CN108034807A - A kind of transforming agent and its application method for being used for the vanadium extraction from vanadium raw ore - Google Patents
A kind of transforming agent and its application method for being used for the vanadium extraction from vanadium raw ore Download PDFInfo
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- CN108034807A CN108034807A CN201711297727.0A CN201711297727A CN108034807A CN 108034807 A CN108034807 A CN 108034807A CN 201711297727 A CN201711297727 A CN 201711297727A CN 108034807 A CN108034807 A CN 108034807A
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- vanadium
- transforming agent
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
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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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- 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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- Manufacturing & Machinery (AREA)
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- Geochemistry & Mineralogy (AREA)
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- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a kind of transforming agent for being used for the vanadium extraction from vanadium raw ore, the transforming agent includes the raw material of following parts by weight：85~95 parts of vanadium silicide, 2~6 parts of vanadic anhydride, 8~15 parts of methyl red sodium salt.The invention also discloses the application method of the transforming agent.Transforming agent disclosed by the invention may be used as the roasting and conversion oxidation of various vanadium raw ores, and adaptable, vanadium conversion rate is fast, high conversion rate.
Description
Technical field
The present invention relates to navajoite vanadium extraction technical field, and in particular to it is a kind of be used for from vanadium raw ore the transforming agent of vanadium extraction and its
Application method.
Background technology
Vanadium and vanadium-containing compound as a kind of extremely important raw material of industry, steel, alloy, chemical industry, medicine, catalysis,
The various fields such as novel pigment and battery technology have a wide range of applications.At present, the market demand of vanadium and vanadium-containing compound
Amount increases year by year, in the situation that supply falls short of demand.
In vanadium raw ore, most vanadium is entered in mineral lattice with three valence states, and such lattice structure is highly stable, its
Middle vanadium is in bound state, it is difficult to is leached by water, acid or alkali soluble solution, therefore, to leach this part vanadium must first destroy these stabilizations
Lattice structure, make to be strapped in the vanadium in lattice structure and discharge, then it is aoxidized and is converted.
At present, the technique of vanadium extraction generally uses high temperature oxidation roasting from vanadium raw ore, and the purpose of high temperature oxidation roasting is broken
Lower valency (trivalent or tetravalence) vanadium, is oxidized to the oxide of five valence state vanadium, then in transforming agent by the institutional framework of bad vanadium raw ore
Under the oxidation of sodium salt (for example, soda ash or sodium chloride), sodium vanadate is generated, it is right in order to water or Ore Leaching sodium vanadate solution
The sodium vanadate solution of leaching carries out precipitation reaction using ammonium reagent (such as ammonium sulfate, ammonium nitrate, amine-oxides) and obtains ammonium metavanadate
Or ammonium poly-vanadate, ammonium metavanadate or ammonium poly-vanadate are calcined to obtain vanadic anhydride, vanadic anhydride is in condition existing for calcium
Under, heat-treated and can obtain vanadium metal.
Using soda ash or sodium chloride as in the roasting process of transforming agent, at roasting initial stage, due to lacking vanadium kind in system
Lure so that transformation time is long, leaching rate is low, meanwhile, mineral pelletizing for a long time be in high-temperature roasting condition, easily sinter and
Reduce, even if increasing the dosage of transforming agent, also do not reach expected conversion and leaching rate, cause that consumption of raw materials is big, production cost
It is high.The navajoite enterprise that about 3,000 tons/year of production capacity consumes about 10~120,000 tons/year of the dosage of soda ash every year, consumes sodium chloride
About 17~180,000 tons/year of dosage, and the conversion of vanadium and leach much fall flat, certainly will so influence total efficiency
And the normal operation of production technology.At the same time, the roasting process for extracting vanadium using sodium chloride as transforming agent, discharge discharge capacity it is exceeded and
The corrosive gas such as chlorine, the hydrogen chloride for causing seriously to pollute to surrounding enviroment.
Therefore, develop a kind of conversion rate of vanadium is fast, leaching rate is high, production cost is low, it is environmentally friendly be used for from
The transforming agent of vanadium extraction has critically important realistic meaning in vanadium raw ore.
The content of the invention
It is an object of the invention to provide a kind of transforming agent and its application method for being used for the vanadium extraction from vanadium raw ore, inventor
Being found surprisingly that transforming agent disclosed by the invention can partly substitute or completely in the compatibility of vanadium raw ore, balling-up and roasting process
The sodium salt (soda ash or sodium chloride) in traditional roasting technique is substituted, accelerates the conversion rate of vanadium, improves the leaching rate of vanadium, and
And the influence of other technological parameters such as the species from vanadium raw ore, the height of content of vanadium and roasting furnace temperature in process of production.
To solve the problems, such as that conversion rate existing in the prior art is slow, conversion ratio is low, consumption of raw materials is big, of high cost, environmental pollution is big.
Specifically, to achieve the above object, the first aspect of the present invention, which provides, a kind of is used for the vanadium extraction from vanadium raw ore
Transforming agent, the transforming agent include the raw material of following parts by weight：85~95 parts of vanadium silicide, 2~6 parts of vanadic anhydride, methyl
Red 8~15 parts of sodium salt.
Further, the transforming agent includes the raw material of following parts by weight：89~92 parts of vanadium silicide, vanadic anhydride
3.5~5.5 parts, 10~12.5 parts of methyl red sodium salt.
Further, at normal temperatures and pressures, weigh and mix regulation parts by weight raw material, stir, and grind
To 60~80 mesh, that is, transforming agent is made.
Wherein, vanadium silicide, chemical formula VSi2, grey metal powder.
Methyl red sodium, also known as 2- [4- (dimethylamino) phenylazo] benzoic acid sodium salt, it can pass through 2- [4- (two
Methylamino) phenylazo] benzoic acid and equimolar amounts soda ash (Na2CO3) in a heated condition reaction be prepared, when anti-
System is answered to be completed there is no during bubble spilling it can be assumed that reacting.
It is produced by the present invention be used for from vanadium raw ore the transforming agent of vanadium extraction there is following physical property：
Relative density D42O is 0.9~1.23g/cm3(being measured according to hydrometer method), refraction fraction (are surveyed for 1.3~1.55
Method is determined referring to GB 614/88), silicone content is 20~40% (assay method is referring to GB/T 28600-2012), oxygen content 30
~50% (assay method is referring to GB/T 2406.1-2005), content of vanadium are 3~6% (assay method is referring to GB 3283-87).
The second aspect of the present invention provides a kind of above-mentioned application method for being used for the transforming agent of vanadium extraction from vanadium raw ore, bag
Include following steps,
Crush vanadium raw ore；Add transforming agent；It is uniformly mixed and adds water ball；Roasting is again through leaching, extracting, precipitating, decomposing work
Skill, you can vanadic anhydride is made.
Further, vanadium raw ore is crushed to the particle that granularity is 60~100 mesh sizes.
Further, the calcination temperature of the roasting is 600~800 DEG C, when roasting time is 3~4 small.
Further, the vanadium raw ore include vanadium slag, Rock coal containing alum, vanadium oxidation mud, one kind in industrial waste containing vanadium or
It is a variety of.
Further, the additive amount of the transforming agent is the 3~6% of vanadium ore quality.
The transforming agent for being used for the vanadium extraction from vanadium raw ore of the present invention, can portion when carrying out compatibility with the vanadium original ore powder of crushing
Divide and substitute or substitute completely the soda ash or sodium chloride originally used.The equipment that transforming agent is added to miberal powder balling-up with vanadium original ore powder
In, pelletizing is made, since the transforming agent of the present invention has splendid adhesive force and affinity, in roasting process, when temperature liter
During to 380 DEG C, transforming agent lure component under the action of, start convert vanadium raw ore inside lower valency vanadium, when temperature rises to
At 600~800 DEG C, decomposed because methyl red sodium salt high-temp combustion and generate carbon dioxide and generation salt is quick-fried in pelletizing, made
Appearance is cellular in pelletizing, while the expansion of silicon increases pelletizing volume, and the vanadium kind in transforming agent further lures lower valency
Vanadium is converted into five valence state vanadium, and the conversion rate under the action of transforming agent of the lower valency vanadium in vanadium raw ore is fast, leaching rate is high, vanadium conversion
Rate can bring up to more than 90% by the 60~70% of traditional handicraft.In addition, the transforming agent of the present invention can be long-term with vanadium original ore powder
Coexist, even if at high temperature, reduction reaction will not occur to the five valence state vanadium for having converted leaching.
The invention has the advantages that：
1st, transforming agent of the invention can significantly destroy the lattice structure containing vanadium mineral in vanadium raw ore at high temperature, promote vanadium pendulum
De- constraint and free, vanadium conversion ratio is up to more than 90%；Utilize the CO that generation is decomposed under high temperature2Make pelletizing loose porous, make
Pelletizing comes into full contact with oxygen, improves reaction efficiency, shortens the reaction time, vanadium high conversion rate.
2nd, transforming agent of the sodium salt that transforming agent of the invention can replace containing chlorion as vanadium raw ore, solves traditional work
Exhaust gas (such as chlorine, hydrogen chloride) is seriously polluted caused by environment in skill route；Meanwhile transforming agent component methyl red of the invention
Sodium salt contains carbon source, and when burning conversion agent releases heat, reduces energy consumption, is that a kind of resource utilization is high, production cost is low, ring
Pollute small or even free of contamination environment-friendly type vanadium raw ore transforming agent in border.
3rd, transforming agent of the invention is adaptable, and the roasting and conversion suitable for various vanadium raw ores aoxidize, and are producing
Cheng Zhong, any equipment and process conditions can reach that leaching velocity is fast, quality is good, high income effect without changing.
Embodiment
Following embodiments are used to illustrate the present invention, but are not limited to the scope of the present invention.Used in following embodiments
The source of reagent is as follows：
Vanadium silicide is purchased from Jiangsu granary the Changjiang river Chemical Co., Ltd., Donghua V-Si Co., Ltd., Suzhou City；
Vanadic anhydride purchased from Hunan newly grand Fan Ye Co., Ltds, Guangxi in Jiang Fan industry Co., Ltd；
Methyl red sodium salt can also pass through 2- [4- purchased from ten thousand Hua Fan industry Co., Ltd of Hunan, Anhui Maanshan chemical company
(dimethylamino) phenylazo] benzoic acid and equimolar amounts soda ash (Na2CO3) reaction be prepared.
Embodiment 1
The transforming agent for being used for the vanadium extraction from vanadium raw ore of the present embodiment, includes the raw material of following parts by weight：Vanadium silicide 85
Part, 2 parts of vanadic anhydride, 8 parts of methyl red sodium salt.At normal temperatures and pressures, weigh and mix regulation parts by weight raw material, fully stir
Mix uniformly, and be ground to 60~80 mesh, that is, transforming agent is made.
97 kilograms of Rock coal containing alum is weighed, vanadium content is 0.8~1% after measured, and it is 60~100 mesh to be crushed to granularity, addition 3
Kilogram above-mentioned transforming agent, i.e. additive amount is 3%, after stirring, the pelletizing that adds water to be made a diameter of 4~5 centimetres, warp
When 600~800 DEG C of roastings 3~4 are small, pelletizing volume increase, diameter increases to about 6~7 centimetres, and pelletizing color is changed into canescence,
Room temperature is cooled to, carries out conventional leaching, vanadic anhydride is made in extraction, precipitation, decomposition technique, is measured according to GB3283-87
Vanadium conversion ratio is 93%.
Embodiment 2
The transforming agent for being used for the vanadium extraction from vanadium raw ore of the present embodiment, includes the raw material of following parts by weight：Vanadium silicide 89
Part, 3.5 parts of vanadic anhydride, 10 parts of methyl red sodium salt.At normal temperatures and pressures, weigh and mix regulation parts by weight raw material group
Point, stir, and be ground to 60~80 mesh, that is, transforming agent is made.
94 kilograms of vanadium slag is weighed, vanadium content is 14~16% after measured, and it is 60~100 mesh to be crushed to granularity, adds 6 kilograms
Above-mentioned transforming agent, i.e. additive amount is 6%, after stirring, the pelletizing that adds water to be made a diameter of 4~5 centimetres, through 600
When~800 DEG C of roastings 3~4 are small, pelletizing volume increase, diameter increases to about 6~7 centimetres, and pelletizing color is changed into having metal glittering
Canescence, be cooled to room temperature, carry out conventional leaching, vanadic anhydride, foundation is made in extraction, precipitation, decomposition technique
GB3283-87 measures vanadium conversion ratio as 92%.
Embodiment 3
The transforming agent for being used for the vanadium extraction from vanadium raw ore of the present embodiment, includes the raw material of following parts by weight：Vanadium silicide 90
Part, 4 parts of vanadic anhydride, 11 parts of methyl red sodium salt.At normal temperatures and pressures, weigh and mix regulation parts by weight raw material components,
Stir, and be ground to 60~80 mesh, that is, transforming agent is made.
90 kilograms of Rock coal containing alum is weighed, vanadium content is 0.8~1% after measured, weighs 6 kilograms of industrial wastes containing vanadium, through surveying
It is 3~8% to determine vanadium content, and it is 60~100 mesh to mix above-mentioned material and be crushed to granularity, the above-mentioned transforming agent of 4 kilograms of addition, i.e.,
Additive amount is 4%, after stirring, the pelletizing that adds water to be made a diameter of 4~5 centimetres, through 600~800 DEG C of roastings 3~4
Hour, pelletizing volume increase, diameter increases to about 6~7 centimetres, and pelletizing color is changed into white and brick-red, is cooled to room temperature, into
Vanadic anhydride is made in the conventional leaching of row, extraction, precipitation, decomposition technique, and measuring vanadium conversion ratio according to GB3283-87 is
90%.
Embodiment 4
The transforming agent for being used for the vanadium extraction from vanadium raw ore of the present embodiment, includes the raw material of following parts by weight：Vanadium silicide 92
Part, 5.5 parts of vanadic anhydride, 12.5 parts of methyl red sodium salt.At normal temperatures and pressures, weigh and mix regulation parts by weight raw material group
Point, stir, and be ground to 60~80 mesh, that is, transforming agent is made.
Vanadium 95 kilograms of mud of oxidation is weighed, vanadium content is 7~12% after measured, and it is 60~100 mesh to be crushed to granularity, addition 5
Kilogram above-mentioned transforming agent, i.e. additive amount is 5%, after stirring, the pelletizing that adds water to be made a diameter of 4~5 centimetres, warp
When 600~800 DEG C of roastings 3~4 are small, pelletizing volume increase, diameter increases to about 6~7 centimetres, and pelletizing color is changed into grey, into
Vanadic anhydride is made in the conventional leaching of row, extraction, precipitation, decomposition technique, and measuring vanadium conversion ratio according to GB3283-87 is
94%.
Embodiment 5
The transforming agent for being used for the vanadium extraction from vanadium raw ore of the present embodiment, includes the raw material of following parts by weight：Vanadium silicide 95
Part, 6 parts of vanadic anhydride, 15 parts of methyl red sodium salt.At normal temperatures and pressures, weigh and mix regulation parts by weight raw material components,
Stir, and be ground to 60~80 mesh, that is, transforming agent is made.
88 kilograms of vanadium slag is weighed, vanadium content is 14~16% after measured, weighs 8 kilograms of industrial wastes containing vanadium, contains after measured
Vanadium amount is 3~8%, and it is 60~100 mesh to mix above-mentioned material and be crushed to granularity, and the above-mentioned transforming agent of 4 kilograms of addition, that is, add
Measure as 4%, after stirring, the pelletizing that adds water to be made a diameter of 4~5 centimetres, through 600~800 DEG C of roastings 3~4 it is small when,
Pelletizing volume increases, and diameter increases to about 6~7 centimetres, and pelletizing color is changed into white and brick-red, carries out conventional leaching, carries
Take, precipitate, vanadic anhydride is made in decomposition technique, measure vanadium conversion ratio according to GB3283-87 as 95%.
Although above with general explanation and specific embodiment, the present invention is described in detail, at this
On the basis of invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Therefore,
These modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to the scope of protection of present invention.
Claims (8)
1. a kind of transforming agent for being used for the vanadium extraction from vanadium raw ore, it is characterised in that the transforming agent includes following parts by weight
Raw material：85~95 parts of vanadium silicide, 2~6 parts of vanadic anhydride, 8~15 parts of methyl red sodium salt.
2. the transforming agent according to claim 1 for being used for the vanadium extraction from vanadium raw ore, it is characterised in that the transforming agent includes
The raw material of following parts by weight：89~92 parts of vanadium silicide, 3.5~5.5 parts of vanadic anhydride, 10~12.5 parts of methyl red sodium salt.
3. the transforming agent according to claim 1 for being used for the vanadium extraction from vanadium raw ore, it is characterised in that at normal temperatures and pressures,
Weigh and mix regulation parts by weight raw material, stir, and be ground to 60~80 mesh, that is, transforming agent is made.
4. the use for being used for the transforming agent of vanadium extraction from vanadium raw ore described in a kind of any one of claims 1 to 3 claim
Method, it is characterised in that comprise the following steps,
Crush vanadium raw ore；Add transforming agent；It is uniformly mixed and adds water ball；Roasting is again through leaching, extracting, precipitating, decomposition technique, i.e.,
Vanadic anhydride can be made.
5. the application method according to claim 4 for being used for the transforming agent of vanadium extraction from vanadium raw ore, it is characterised in that by vanadium
Raw ore is crushed to the particle that granularity is 60~100 mesh sizes.
6. the application method according to claim 4 for being used for the transforming agent of vanadium extraction from vanadium raw ore, it is characterised in that described
The calcination temperature of roasting is 600~800 DEG C, when roasting time is 3~4 small.
7. the application method according to claim 4 for being used for the transforming agent of vanadium extraction from vanadium raw ore, it is characterised in that described
Vanadium raw ore includes the one or more in vanadium slag, Rock coal containing alum, vanadium oxidation mud, industrial waste containing vanadium.
8. the application method according to claim 4 for being used for the transforming agent of vanadium extraction from vanadium raw ore, it is characterised in that described
The additive amount of transforming agent is the 3~6% of vanadium ore quality.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116005010A (en) * | 2023-01-17 | 2023-04-25 | 中钒劲宏(苏州)新材料发展有限公司 | Vanadium conversion agent, preparation method and application thereof, and method for extracting vanadium |
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| US4039614A (en) * | 1972-07-17 | 1977-08-02 | Slotvinsky Sidak Nikolai Petro | Method of preparing vanadium pentoxide from metallurgical slags containing vanadium |
| CN103643045A (en) * | 2013-12-09 | 2014-03-19 | 攀钢集团研究院有限公司 | Treatment method of vanadium extraction tailings |
| CN104294033A (en) * | 2013-07-16 | 2015-01-21 | 无锡华冶钢铁有限公司 | Vanadium extracting process for silicate type vanadium ore |
| CN105648220A (en) * | 2016-02-03 | 2016-06-08 | 台州天天环保科技有限公司 | Technology for recycling vanadium from hydrogenation tail oil of suspended bed |
| CN106755958A (en) * | 2016-11-30 | 2017-05-31 | 武汉科技大学 | A kind of method that Rock coal containing alum is calcined vanadium extraction |
-
2017
- 2017-12-08 CN CN201711297727.0A patent/CN108034807B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4039614A (en) * | 1972-07-17 | 1977-08-02 | Slotvinsky Sidak Nikolai Petro | Method of preparing vanadium pentoxide from metallurgical slags containing vanadium |
| CN104294033A (en) * | 2013-07-16 | 2015-01-21 | 无锡华冶钢铁有限公司 | Vanadium extracting process for silicate type vanadium ore |
| CN103643045A (en) * | 2013-12-09 | 2014-03-19 | 攀钢集团研究院有限公司 | Treatment method of vanadium extraction tailings |
| CN105648220A (en) * | 2016-02-03 | 2016-06-08 | 台州天天环保科技有限公司 | Technology for recycling vanadium from hydrogenation tail oil of suspended bed |
| CN106755958A (en) * | 2016-11-30 | 2017-05-31 | 武汉科技大学 | A kind of method that Rock coal containing alum is calcined vanadium extraction |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116005010A (en) * | 2023-01-17 | 2023-04-25 | 中钒劲宏(苏州)新材料发展有限公司 | Vanadium conversion agent, preparation method and application thereof, and method for extracting vanadium |
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