CN107299223A - A kind of bone coal is combined alkaline-leaching and vanadium extraction method and its system - Google Patents
A kind of bone coal is combined alkaline-leaching and vanadium extraction method and its system Download PDFInfo
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- CN107299223A CN107299223A CN201710713542.7A CN201710713542A CN107299223A CN 107299223 A CN107299223 A CN 107299223A CN 201710713542 A CN201710713542 A CN 201710713542A CN 107299223 A CN107299223 A CN 107299223A
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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
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- 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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Abstract
Alkaline-leaching and vanadium extraction method and its system are combined the present invention relates to a kind of bone coal, specifically there is provided a kind of method and system of the vanadium extraction from bone coal, methods described includes：A, by stone coal powder roasting obtain bone coal fired slags；B, with compound alkali leaching agent bone coal fired slags are impregnated, obtain leachate and leached mud after separation of solid and liquid；C, leached mud is washed with water, separation of solid and liquid obtains cleaning solution and washing residue；D, cleaning solution and part leachate are added into after compound alkali return to step B are used as compound alkali leaching agent；Removal of impurities liquid is obtained after E, the addition calcium compound reaction into remaining leachate, separation of solid and liquid；F, it is passed through into removal of impurities liquid carbonate and rich vanadium solution that carbon dioxide obtained after carbon point, the carbonate of precipitated sodium, separation of solid and liquid sodium.
Description
Technical field
The present invention relates to extracting vanadium from stone coal technical field, and in particular to a kind of bone coal is combined alkaline-leaching and vanadium extraction method and its system.
Background technology
Vanadium is a kind of important alloying element, there is extensive purposes.Bone coal be China it is important contain vanadium resource, reserves are huge
It is big and widely distributed.Determination of Different Valence States result of study of the vanadium in bone coal shows that vanadium is main in bone coal exists in four kinds of forms：(1)V
(III) it is present in isomorph substitution Al (III) in mica mineral, it is the topmost existence form of vanadium in bone coal；
(2) vanadium is present in the surface of clay mineral and ferriferous oxide colloid in ADSORPTION STATE form；(3) vanadium is in metallo-organic complex form
In the presence of；(4) vanadium exists in Within Monominerals form.Just because of existence form variation of the vanadium in bone coal, so big to extracting vanadium from stone coal
Add difficulty greatly.
Traditional sodium roasting and the technique rate of recovery of calcification baking extracting vanadium from stone coal are preferable not enough, and the former has serious ring
Border pollution problem, requirement of the latter to bone coal original ore property is harsher.Although process for extracting vanadium by acid leaching can improve the leaching rate of vanadium
And the rate of recovery, reduce environmental pollution, but sour large usage quantity, it is serious to equipment corrosion, foreign ion species and contain in pickle liquor
Amount is high, and subsequent treatment is complex, and the waste water and dregs of generation are difficult, is restricted etc. and to ask in technology and equipment development level
Topic.
The rise of current alkaline-leaching and vanadium extraction technique, alleviates environmental protection pressure, during alkali leaching selectivity preferably, Fe in bone coal,
Ca, Mg etc. are not leached, and the major impurity in leachate is Si, P, and removal of impurities is relatively easy, anti-corrosion of the alkali soaking technology to equipment
It is required that it is low, equipment construction and maintenance cost are reduced, therefore the method soaked using alkali is the important development direction of extracting vanadium from stone coal.But
The main deficiency of current alkali soaking technology is in alkali consumption height, leachate that however, residual base utilization rate is low, and leachate concentration containing vanadium is low, after
Continuous treating capacity is big, increases production cost, difficulty realizes popularization and application.
The content of the invention
High, the high energy consumption present invention aim to address production cost present in original technique, environmental pollution is serious, subsequently
Handle complicated shortcoming there is provided a kind of clean environment firendly, higher vanadium recovery can be realized, alkaline consumption can be reduced again and is produced into
This vanadium extract technology.
To achieve these goals, one aspect of the present invention provides a kind of method of the vanadium extraction from bone coal, methods described bag
Include：
A, by stone coal powder roasting obtain bone coal fired slags；
B, with compound alkali leaching agent bone coal fired slags are impregnated, obtain leachate and leached mud after separation of solid and liquid；
C, leached mud is washed with water, separation of solid and liquid obtains cleaning solution and washing residue；
D, cleaning solution and part leachate are added into after compound alkali return to step B are used as compound alkali leaching agent；
Removal of impurities liquid is obtained after E, the addition calcium compound reaction into remaining leachate, separation of solid and liquid；
F, it is passed through into removal of impurities liquid the carbon that carbon dioxide obtained after carbon point, the carbonate of precipitated sodium, separation of solid and liquid sodium
Hydrochlorate and rich vanadium solution.
Preferably, method of the invention can also include：The flue gas of generation is collected in step；The flue gas of collection is net
It is passed through after change in step F in removal of impurities liquid and carries out carbon point.
Preferably, method of the invention can also include preparing vanadium product with rich vanadium solution, such as ammonium vanadate, five oxidations two
Vanadium etc..In one embodiment, ammonium vanadate can be prepared with rich vanadium solution, ammonium vanadate roasting is then obtained into five oxidations two
Vanadium.
In step, the particle diameter of stone coal powder is not specifically limited, as long as not influenceing roasting effect.However, it is preferred to
The granularity of stone coal powder is more than 60 mesh, more preferably more than 80 mesh, such as more than 100 mesh.Do not have to the lower limit of bone coal Powder Particle Size
Limit, but it is meticulous can increase grinding cost, it is therefore general below 300 mesh, such as below 200 mesh.For example, stone coal powder can
To prepare as follows：Will be levigate with ball mill after bone coal coarse crushing, sieved with 100 mesh sieves, extracting screen underflow obtains stone coal powder.
In step, the purpose of roasting is to remove the charcoal and volatile oxide in bone coal, and that destroys bone coal contains vanadium
Mineral structure, makes the Low Valent Vanadium in bone coal be oxidized to high price vanadium, contributes to the leaching of vanadium.The temperature and time of roasting is not special
Limit, as long as above-mentioned purpose can be realized.Preferably, roasting can be carried out at 800 DEG C~1000 DEG C, and the time can be
1~4h, preferably 2~3h.In addition, roasting can be carried out in any suitable equipment, such as carried out in Muffle furnace.
In step, the step of preferably also including crushing bone coal fired slags.Granularity after crushing can be in 60 mesh to 300
Between mesh, preferably 100~200 mesh.For example, the pulverising step can prepare it is as follows：Bone coal after roasting is thin through ball mill
Sieved after broken with 100 mesh sieves, extracting screen underflow obtains bone coal fired slags powder.Bone coal fired slags are crushed and can further be increased
Strong leaching effect.
In step, the flue gas of generation can also be collected standby.The Main Ingredients and Appearance of flue gas is C, S, N oxide,
Such as CO2、SO3、SO2、NO、NO2Deng, thus can be used for step F carbon point.So, the flue gas on the one hand produced is recycled
Recycle, it is therefore prevented that air pollution, on the other hand the carbonate of gained sodium can return to leaching section and recycle, and reduce life
Cost is produced, while the basicity of removal of impurities liquid can be reduced, greatly reduces the acid amount adjusted when subsequently preparing ammonium vanadate needed for pH value.
In stepb, being combined alkali is used for the sial acid reaction in bone coal, the vanadium wrapped up with dissolution by alumino-silicate.It is multiple
Alkali is closed to be made up of sodium hydroxide, sodium carbonate and optional sodium acid carbonate.In the present invention, using the NaHCO of lower cost3、Na2CO3
Fired slags are leached with the compound alkali leaching agent that NaOH is made into, can have been saved in the case where not influenceing V leaching rate into
This.
The compound alkali leaching agent is the aqueous solution of compound alkali, and basicity (in terms of sodium hydroxide) is 60~250g/l, preferably
For 80~150g/l.Preferably, with sodium hydroxide, sodium acid carbonate and sodium carbonate be respectively 40~80g/l, 0~60g/l and 10~
60g/l, respectively preferably 50~70g/l, 0~50g/l, 20~50g/l consumption prepare compound alkali leaching agent.
When being impregnated, the bone coal fired slags based on 1 parts by weight, the consumption for being combined alkali leaching agent is preferably 1~4 weight
Part, more preferably 2~3 parts by weight.Dipping is preferably carried out under agitation.Dipping temperature is not particularly limited, as long as can carry out anti-
Should, it is preferred that for 70~100 DEG C, more preferably 80~95 DEG C.Dip time is not particularly limited, as long as can complete
Reaction, it is preferred that being 1~4h, more preferably 2~3h.
In stepb, leachate and leached mud are obtained after separation of solid and liquid.
In step C, leached mud is washed with water and obtains cleaning solution and washing residue.Wash for by the residual alkali in leached mud
Washed out with remaining solvable vanadium.Washing may be carried out batchwise or be carried out continuously.In the case where interval is carried out, do not have to washing times
It is specifically limited, as long as realizing washing purpose.1~3 time, preferably 1~2 time can for example be washed.What is repeatedly washed
In the case of, rear washing gained cleaning solution is preferably recycled to previous washing.For example in the case where wash twice, by the
Cleaning solution obtained by secondary washing is back to be washed for washing leached mud for the first time., can in the case where being carried out continuously washing
To carry out countercurrent washing to leached mud with water.The consumption of water is not specifically limited, but based on the leached mud of 1 parts by weight, preferably
The consumption of water is 1~3 parts by weight, more preferably 1~2 parts by weight.
It is mainly silicate and alumino-silicate to wash residue, may be used as preparing cement building material.
In step D, cleaning solution obtained by step C and part leachate are added into return to step B after compound alkali allotment to be used as
Compound alkali leaching agent.The amount of return to step B leachate is not particularly limited, it is preferred that for leachate total amount about 1/4 to
3/4, even more preferably about 1/2.After multiple leachate reflux cycle, the vanadium concentration in leachate is gradually stablized.Using leachate
Vanadium concentration increase in alkali and water consumption, and obtained final leachate can be substantially reduced after reflux cycle extract technology, is had
Beneficial to follow-up vanadium extraction everything goes well with your work carry out.The compound alkali number added is not particularly limited, it is preferred that to mend to 60~250g/l
(basicity is in terms of sodium hydroxide in the present invention), more preferably 80~150g/l.
In step E, removal of impurities liquid is obtained after calcium compound reaction, separation of solid and liquid are added into remaining leachate.In alkali leaching
During, the metal ion such as Fe, Ca, Mg in bone coal fired slags is not leached under basic conditions, main in leachate
Impurity is Si, P, with SiO3 2-、PO4 3-Form is present.Leachate is strong basicity, its pH>14.Directly calcium can be added to leachate
Compound is reacted to remove the Si and P in leachate.The calcium compound can for example be selected from Ca (OH)2、CaCl2With
CaO, preferably CaO.It is not particularly limited for reaction temperature and time, as long as enabling to Si and P and the calcium in leachate
Compound is reacted.Preferable reaction temperature is between 60~100 DEG C, more preferably between 70~95 DEG C, is, for example, about 90 DEG C.
Reaction time can be about more than 10 minutes, more than about 30 minutes, e.g., from about 1h.After reaction removal of impurities liquid is obtained through separation of solid and liquid.
Solid is calcium-silicon slag, can be used for preparing cement building material.
In step F, carbon dioxide is passed through into removal of impurities liquid and obtained after carbon point, the carbonate of precipitated sodium, separation of solid and liquid
To the carbonate and rich vanadium solution of sodium.The carbon dioxide can be partly or entirely with the flue gas after collection and purification in step
Instead of can so cause the flue gas that step A is produced to be recycled recycling, air pollution be prevented, moreover, S, N in flue gas
Oxide can neutralize the basicity of removal of impurities liquid, and the acid amount needed for pH value is adjusted when subsequently preparing ammonium vanadate so as to greatly reduce.
The gas cleaning refers to removing bulky grain mine dust and harmful components in flue gas, such as arsenic, selenium compound.Obtained sodium
Carbonate be mainly sodium acid carbonate, be mingled with the sodium carbonate of sub-fraction.The carbonate of sodium can be used for preparing compound alkali leaching
Agent, returns to leaching section and recycles, reduce production cost.Therefore, step F may further include resulting sodium
The step of carbonate is used to prepare compound alkali leaching agent.
Gained richness vanadium solution can be further used for preparing vanadium product, such as ammonium vanadate, vanadic anhydride.For example, first
First by rich vanadium solution adjust pH to 2~3, then through D201 resins carry out ion exchange with remove the impurity in rich vanadium solution sun from
Son, such as K+, increase the purity of vanadium product.The solubility due to potassium metavanadate can be eliminated by carrying out ion exchange through D201 resins
It is small compared with ammonium metavanadate to cause in the case where not removing, substantial amounts of potassium metavanadate can be mixed with obtained ammonium metavanadate, is influenceed
The problem of product purity.Loaded resin obtains the vanadium solution of high concentration after elution, and high concentration vanadium liquid is adjusted into pH to 2
Acid ammonium salt precipitation vanadium is added after~3 thereto and obtains ammonium vanadate solid.Described acid ammonium salt can be ammonium chloride, sulfuric acid
Ammonium, ammonium nitrate etc..Described eluent can be one or both of sodium hydroxide or sodium chloride solution, wherein sodium hydroxide
Mass fraction with sodium chloride can be 1%~14%, preferably 3%~10%.Ammonium vanadate is calcined 2 at 500~600 DEG C
Impurity component is obtained after~3h and content meets the vanadic anhydride product of the quality standards of GB3283-87.
The system that another aspect of the present invention provides the vanadium extraction from bone coal, the system includes：
First calciner, it is used to stone coal powder roasting obtaining bone coal fired slags；
Compound alkali leaching agent storing apparatus, it is used to store compound alkali leaching agent；
Leaching device, it receives bone coal fired slags from the first calciner and from compound alkali leaching agent storing apparatus
Compound alkali leaching agent, for compound alkali leaching agent impregnate bone coal fired slags；
First equipment for separating liquid from solid, it receives the mixing of compound alkali leaching agent and bone coal fired slags from leaching device
Leachate and leached mud are obtained after thing, separation of solid and liquid；
Wash mill, it receives the leached mud from the first equipment for separating liquid from solid of connection, for leached mud to be washed with water；
After second equipment for separating liquid from solid, the mixture of leached mud and water of its receiving from wash mill, separation of solid and liquid
To cleaning solution and washing residue；
Liquid conveyer, it receives cleaning solution from the second equipment for separating liquid from solid and from the first equipment for separating liquid from solid
Part leachate, and they are transported to compound alkali leaching agent storing apparatus；
First reaction unit, it receives the leachate from the first equipment for separating liquid from solid, in the first reaction unit, leaches
Liquid reacts with the calcium compound added；
3rd equipment for separating liquid from solid, it is removed after receiving the reactant mixture from the first reaction unit, separation of solid and liquid
Miscellaneous liquid and calcium-silicon slag；
Carbon dioxide storing apparatus, it is used to store carbon dioxide；
Carbon point reaction unit, it receives removal of impurities liquid from the 3rd equipment for separating liquid from solid and from carbon dioxide storing apparatus
Carbon dioxide, for carrying out carbon point reaction；
4th equipment for separating liquid from solid, it obtains sodium after receiving the reactant mixture from carbon point reaction unit, separation of solid and liquid
Carbonate and rich vanadium solution；
Solid conveyer, it receives the carbonate of the sodium from the 4th equipment for separating liquid from solid, and carries it to compound
Alkali leaching agent storing apparatus.
The system of vanadium extraction from bone coal of the present invention can also include smoke gas collecting apparatus, and it receives and collects calciner
The flue gas produced in roasting process.
The system of vanadium extraction from bone coal of the present invention can also include smoke eliminator, and it receives from fume collection dress
The flue gas put, and purified.
The smoke gas collecting apparatus and smoke eliminator of the present invention, which can also be combined, realizes fume collection and purification
Function, such as flue gas cleaner.
The system of vanadium extraction from bone coal of the present invention can also include gas transport device, and it receives from gas cleaning dress
Flue gas after the purification put, and carbon point reaction unit is conveyed to for being passed through progress carbon point in removal of impurities liquid.
The system of vanadium extraction from bone coal of the present invention can also include：
PH adjusting meanss, it receives the rich vanadium solution from the 4th equipment for separating liquid from solid, by rich vanadium in pH adjusting meanss
The pH of solution is adjusted to 2~3；
Pro-concentration with ion exchange process vanadium extraction device, it receives the rich vanadium solution after the pH regulations from pH adjusting meanss, and carries out
Then ion exchange obtains vanadium solution to remove the impurity cationic in rich vanadium solution after elution；
Settler, it receives the vanadium solution from Pro-concentration with ion exchange process vanadium extraction device, in settler, by vanadium solution
PH is adjusted to 2~3, then adds acid ammonium salt precipitation vanadium；
5th equipment for separating liquid from solid, it receives the precipitation reaction mixture from settler, and separation of solid and liquid obtains vanadic acid
Ammonium solid.
The system of vanadium extraction from bone coal of the present invention can also include：Second calciner, it receives to come from the 5th solid-liquid
The ammonium vanadate solid of separator is simultaneously roasted to vanadic anhydride.
The system of vanadium extraction from bone coal of the present invention can also include breaker, for bone coal to be crushed to suitable grain
Degree, such as disintegrating machine, ball mill.
The said apparatus of the present invention is not particularly limited, as long as described function can be realized, can use ability
The device conventionally used for realizing the function in domain.For example, calciner can be calcining kiln, roaster, calcining furnace, fusing
Stove etc..Storing apparatus can be storage tank, storage tank etc..Leaching device, wash mill, the first reaction unit, carbon point reaction unit, pH
Adjusting means and settler can be slot type reaction unit (such as tank diameter), reactor.Equipment for separating liquid from solid can be
Filter press (such as plate and frame filter press), centrifuge, nutsch filter.Pro-concentration with ion exchange process vanadium extraction device can be anion exchanger
Deng such as anion-exchange resin column.
In addition, as needed, in the visual field of those skilled in the art, can on said apparatus inlet porting and/or
Outlet, with the connection needed for realizing, charging or discharging.In addition, as needed, in the visual field of those skilled in the art, may be used also
To increase servicing unit, such as agitating device, drying device, pipeline, pump (such as measuring pump, circulating pump, delivery pump), valve
Door, heat exchanger (such as plate type heat exchanger), condensing unit, heater, conveyer, batcher.
The present invention from bone coal in the system of vanadium extraction, the raw material and description and the foregoing teachings of condition used for technique
It is identical, it will not be repeated here.
Beneficial effect
1st, the present invention uses alkaline matter preferable to ion selectivity as leaching agent vanadium extraction, Fe in bone coal fired slags, Ca,
The metal ions such as Mg are not leached, and the major impurity in leachate is Si, P, and removal of impurities is relatively easy, low for equipment requirements, leaching
Extracting rate is high.
2nd, the present invention considers that sodium hydroxide concentration is big, and production cost is high, therefore uses the NaHCO of lower cost3、Na2CO3
Fired slags are leached as leaching agent with the compound alkali that NaOH is made into, saved in the case where not influenceing V leaching rate into
This.
3rd, the present invention is using after the leachate reflux cycle extract technology of part, and alkali and water consumption are substantially reduced, and are obtained
Leachate in the increase of vanadium concentration, be conducive to follow-up vanadium extraction everything goes well with your work progress.
4th, leachate uses calcium compound in pH in the present invention>Removal of impurities under 14 alkalescence condition, first tune pH as compared with the past
To alkalescent removal of impurities again, without acid consumption, and removal of impurities is thorough.
5th, the flue gas that the present invention is produced after being calcined using bone coal carries out carbon point and reclaims sodium acid carbonate, the flue gas on the one hand produced
Being recycled recycling prevents air pollution, and another aspect sodium acid carbonate returns again to leaching section and recycled, and reduces production
Cost, while the basicity of removal of impurities liquid is also reduced, acid amount greatly reduces needed for adjusting pH value.
6th, operating procedure of the present invention is simple, it is easy to industrialization promotion, has certain economic effect under current technical conditions
Pollutant is not produced in benefit and production process, is had the advantages that environment-friendly.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1：
Raw material：Rock coal containing alum is derived from Anhui province, and vanadium grade is 0.71%.
Bone coal is with levigate to less than 150 μm by ball mill again after disintegrating machine coarse crushing, by bone coal through 850 DEG C in roaster
Fired slags are obtained after roasting 3.0h, it is standby to collect gas cleaning with flue gas cleaner.
Bone coal fired slags are levigate with ball mill, sieved with 100 mesh sieves, extracting screen underflow is added in leaching tanks, by liquid
Gu it is 2 than (weight ratio):1 ratio adds compound alkali leaching agent from compound alkali leaching agent storage tank, wherein in compound alkali leaching agent
Sodium hydroxide and concentration of sodium carbonate are respectively 70g/l and 40g/l, and basicity is 142g/l.The stirring reaction under 95 DEG C of waters bath with thermostatic control
2h。
During the mixture discharged from leaching tanks is imported into plate and frame filter press, leachate and leached mud are obtained after separation of solid and liquid,
It is 35% or so to control water content in slag.
Leached mud is carried out to clear water washing twice in sink, wash water reversely flows back towards use, through plate and frame filter press separation of solid and liquid
Cleaning solution and washing residue are obtained, it is 35% or so to control water content in slag.Washing residue is stored up.
Compound alkali leaching agent is formulated as after cleaning solution and 1/2 volume leachate are returned into compound alkali leaching agent storage tank benefit alkali,
It is 148g/l to mend basicity after alkali.
The content of vanadium in leached mud is determined with potassium permanganate-iron ammonium sulfate method, the rate of recovery of vanadium is extrapolated, once follows
Vanadium recovery is 89.06% after ring, and vanadium recovery is stable 84.00% or so after repeatedly circulation.
Remaining leachate is imported in reactor, calcium oxide is added into leachate 1h, reaction mixing is reacted at 90 DEG C
Thing obtains removal of impurities liquid and calcium-silicon slag after importing plate and frame filter press separation of solid and liquid.Calcium-silicon slag is stored up.
Removal of impurities liquid is imported in reactor, the flue gas after collection and purification is passed through and carries out carbon point, separate out sodium acid carbonate and carbonic acid
The salt-mixture of sodium.Mixture after carbon point is imported in plate and frame filter press, sodium acid carbonate is obtained after separation of solid and liquid and (is wherein mingled with
Sodium carbonate) and rich vanadium solution.Solid mixture is transported into compound alkali leaching agent storage tank is used to prepare compound alkali leaching agent.By richness
Vanadium liquid adds sulfuric acid to adjust pH to 2.0 again, crosses D201 ion exchange resin column Vanadium Concentrationins.Loaded resin mass fraction is 4%
The vanadium solution of high concentration is obtained after NaOH solution elution.
The vanadium solution of high concentration is obtained into brick-red vanadium with being added thereto after sulphur acid for adjusting pH to 2.0 after ammonium sulfate precipitation
Cake, the mixture after precipitation is imported in plate and frame filter press, liquid after ammonium metavanadate and precipitation is obtained after separation of solid and liquid.By metavanadic acid
Ammonium obtains impurity component after 550 DEG C of roasting kiln roasting 2h and content meets the vanadic anhydride of the quality standards of GB3283-87
Product.
Embodiment 2：
Raw material：Rock coal containing alum is derived from Anhui province, and vanadium grade is 0.71%.
Bone coal is with levigate to less than 150 μm by ball mill again after disintegrating machine coarse crushing, by bone coal through 850 DEG C in roaster
Fired slags are obtained after roasting 2.5h, it is standby to collect gas cleaning with flue gas cleaner.
Bone coal fired slags are levigate with ball mill, sieved with 100 mesh sieves, extracting screen underflow is added in leaching tanks, by liquid
Gu it is 2 than (weight ratio):1 ratio adds compound alkali leaching agent from compound alkali leaching agent storage tank, wherein in compound alkali leaching agent
Sodium hydroxide and sodium acid carbonate concentration are respectively 65g/l and 38g/l, and basicity is 132g/l.Stirred under 90 DEG C of waters bath with thermostatic control anti-
Answer 2.0h.
During the mixture discharged from leaching tanks is imported into plate and frame filter press, leachate and leached mud are obtained after separation of solid and liquid.
Leached mud carries out in sink to clear water washing twice, wash water reversely flows back towards uses, separation of solid and liquid obtain cleaning solution with
Wash residue.Washing residue is stored up.
Compound alkali leaching agent is formulated as after cleaning solution and 1/2 volume leachate are returned into compound alkali leaching agent storage tank benefit alkali,
It is 136g/l to mend basicity after alkali.
The content of vanadium in leached mud is determined with potassium permanganate-iron ammonium sulfate method, the rate of recovery of vanadium is extrapolated, once follows
Vanadium recovery is 87.83% after ring, and vanadium recovery is stable 83.16% or so after repeatedly circulation.
Remaining leachate is imported in reactor, calcium chloride is added into leachate 1.5h is reacted at 90 DEG C, reaction is mixed
Compound obtains removal of impurities liquid and calcium-silicon slag after importing plate and frame filter press separation of solid and liquid.Calcium-silicon slag is stored up.
Removal of impurities liquid is imported in reactor, the flue gas after collection and purification is passed through and carries out carbon point, separate out sodium acid carbonate and carbonic acid
The salt-mixture of sodium.Mixture after carbon point is imported in plate and frame filter press, sodium acid carbonate is obtained after separation of solid and liquid and (is wherein mingled with
Sodium carbonate) and rich vanadium solution.Solid mixture is transported into compound alkali leaching agent storage tank is used to prepare compound alkali leaching agent.By richness
Vanadium liquid adds sulfuric acid to adjust pH to 2.1 again, crosses D201 ion exchange resin column Vanadium Concentrationins.Loaded resin is 3%NaOH+ with mass fraction
The vanadium solution of high concentration is obtained after the elution of 5%NaCl solution.
The vanadium solution of high concentration is obtained into brick-red vanadium with being added thereto after sulphur acid for adjusting pH to 2.0 after ammonium sulfate precipitation
Cake, the mixture after precipitation is imported in plate and frame filter press, liquid after ammonium metavanadate and precipitation is obtained after separation of solid and liquid.By metavanadic acid
Ammonium obtains impurity component after 550 DEG C of roasting kiln roasting 2h and content meets the vanadic anhydride of the quality standards of GB3283-87
Product.
Claims (10)
1. a kind of method of the vanadium extraction from bone coal, methods described includes：
A, by stone coal powder roasting obtain bone coal fired slags；
B, with compound alkali leaching agent bone coal fired slags are impregnated, obtain leachate and leached mud after separation of solid and liquid；
C, leached mud is washed with water, separation of solid and liquid obtains cleaning solution and washing residue；
D, cleaning solution and part leachate are added into after compound alkali return to step B are used as compound alkali leaching agent；
Removal of impurities liquid is obtained after E, the addition calcium compound reaction into remaining leachate, separation of solid and liquid；
F, it is passed through into removal of impurities liquid the carbonate that carbon dioxide obtained after carbon point, the carbonate of precipitated sodium, separation of solid and liquid sodium
With rich vanadium solution.
2. according to the method described in claim 1, wherein,
In step,
The granularity of stone coal powder is more than 60 mesh, more preferably more than 80 mesh, such as more than 100 mesh；And/or
Roasting is carried out at 800 DEG C~1000 DEG C, and the time is 1~4h, preferably 2~3h；And/or
In stepb,
Compound alkali is made up of sodium hydroxide, sodium carbonate and optional sodium acid carbonate；And/or
The compound alkali leaching agent is the aqueous solution of compound alkali, and basicity is calculated as 60~250g/l with sodium hydroxide, preferably 80~
150g/l；Preferably, it is respectively 40~80g/l, 0~60g/l and 10~60g/l with sodium hydroxide, sodium acid carbonate and sodium carbonate,
It is preferred that being respectively 50~70g/l, 0~50g/l, 20~50g/l compound alkali leaching agent of consumption preparation；And/or
When being impregnated, the bone coal fired slags based on 1 parts by weight, the consumption for being combined alkali leaching agent is preferably 1~4 parts by weight,
More preferably 2~3 parts by weight；And/or
Dipping temperature is 70~100 DEG C, more preferably 80~95 DEG C；Dip time is 1~4h, preferably 2~3h；
In step C,
Washing times are 1~5 time, preferably 2~3 times；And/or
In the case where repeatedly wash, rear washing gained cleaning solution is recycled to previous washing；And/or
It is preferred that carrying out countercurrent washing to leached mud with water；And/or
Based on the leached mud of 1 parts by weight, the consumption of water is 1~3 parts by weight, preferably 1~2 parts by weight；And/or
In step D,
The amount of return to step B leachate is 1/4 to 3/4, more preferably the 1/2 of leachate total amount；And/or
The compound alkali number added is calculated as 60~250g/l, more preferably 80~150g/l to basicity for benefit with sodium hydroxide；And/or
In step E,
The calcium compound is selected from Ca (OH)2, CaO and CaCl2, preferably CaO；And/or
Reaction temperature is between 60~100 DEG C, more preferably between 70~95 DEG C, and/or
Reaction time is more than 10 minutes, preferably more than 30 minutes；And/or
In step F,
The carbon dioxide is partly or entirely with the flue gas after collection and purification in step.
3. according to the method described in claim 1, it further comprises：
In step,
Collect the flue gas produced；It will be passed through after the gas cleaning of collection in step F in removal of impurities liquid and carry out carbon point；And/or
Bone coal fired slags are crushed, the granularity after preferably crushing in 60 mesh between 300 mesh, more preferably 100~200 mesh；With/
Or
In step C, washing residue is used as preparing cement building material；And/or
In step E, the solid that separation of solid and liquid is obtained is used to prepare cement building material；And/or
In step F, the carbonate of resulting sodium is used to prepare compound alkali leaching agent.
4. according to the method described in claim 1, it further comprises：The rich vanadium solution of gained is used to prepare vanadium product.
5. method according to claim 4, wherein, rich vanadium solution is adjusted into pH to 2~3, then through D201 resins carry out from
Son is exchanged to remove the impurity cationic in rich vanadium solution, and loaded resin obtains the vanadium solution of high concentration after elution,
Ammonium vanadate solid is obtained by acid ammonium salt precipitation vanadium is added thereto after high concentration vanadium liquid regulation pH to 2~3；
Preferably, described acid ammonium salt is selected from ammonium chloride, ammonium sulfate and ammonium nitrate；And/or, described eluent is selected from hydrogen
The mass fraction of one or both of sodium oxide molybdena and sodium chloride solution, preferably sodium hydroxide and sodium chloride is 1%~14%, more
Preferably 3%~10%.
6. method according to claim 5, wherein, methods described further comprises ammonium vanadate in 500~600 DEG C of roastings
Impurity component is obtained after 2~3h and content meets the vanadic anhydride product of the quality standards of GB3283-87.
7. a kind of system of the vanadium extraction from bone coal, the system includes：
First calciner, it is used to stone coal powder roasting obtaining bone coal fired slags；
Compound alkali leaching agent storing apparatus, it is used to store compound alkali leaching agent；
Leaching device, it receives from the bone coal fired slags of the first calciner and answering from compound alkali leaching agent storing apparatus
Alkali leaching agent is closed, for impregnating bone coal fired slags with compound alkali leaching agent；
First equipment for separating liquid from solid, the mixture of compound alkali leaching agent and bone coal fired slags of its receiving from leaching device, Gu
Leachate and leached mud are obtained after liquid separation；
Wash mill, it receives the leached mud from the first equipment for separating liquid from solid of connection, for leached mud to be washed with water；
Washed after second equipment for separating liquid from solid, the mixture of leached mud and water of its receiving from wash mill, separation of solid and liquid
Wash liquid and washing residue；
Liquid conveyer, it receives the cleaning solution from the second equipment for separating liquid from solid and the portion from the first equipment for separating liquid from solid
Divide leachate, and they are transported to compound alkali leaching agent storing apparatus；
First reaction unit, its receive leachate from the first equipment for separating liquid from solid, in the first reaction unit, leachate with
The calcium compound reaction of addition；
3rd equipment for separating liquid from solid, it obtains removal of impurities liquid after receiving the reactant mixture from the first reaction unit, separation of solid and liquid
And calcium-silicon slag；
Carbon dioxide storing apparatus, it is used to store carbon dioxide；
Carbon point reaction unit, it receives removal of impurities liquid from the 3rd equipment for separating liquid from solid and two from carbon dioxide storing apparatus
Carbonoxide, for carrying out carbon point reaction；
4th equipment for separating liquid from solid, it receives the carbon that sodium is obtained after the reactant mixture from carbon point reaction unit, separation of solid and liquid
Hydrochlorate and rich vanadium solution；
Solid conveyer, it receives the carbonate of the sodium from the 4th equipment for separating liquid from solid, and carries it to the leaching of compound alkali
Go out agent storing apparatus.
8. system according to claim 7, it also includes：
Smoke gas collecting apparatus, it receives and collected the flue gas that calciner is produced in roasting process；It is preferred that it is net also to include flue gas
Makeup is put, and it receives the flue gas from smoke gas collecting apparatus, and is purified；More preferably also include gas transport device, it connects
By the flue gas after the purification of smoke eliminator, and carbon point reaction unit is conveyed to for being passed through progress in removal of impurities liquid
Carbon point；And/or
Breaker, for bone coal to be crushed to suitable granularity.
9. system according to claim 7, it also includes：
PH adjusting meanss, it receives the rich vanadium solution from the 4th equipment for separating liquid from solid, by rich vanadium solution in pH adjusting meanss
PH adjust to 2~3；
Pro-concentration with ion exchange process vanadium extraction device, it receives the rich vanadium solution after the pH regulations from pH adjusting meanss, and carries out ion
Exchange to remove the impurity cationic in rich vanadium solution, then obtain vanadium solution after elution；
Settler, it receives the vanadium solution from Pro-concentration with ion exchange process vanadium extraction device, in settler, vanadium solution pH is adjusted
Then section adds acid ammonium salt precipitation vanadium to 2~3；
5th equipment for separating liquid from solid, it receives the precipitation reaction mixture from settler, and separation of solid and liquid obtains ammonium vanadate and consolidated
Body.
10. system according to claim 9, it also includes：Second calciner, it receives from the 5th separation of solid and liquid dress
The ammonium vanadate solid put simultaneously is roasted to vanadic anhydride.
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| CN115725863A (en) * | 2022-11-22 | 2023-03-03 | 东北大学 | Method for extracting vanadium from vanadium shale by microwave roasting in stages and alkaline leaching step by step |
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