three sets of different devices are carried out respectively.First step drying adopts pneumatic conveying dryer, the hot blast of heated by natural gas and aqueous
20% about ammonium poly-vanadate is made a gift to someone in drying machine together, and moment can make its moisture drying to less than 1%；Second step deamination is
By the APV after dehydration in the rustless steel rotary furnace of outside heated by natural gas, under oxidizing atmosphere, through 550 DEG C about deaminations
Obtain powdery V2O5；3rd step be in three-phawse arc furnace 800 DEG C about by powdery vanadic anhydride melt, come out of the stove, through be granulated platform
Film-making.Melt vanadic anhydride with melting furnace, the vanadium that accumulates over a long period immersion is built in stove refractory brick.Tear the furnace rear material of brick open to discard.And in brick
Containing useful elements such as vanadium, can extract and be used.Take waste refractory bricks, crush and do energy spectrum analysiss.Wherein contain V2OX3～4%,
Al2O320～30%, SiO240～50%.Every year, ammonium vanadate smelting furnace fire resisting discarded by a vanadic anhydride tablet manufacturing line
300 tons of brick, loss vanadium oxide (is converted to V2O5) total amount >=12t.
CN 102898161 A discloses a kind of method of purification of discarded zirconia-corundum refractory brick, and the method includes：(1) raw material
Pretreatment；(2) dispensing with mix；(3) purify；(4) ball is blown in compressed air and water under high pressure mixing；(5) adjustment ball form and
The ratio of wherein hollow ball and medicine ball.The method can make the ZrO in discarded zirconia-corundum refractory brick2、Al2O3Obtain Deng efficient resource
To secondary utilization.But by the method, the vanadium aluminium element in the waste refractory bricks in vanadic anhydride production process cannot be carried out
Effectively extract.
Yao Xianzhao etc. (Fiberglass Industry give up refractory brick in platinum rhodium metal microwave alkali fusion activation-water-soluble acidleach process of enriching [J].
Process engineering journal, 2011,11 (4):579-584), glass work is processed using microwave alkali fusion activation-water-soluble acidleach process of enriching
Industry give up the fire resisting material of brick so as in platinum rhodium metal be enriched with acid leaching residue.By microwave heating alkali fusion and conventional heating alkali
Molten contrast experiment, has investigated alkali fusion temperature, temperature retention time, has joined the impact to alkali fusion process for the alkali number.Result shows, microwave exposure temperature
When 800 DEG C of degree, temperature retention time 30min, alkali fusion agent NaOH are 1.4 times of sample quality, alkali fusion reaction is carried out thoroughly.Grog is through water
After molten, acidleach in optimal conditions, under conditions of concentration of hydrochloric acid 3mol/L, extraction time 5min, acid material are than 15mL/g, slip
Strainability is good, slag yield 2.98%, and platinum rhodium metal can be enriched with about 33 times.But the method need to adopt microwave heating, power consumption is high,
Be not suitable for industrialized production, and platinum rhodium is very big with the nature difference of vanadium, aluminum, that is to apply to the extraction work of vanadium aluminum in useless refractory brick
In skill.
JP 2004-307926 discloses a kind of method extracting copper from waste refractory bricks, and methods described passes through mechanical powder
Broken, using converter, it is higher than the feature of copper using refractory brick fusing point, copper is fused into liquid so as to be separated with refractory brick, obtains by high temperature
To refractory brick waste residue again go into converter, extract copper further using above-mentioned steps.The method adopts physical method to useless
Copper in refractory brick is reclaimed, it is to avoid the problems such as acidic and alkaline waste water that chemical recovery method brings is processed, but converter melting copper
Required temperature is high, and power consumption is big, and aluminum oxide fusing point high it is difficult to by melting method separately.
Therefore, in order to reduce the loss of the element such as vanadium aluminum in vanadic anhydride production process, a kind of power consumption of research is low, available
In industrialized production, and it is particularly significant to extract the method for the elements such as vanadium aluminum effectively from vanadium oxide smelting furnace waste refractory bricks.
Content of the invention
Immerse refractory brick for valuable elements such as vanadium aluminum in vanadic anhydride production process in prior art, refractory brick is discarded
The problem that the valuable elements such as Shi Zaocheng vanadium aluminum waste.The present invention proposes vanadium aluminum in a kind of discarded vanadium oxide smelting furnace refractory brick and synchronously carries
Take method.Methods described, by waste refractory bricks are added to Leaching Vanadium aluminium element in organic acid, adds ammonium salt crystallization to go out aluminum ammonium
Double salt；After crystallization, liquid adds oxidant, adds aqueous slkali after oxidation reaction, is filtrated to get ammonium poly-vanadate precipitation；Institute's much vanadic acid
Ammonium precipitates roasting, obtains vanadic anhydride.Described vanadium aluminum extracting method altogether, high to the response rate of the v element of immersion refractory brick, and
The purity of gained aluminum ammonium double salt and vanadic anhydride product is high, decreases the waste of the valuable metals such as vanadium aluminum, has saved production
Cost.
For reaching this purpose, the present invention employs the following technical solutions：
The invention provides vanadium aluminum synchronous extraction method in a kind of discarded vanadium oxide smelting furnace refractory brick, methods described include with
Lower step：
(1) useless refractory brick is added in inorganic acid solution, heated and stirred leaches, solid-liquid separation obtains leachate；
(2) ammonium salt, dissolving, crystallization are added in the leachate being obtained to step (1), solid-liquid separation obtains aluminum ammonium double salt crystal
And liquid after crystallization；
(3) add oxidant in the liquid to after the described crystallization of step (2), add alkaline solution and stir, be filtrated to get many
Ammonium vanadate precipitates；
(4) optional, the ammonium poly-vanadate that step (3) obtains precipitates fired, prepared vanadic anhydride.
Following as currently preferred technical scheme, but the restriction of the technical scheme providing not as the present invention, pass through
Technical scheme below, can preferably reach and realize technical purpose and the beneficial effect of the present invention.
As currently preferred technical scheme, described useless refractory brick is through pretreated refractory brick.
Preferably, the pretreatment of described useless refractory brick is that described useless refractory brick is prepared into granule.
Preferably, described useless refractory brick is prepared into granule using broken and/or grinding.
Preferably, the particle diameter that described useless refractory brick is prepared into granule is less than 0.150mm, such as 0.150mm, 0.145mm,
0.140mm, 0.135mm, 0.130mm, 0.120mm, 0.100mm, 0.090mm, 0.055mm or 0.050mm etc., but and not only limit
In cited numerical value, this numerical range, other unrequited numerical value are equally applicable.
As currently preferred technical scheme, mineral acid described in step (1) is strong acid it is preferable that described mineral acid
For sulphuric acid, nitric acid or hydrochloric acid any one or at least two combination, described combination typical case but non-limiting examples have：Sulphuric acid
The combination of the combination of the combination with nitric acid, sulphuric acid and hydrochloric acid, nitric acid and hydrochloric acid and the combination of sulphuric acid and nitric acid and hydrochloric acid, enter one
Step is preferably sulphuric acid.Because sulphuric acid price is relatively low, low cost.
Preferably, the concentration of mineral acid described in step (1) is 30wt%～50wt%, such as 30wt%, 31wt%,
32wt%, 33wt%, 34wt%, 35wt%, 38wt%, 40wt%, 42wt%, 45wt%, 46wt%, 47wt%, 48wt%,
49wt% or 50wt% etc., it is not limited to other unrequited numerical value are equally suitable in cited numerical value, this numerical range
With preferably 40wt%～45wt%.
Preferably, the described solid-to-liquid ratio of step (1) is 1:(1～4), such as 1:1、1:1.5、1:2、1:2.5、1:3、1:3.5 or
1:4 etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, this numerical range, excellent further
Elect 1 as:(2.5～3.5).
As currently preferred technical scheme, the method leaching described in step (1) is heating and/or leaching.
Preferably, the temperature of described heating is 50～200 DEG C, such as 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 120
DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C or 200 DEG C etc., it is not limited to cited numerical value, this numerical range
Other unrequited numerical value interior are equally applicable, more preferably 80～200 DEG C.
Preferably, the speed of described stirring is 50～400r/min, such as 50r/min, 100r/min, 150r/min, 200r/
Min, 250r/min, 300r/min, 350r/min or 400r/min etc., it is not limited to cited numerical value, this numerical value model
In enclosing, other unrequited numerical value are equally applicable, more preferably 100r/min～300r/min.
Preferably, the time of described stirring is 1～4h, such as 1h, 1.5h, 2h, 2.5h, 3h, 3.5h or 4h etc., but and not only
It is limited to other unrequited numerical value in cited numerical value, this numerical range equally applicable, more preferably 2～4h.
Preferably, the described solid-liquid separating method of step (1) includes filtering, settle or being centrifuged, and more preferably filters.With
In production, filter fast yield high.
As currently preferred technical scheme, described in step (2), the addition of ammonium salt is：Ammonium salt and described leachate
In aluminum mol ratio be (5～1):1, such as 5:1、4.5:1、4:1、3.5:1、3:1、2.5:1、2:1、1.5:1、1:1 or 0.5:1
Deng, it is not limited to other unrequited numerical value are equally applicable in cited numerical value, this numerical range, preferably (3～
0.5):1.
Preferably, the described ammonium salt of step (2) includes ammonium sulfate and/or ammonium hydrogen sulfate, more preferably ammonium sulfate.Sulphuric acid
Ammonium valency is low, easy to use.
As currently preferred technical scheme, the method for the described dissolving of step (2) is heating for dissolving.
Preferably, the method for crystallization described in step (2) is crystallisation by cooling, evaporative crystallization and dilution crystallization, further
It is preferably crystallisation by cooling.
Preferably, the described crystallisation by cooling time is 0.5～6h, such as 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h,
4.5h, 5h, 5.5h or 6h etc., it is not limited to other unrequited numerical value are same in cited numerical value, this numerical range
It is suitable for, more preferably 2.5h～6h.
Preferably, described crystallisation by cooling temperature is 1～10 DEG C, such as 1 DEG C, 2 DEG C, 3 DEG C, 4 DEG C, 5 DEG C, 6 DEG C 7 DEG C, 8 DEG C, 9
DEG C, 10 DEG C etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, this numerical range, enter one
Step is preferably 2～5 DEG C.
Preferably, leach described useless refractory brick further in the direct return to step of liquid (1) after crystallizing described in step (2),
Until vanadium concentration >=20g/L in liquid after crystallization.
Preferably, leach described useless refractory brick further in the direct return to step of liquid (1) after crystallizing described in step (2)
Before, mineral acid need to be added before crystallisation by cooling extremely identical with the concentration of the described mineral acid of step (1).
Preferably, the described solid-liquid separating method of step (2) includes filtering, settle or being centrifuged, and more preferably filters.
Leach useless refractory brick further in liquid return to step (1) after crystallization, decrease the consumption of acid in leaching step, simultaneously
Decrease the content of acid in the waste liquid after extraction, reduce liquid waste processing difficulty；In liquid after crystallization during vanadium concentration >=20g/L, have
Oxidation further beneficial to vanadium and precipitation, decrease the consumption of oxidant and aqueous slkali, save the cost extracting vanadium aluminum.
As the preferred technical scheme of the application, in step (3), the addition of oxidant is：Vanadium in liquid after crystallization and oxygen
The mol ratio of agent is 1:(1～10), such as 1:1、1:2、1:3、1:4、1:5、1:6、1:7、1:8、1:9 or 1:10 etc., but not
It is only limitted to other unrequited numerical value in cited numerical value, this numerical range equally applicable, preferably 1:(1～8).
Preferably, oxidant described in step (3) includes appointing in sodium chlorate, sodium hypochlorite, oxygen, ozone or hydrogen peroxide
Meaning a kind of or at least two combinations, described combination typical case but non-limiting examples have：The combination of sodium chlorate and sodium hypochlorite, chlorine
The group of the combination of the combination of the combination of sour ammonium and oxygen, sodium hypochlorite and oxygen, sodium hypochlorite and ozone, ammonium chlorate and hydrogen peroxide
Combination of conjunction or sodium hypochlorite, sodium chlorate and oxygen etc..
Preferably, the temperature of the described oxidation reaction of step (3) is 20～100 DEG C, such as 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60
DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 100 DEG C etc., it is not limited to other are unrequited in cited numerical value, this numerical range
Numerical value is equally applicable, more preferably 50 DEG C～85 DEG C.
Preferably, the response time of described oxidation reaction be, more preferably 0.2h～2h, such as 0.2h, 0.3h,
0.4h, 0.5h, 0.6h, 0.7h0.8h, 0.9h, 1h, 1.2h, 1.5h, 1.8h or 2h etc., it is not limited to cited number
Value, in this numerical range, other unrequited numerical value are equally applicable, more preferably 0.5～1h.
As currently preferred technical scheme, the described aqueous slkali of step (3) includes ammonia.
Preferably, the described aqueous slkali of step (3) includes ammonia or ammonium salt and sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid
The combination of at least one of potassium, sodium bicarbonate or potassium bicarbonate, described combination is typical but non-limiting examples have：Ammonium salt and hydrogen-oxygen
Change the combination of the combination of the combination of combination, ammonium salt and potassium hydroxide, ammonium salt and sodium carbonate, ammonium salt and potassium carbonate of sodium, ammonium salt and
The combination of the combination of sodium bicarbonate, sodium salt and potassium bicarbonate, ammonia and sodium hydroxide, ammonia and potassium hydroxide, ammonia and carbonic acid
The combination of the combination of sodium, ammonia and potassium carbonate, ammonium salt and sodium hydroxide and sodium carbonate, ammonium salt and potassium hydroxide and potassium carbonate, ammonium
Combination of the combination of salt and sodium carbonate and sodium bicarbonate or ammonium salt and potassium carbonate and potassium bicarbonate etc..
Preferably, described ammonium salt includes ammonium sulfate and/or ammonium hydrogen sulfate, more preferably ammonium sulfate.
Preferably, the Adding Way of the described alkali liquor of step (3) is Deca.
Preferably, after step (3) adds described aqueous slkali, the pH of solution is 1.0～3.0, such as 1.0,1.1,1.2,1.3,
1.4th, 1.5,1.8,2.0,2.2,2.5,2.6,2.7,2.8,2.9 or 3.0 etc., it is not limited to cited numerical value, this number
In the range of value, other unrequited numerical value are equally applicable, and more preferably 1.5～2.1.
As currently preferred technical scheme, step (3) includes liquid after the crystallization adding after alkaline solution is stirred
Mix；
Preferably, the temperature of described stirring is >=20 DEG C, such as 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90
DEG C or 100 DEG C etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, this numerical range, enter
One step is preferably >=50 DEG C, particularly preferably >=90 DEG C.
Preferably, the time of described stirring is≤3h, such as 0.5h, 1h, 1.5h, 2h, 2.5h or 3h etc., it is not limited to
Cited numerical value, in this numerical range, other unrequited numerical value are equally applicable, more preferably≤2h, particularly preferably
≤1h.
Preferably, the speed of described stirring is 50r/min～400r/min, such as 50r/min, 100r/min, 150r/min,
200r/min, 250r/min, 300r/min, 350r/min or 400r/min etc., it is not limited to cited numerical value, this number
In the range of value, other unrequited numerical value are equally applicable, more preferably 100r/min～300r/min.
Preferably, the sintering temperature of step (4) described ammonium poly-vanadate precipitation is 400～800 DEG C, such as 400 DEG C, 450 DEG C,
500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C or 800 DEG C etc., it is not limited to cited numerical value, this numerical value
In the range of other unrequited numerical value equally applicable, more preferably 400～600 DEG C.
Preferably, the time of the described roasting of step (4) is 1～5h, such as 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h
Or 5h etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, this numerical range, excellent further
Elect 1h～3h as.
As the present invention preferably technical scheme, methods described includes：
(1) described useless refractory brick is crushed, pulverizes, by described useless refractory brick powder be added to concentration be 30%～
In the mineral acid of 50wt%, solid-to-liquid ratio is 1:(1～4), under rotating speed 50～400r/min, stirs 1～4h, it is heated to 50～
200 DEG C of leachings, are filtrated to get leachate；
(2) mol ratio adding the aluminum in ammonium salt, ammonium salt and described leachate in the leachate being obtained to step (1) is (5
～0.5):1；Heating for dissolving, adds mineral acid, crystallisation by cooling 0.5～6h, and solid-liquid separation obtains aluminum ammonium double salt crystal and crystallization
Liquid afterwards；Described useless refractory brick is leached further in the direct return to step of liquid (1) after crystallizing described in step (2), until after crystallization
Vanadium concentration >=20g/L in liquid；
(3) add oxidant in the liquid to after the described crystallization of step (2), at 20～100 DEG C, react 0.2h～2h, crystallization
Vanadium in liquid and the mol ratio of oxidant are 1 afterwards:1～10；Deca alkaline solution again, adjusts pH to 1.0～3.0, at least 20
At DEG C, stirring is less than 3h, is filtrated to get ammonium poly-vanadate precipitation；
(4) described ammonium poly-vanadate is deposited in roasting 1～5h at 400～800 DEG C, prepared vanadic anhydride.
Compared with prior art, the invention has the advantages that：
(1) present invention application Ore Leaching process reclaims vanadium oxide smelting furnace refractory brick valuable element, vanadium recovery
Reach more than 90%；
(2) spent acid producing during present invention process can be recycled effectively, no spent acid, waste gas, and waste liquid is arranged
Put；
(3) application of the operation such as aluminum ammonium complex salt crystal of the present invention, ammonium salt precipitation can achieve that the distribution of valuable element is extracted, and obtains
Purity to aluminum ammonium double salt can reach more than 97%, obtains purity of vanadium pentoxide and can reach more than 98%, can be directly as work
Industry raw material puts into production；
(4) present invention is the rational utilization to industrial waste, and decreasing vanadium aluminum etc. in technique for producing vanadium pentoxide has
The waste of valency element, has technical process simply, low cost, eco-friendly feature.
Brief description
Fig. 1 is the technological process of vanadium aluminum synchronous extraction method in a kind of discarded vanadium oxide smelting furnace refractory brick of the present invention
Figure.
Specific embodiment
For the present invention is better described, readily appreciate technical scheme, below to the present invention further specifically
Bright.But following embodiments is only the simple example of the present invention, does not represent or limit the scope of the present invention, this
Invention protection domain is defined by claims.
The invention provides vanadium aluminum synchronous extraction method in a kind of discarded vanadium oxide smelting furnace refractory brick, methods described include with
Lower step：
(1) useless refractory brick is added in mineral acid, leaches, solid-liquid separation obtains leachate；
(2) ammonium salt, dissolving, crystallization are added in the leachate obtaining to step (1), solid-liquid separation obtains aluminum ammonium double salt crystal
And liquid after crystallization；
(3) add oxidant in the liquid to after the described crystallization of step (2), add alkaline solution, solid-liquid separation obtains many vanadium
Sour ammonium precipitation；
(4) alternatively, the ammonium poly-vanadate that step (3) obtains precipitates fired, prepared vanadic anhydride.It is below the present invention
Typical case but non-limiting example：
Embodiment 1
Present embodiments provide vanadium aluminum synchronous extraction method in a kind of discarded vanadium oxide smelting furnace refractory brick, methods described includes
Following steps：
(1) described useless refractory brick is crushed, pulverize, it is 40wt%'s that described useless refractory brick powder is added to concentration
In sulfuric acid solution, it is 1 that sulfuric acid dosage presses solid-liquid mass ratio:3, it is heated to 150 DEG C, under rotating speed 400r/min, leaching 3h,
It is filtrated to get leachate；
(2) add the mol ratio of the aluminum in ammonium sulfate, ammonium sulfate and described leachate in the leachate being obtained to step (1)
For 2:1；Heating for dissolving, 5 DEG C of crystallization 3h of chilling temperature, solid-liquid separation obtains liquid after ammonium aluminum sulfate crystal and crystallization；
(3) add sodium chlorate in the liquid to after the described crystallization of step (2), at 40 DEG C, react 0.5h, the vanadium in liquid after crystallization
Mol ratio with sodium chlorate is 1:2；Deca sodium hydroxide and ammonia, adjust pH to 2.0, stir 0.5h, filter at 90 DEG C
To ammonium poly-vanadate precipitation；Described ammonium poly-vanadate is deposited in roasting 2h at 450 DEG C, obtains vanadic anhydride.
The purity of gained Burnt ammonium alum is 98.5%, and gained purity of vanadium pentoxide is 98.3%, and vanadium recovery is
92.5%.
Embodiment 2
Present embodiments provide vanadium aluminum synchronous extraction method in a kind of discarded vanadium oxide smelting furnace refractory brick, methods described includes
Following steps：
(1) described useless refractory brick is crushed, pulverize, it is 45wt%'s that described useless refractory brick powder is added to concentration
In sulfuric acid solution, it is 1 that sulfuric acid dosage presses solid-liquid mass ratio:2.5, it is heated to 100 DEG C, under rotating speed 300r/min, leaching
2h, is filtrated to get leachate；
(2) add the mol ratio of the aluminum in ammonium sulfate, ammonium sulfate and described leachate in the leachate being obtained to step (1)
For 4:1；Heating for dissolving, 5 DEG C of chilling temperature, crystallize 4h, solid-liquid separation obtains liquid after ammonium aluminum sulfate crystal and crystallization；
(3) add hydrogen peroxide in the liquid to after the described crystallization of step (2), at 40 DEG C, react 0.5h, the vanadium in liquid after crystallization
Mol ratio with hydrogen peroxide is 1:2；Deca sodium carbonate and ammonia, adjust pH to 1.9, stir 0.8h, be filtrated to get at 100 DEG C
Ammonium poly-vanadate precipitates；Described ammonium poly-vanadate is deposited in roasting 3h at 500 DEG C, obtains vanadic anhydride.
The purity of gained Burnt ammonium alum is 97.3%, and gained purity of vanadium pentoxide is 98.7%, and vanadium recovery is
93.0%.
Embodiment 3
Present embodiments provide vanadium aluminum synchronous extraction method in a kind of discarded vanadium oxide smelting furnace refractory brick, methods described includes
Following steps：
(1) described useless refractory brick is crushed, pulverize, it is 35wt%'s that described useless refractory brick powder is added to concentration
In sulfuric acid solution, it is 1 that sulfuric acid dosage presses solid-liquid mass ratio:3.5, it is heated to 80 DEG C, under rotating speed 200r/min, leaching
3h, is filtrated to get leachate；
(2) add the mol ratio of the aluminum in ammonium sulfate, ammonium sulfate and described leachate in the leachate being obtained to step (1)
For 3:1；Heating for dissolving, 4 DEG C of chilling temperature, crystallize 6h, solid-liquid separation obtains liquid after ammonium aluminum sulfate crystal and crystallization；
(3) add sodium chlorate in the liquid to after the described crystallization of step (2), at 80 DEG C, react 0.5h, the vanadium in liquid after crystallization
Mol ratio with sodium chlorate is 1:2.5；Deca ammonia, adjusts pH to 2.1, stirs 0.6h, be filtrated to get many vanadic acid at 95 DEG C
Ammonium precipitates；Described ammonium poly-vanadate is deposited in roasting 2.5h at 550 DEG C, obtains vanadic anhydride.
The purity of gained Burnt ammonium alum is 97.9%, and gained purity of vanadium pentoxide is 98.1%, and vanadium recovery is
92.1%.
Embodiment 4
Present embodiments provide vanadium aluminum synchronous extraction method in a kind of discarded vanadium oxide smelting furnace refractory brick, methods described includes
Following steps：
(1) described useless refractory brick is crushed, pulverize, it is 40wt%'s that described useless refractory brick powder is added to concentration
In sulfuric acid solution, it is 1 that sulfuric acid dosage presses solid-liquid mass ratio:4, it is heated to 60 DEG C, under rotating speed 100r/min, leaching
2.5h, is filtrated to get leachate；
(2) add the mol ratio of the aluminum in ammonium sulfate, ammonium sulfate and described leachate in the leachate being obtained to step (1)
For 5:1；Heating for dissolving, adds sulphuric acid to 40wt%, chilling temperature to 3 DEG C, crystallizes 4h, solid-liquid separation obtains ammonium aluminum sulfate crystal
And liquid after crystallization；Described useless refractory brick is leached further, directly in the direct return to step of liquid (1) after crystallizing described in step (2)
Vanadium concentration >=20g/L in the liquid to after crystallize；
(3) be passed through oxygen in liquid to after the described crystallization of step (2), at 95 DEG C, react 0.6h, the vanadium in liquid after crystallization with
The mol ratio of oxygen is 1:1；Deca sodium hydroxide and ammonium sulfate, adjust pH to 2.0, stir 1h, be filtrated to get many at 95 DEG C
Ammonium vanadate precipitates；Described ammonium poly-vanadate is deposited in roasting 1.5h at 400 DEG C, obtains vanadic anhydride.
The purity of gained Burnt ammonium alum is 98.1%, and gained purity of vanadium pentoxide is 97.9%, and vanadium recovery is
92.7%.
Embodiment 5
Present embodiments provide vanadium aluminum synchronous extraction method in a kind of discarded vanadium oxide smelting furnace refractory brick, methods described includes
Following steps：
(1) described useless refractory brick is crushed, pulverize, it is 50wt%'s that described useless refractory brick powder is added to concentration
In sulfuric acid solution, it is 1 that sulfuric acid dosage presses solid-liquid mass ratio：2, it is heated to 90 DEG C, under rotating speed 50r/min, leaching 2h, mistake
Filter obtains leachate；
(2) add the mol ratio of the aluminum in ammonium sulfate, ammonium sulfate and described leachate in the leachate being obtained to step (1)
For 0.5:1；Heating for dissolving, adds sulphuric acid to 50wt%, 2 DEG C of chilling temperature, crystallizes 5h, solid-liquid separation obtains ammonium aluminum sulfate crystal
And liquid after crystallization；Described useless refractory brick is leached further, directly in the direct return to step of liquid (1) after crystallizing described in step (2)
Vanadium concentration >=20g/L in the liquid to after crystallize；
(3) add the compositionss (amount 1 of material of sodium chlorate and sodium hypochlorite in the liquid to after the described crystallization of step (2):1),
At 100 DEG C, react 1h, the vanadium in liquid after crystallization is 1 with the mol ratio of sodium chlorate and sodium hypochlorite compositionss:3；Deca hydrogen-oxygen
Change potassium and ammonium sulfate, adjust pH to 2.0, at 95 DEG C, stir 0.4h, be filtrated to get ammonium poly-vanadate precipitation；Described ammonium poly-vanadate sinks
Form sediment roasting 2.5h at 600 DEG C, obtains vanadic anhydride.
The purity of gained Burnt ammonium alum is 98.2%, and gained purity of vanadium pentoxide is 98.8%, and vanadium recovery is
88.5%.
Embodiment 6
Present embodiments provide vanadium aluminum synchronous extraction method in a kind of discarded vanadium oxide smelting furnace refractory brick, methods described includes
Following steps：
(1) described useless refractory brick is crushed, pulverize, it is 30wt%'s that described useless refractory brick powder is added to concentration
In sulfuric acid solution, it is 1 that sulfuric acid dosage presses solid-liquid mass ratio:3.5, it is heated to 120 DEG C, under rotating speed 150r/min, leaching
2h, is filtrated to get leachate；
(2) add the mol ratio of the aluminum in ammonium sulfate, ammonium sulfate and described leachate in the leachate being obtained to step (1)
For 0.5:1；Heating for dissolving, adds sulphuric acid to 30wt%, 5 DEG C of crystallization 5h of chilling temperature, solid-liquid separation obtains ammonium aluminum sulfate crystal
And liquid after crystallization；Described useless refractory brick is leached further, directly in the direct return to step of liquid (1) after crystallizing described in step (2)
Vanadium concentration >=20g/L in the liquid to after crystallize；
(3) add sodium chlorate in the liquid to after the described crystallization of step (2), at 100 DEG C, react 1h, the vanadium in liquid after crystallization
Mol ratio with sodium chlorate is 1:1.5；Deca potassium carbonate and ammonium sulfate, adjust pH to 2.0, stir 0.4h at 95 DEG C, filter
Obtain ammonium poly-vanadate precipitation；Described ammonium poly-vanadate is deposited in roasting 2.5h at 500 DEG C, obtains vanadic anhydride.
The purity of gained Burnt ammonium alum is 98.3%, and gained purity of vanadium pentoxide is 98.1%, and vanadium recovery is
88.7%.
Embodiment 7
Embodiment provides vanadium aluminum synchronous extraction method in a kind of discarded vanadium oxide smelting furnace refractory brick, methods described include with
Lower step：
(1) described useless refractory brick is crushed, pulverize, it is 30wt%'s that described useless refractory brick powder is added to concentration
In hydrochloric acid solution, it is 1 that hydrochloric acid consumption presses solid-liquid mass ratio:5, it is heated to 150 DEG C, under rotating speed 300r/min, leaching 4h,
It is filtrated to get leachate；
(2) add rubbing of the aluminum in ammonium hydrogen sulfate, ammonium hydrogen sulfate and described leachate in the leachate being obtained to step (1)
That ratio is 5:1；Heating for dissolving, adds hydrochloric acid to 30wt%, 5 DEG C of crystallization 5h of chilling temperature, it is brilliant that solid-liquid separation obtains Burnt ammonium alum
Liquid after body and crystallization；Described useless refractory brick is leached further in the direct return to step of liquid (1) after crystallizing described in step (2),
Until vanadium concentration >=20g/L in liquid after crystallization；
(3) add ozone in liquid to after the described crystallization of step (2), at 100 DEG C, react 1h, the vanadium in liquid after crystallization with
The mol ratio of ozone is 1:2；Deca ammonia, adjusts pH to 1.9, stirs 0.6h at 100 DEG C, is filtrated to get ammonium poly-vanadate and sinks
Form sediment；Described ammonium poly-vanadate is deposited in roasting 2.5h at 500 DEG C, obtains vanadic anhydride.
The purity of gained Burnt ammonium alum is 95.6%, and gained purity of vanadium pentoxide is 95.2%, vanadium recovery 85.5
For %.
Applicant states, the present invention illustrates the detailed construction feature of the present invention by above-described embodiment, but the present invention is simultaneously
It is not limited to above-mentioned detailed construction feature, that is, do not mean that the present invention has to rely on above-mentioned detailed construction feature and could implement.Institute
Belong to those skilled in the art it will be clearly understood that any improvement in the present invention, the equivalence replacement to part selected by the present invention
And the increase of accessory, selection of concrete mode etc., all fall within protection scope of the present invention and open within the scope of.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, multiple simple variant can be carried out to technical scheme, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific 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 various can
The compound mode of energy no longer separately illustrates.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it equally should be considered as content disclosed in this invention.
Claims (10)
1. in a kind of discarded vanadium oxide smelting furnace refractory brick vanadium aluminum simultaneous extraction method it is characterised in that methods described include with
Lower step：
(1) useless refractory brick is added in mineral acid, leaches, solid-liquid separation obtains leachate；
(2) in the leachate obtaining to step (1) add ammonium salt, dissolving, crystallization, solid-liquid separation obtain aluminum ammonium double salt crystal and
Liquid after crystallization；
(3) add oxidant in the liquid to after the described crystallization of step (2), add alkaline solution, solid-liquid separation obtains ammonium poly-vanadate
Precipitation；
(4) alternatively, the ammonium poly-vanadate that step (3) obtains precipitates fired, prepared vanadic anhydride.
2. according to claim 1 method it is characterised in that described useless refractory brick is through pretreated refractory brick；
Preferably, the pretreatment of described useless refractory brick is：Described useless refractory brick is prepared into granule；
Preferably, described useless refractory brick is prepared into granule using broken and/or grinding；
Preferably, the grain diameter that described useless refractory brick is prepared into is less than 0.150mm.
3. method according to claim 1 or claim 2 is it is characterised in that mineral acid described in step (1) is strong acid；
Preferably, described mineral acid be sulphuric acid, nitric acid or hydrochloric acid any one or at least two combination, more preferably
Sulphuric acid；
Preferably, mineral acid mass concentration described in step (1) is 30wt%～50wt%, more preferably 40wt%-
45wt%；
Preferably, useless refractory brick described in step (1) and the solid-to-liquid ratio of mineral acid are 1:(1～4), more preferably 1:(2.5
～3.5).
4. the method according to any one of claim 1-3 is it is characterised in that the method for the described leaching of step (1) is
Heating and/or leaching；
Preferably, the temperature of described heating is 50～200 DEG C, more preferably 80～200 DEG C；
Preferably, the rotating speed of described stirring is 50～400r/min, more preferably 100～300r/min；
Preferably, the time that is described plus mixing is 1～4h, more preferably 2～3h.
Preferably, the described solid-liquid separating method of step (1) includes filtering, settle or being centrifuged, and more preferably filters.
5. the method according to any one of claim 1-4 is it is characterised in that the addition of ammonium salt described in step (2)
Measure and be：The mol ratio of the aluminum in ammonium salt and described leachate is (5～0.5):1, preferably (3～0.5):1；
Preferably, the described ammonium salt of step (2) includes ammonium sulfate and/or ammonium hydrogen sulfate, more preferably ammonium sulfate.
6. the method according to any one of claim 1-5 is it is characterised in that the method for the described dissolving of step (2) is
Heating for dissolving；
Preferably, the method for the described crystallization of step (2) is crystallisation by cooling, evaporative crystallization or dilution crystallization, more preferably cold
But crystallize；
Preferably, the time of described crystallisation by cooling is 0.5～6h, more preferably 2.5～6h；
Preferably, the temperature of described crystallisation by cooling is 1～10 DEG C, more preferably 2～5 DEG C；
Preferably, leach described useless refractory brick further in the direct return to step of liquid (1) after crystallizing described in step (2), until
Vanadium concentration >=20g/L in liquid after crystallization；
Preferably, before leaching described useless refractory brick further in the direct return to step of liquid (1) after crystallizing described in step (2), need
Add mineral acid extremely identical with the concentration of the described mineral acid of step (1) before crystallisation by cooling；
Preferably, the described solid-liquid separating method of step (2) includes filtering, settle or being centrifuged, and more preferably filters.
7. the method according to any one of claim 1-6 it is characterised in that oxidant described in step (3) plus
Entering amount is：Vanadium in liquid after crystallization and oxidant mol ratio are 1:(1～10), preferably 1:(1～8)；
Preferably, the described oxidant of step (3) includes any one in sodium chlorate, sodium hypochlorite, oxygen, ozone or hydrogen peroxide
Or at least two combination；
Preferably, the temperature of oxidation reaction described in step (3) is 20～100 DEG C, more preferably 50～85 DEG C；
Preferably, the response time of oxidation reaction described in step (3) is 0.2～2h, more preferably 0.5～1h.
8. the method according to any one of claim 1-7 is it is characterised in that the described aqueous slkali of step (3) includes ammonia
Water；
Preferably, the described aqueous slkali of step (3) include ammonia or ammonium salt and sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
The combination of at least one of sodium bicarbonate or potassium bicarbonate；
Preferably, described ammonium salt includes ammonium sulfate and/or ammonium hydrogen sulfate, more preferably ammonium sulfate；
Preferably, the Adding Way of alkali liquor described in step (3) is Deca；
Preferably, after adding described aqueous slkali in step (3), the pH of solution is 1.0～3.0, more preferably 1.5～2.1.
9. the method according to any one of claim 1-8 it is characterised in that step (3) include to add alkalescence molten
After crystallization after liquid, liquid is stirred；
Preferably, the temperature of described stirring is >=20 DEG C, more preferably >=50 DEG C, particularly preferably >=90 DEG C；
Preferably, the time of described stirring is≤3h, more preferably≤2h, particularly preferably≤1h；
Preferably, the speed of described stirring is 50～400r/min, more preferably 100～300r/min；
Preferably, the sintering temperature of step (4) described ammonium poly-vanadate precipitation is 400～800 DEG C, more preferably 400～600
℃；
Preferably, the described roasting time of step (4) is 1～5h, more preferably 1～3h.
10. the method according to any one of claim 1-9 it is characterised in that, the method comprising the steps of：
(1) described useless refractory brick is crushed, pulverize, it is 30%～50wt% that described useless refractory brick powder is added to concentration
Mineral acid in, solid-to-liquid ratio be 1:(1～4), under rotating speed 50～400r/min, stirs 1～4h, is heated to 50～200 DEG C of leachings
Go out, be filtrated to get leachate；
(2) mol ratio adding the aluminum in ammonium salt, ammonium salt and described leachate in the leachate being obtained to step (1) be (5～
0.5):1；Heating for dissolving, adds mineral acid, crystallisation by cooling 0.5～6h, after solid-liquid separation obtains aluminum ammonium double salt crystal and crystallization
Liquid；Described useless refractory brick is leached further in the direct return to step of liquid (1) after described crystallization, until vanadium concentration in liquid after crystallization >=
20g/L；
(3) add oxidant in the liquid to after the described crystallization of step (2), at 20～100 DEG C, react 0.2～2h, in liquid after crystallization
The mol ratio of vanadium and oxidant be 1:1～10；Deca alkaline solution again, adjusts pH to 1.0～3.0, stirs at least 20 DEG C
Mix less than 3h, be filtrated to get ammonium poly-vanadate precipitation；
(4) described ammonium poly-vanadate is deposited in roasting 1～5h at 400～800 DEG C, prepared vanadic anhydride.
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