CN107299223B - A kind of compound alkaline-leaching and vanadium extraction method of bone coal and its system - Google Patents
A kind of compound alkaline-leaching and vanadium extraction method of bone coal and its system Download PDFInfo
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- CN107299223B CN107299223B CN201710713542.7A CN201710713542A CN107299223B CN 107299223 B CN107299223 B CN 107299223B CN 201710713542 A CN201710713542 A CN 201710713542A CN 107299223 B CN107299223 B CN 107299223B
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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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- 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
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- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
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Abstract
The present invention relates to a kind of compound alkaline-leaching and vanadium extraction method of bone coal and its systems, specifically, providing a kind of method and system of vanadium extraction from bone coal, which comprises A, roast stone coal powder to obtain bone coal fired slags；B, bone coal fired slags are impregnated with compound alkali leaching agent, obtains 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, return step B is used as compound alkali leaching agent after cleaning solution and part leachate being added compound alkali；E, calcium compound reaction is added in Xiang Qiyu leachate, removal of impurities liquid is obtained after separation of solid and liquid；F, it is passed through carbon dioxide progress carbon into removal of impurities liquid to divide, the carbonate of precipitated sodium, the carbonate and rich vanadium solution of sodium is obtained after separation of solid and liquid.
Description
Technical field
The present invention relates to extracting vanadium from stone coal technical fields, and in particular to a kind of compound alkaline-leaching and vanadium extraction method of bone coal and its system.
Background technique
Vanadium is a kind of important alloying element, there is extensive purposes.Bone coal be China it is important containing 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 mainly exists in the form of four kinds in bone coal: (1) V
(III) replace Al (III) to be present in mica mineral with isomorph, be the most important existence form of vanadium in bone coal；
(2) vanadium is present in the surface of clay mineral and ferriferous oxide colloid in the form of ADSORPTION STATE；(3) vanadium is in the form of metallo-organic complex
In the presence of；(4) vanadium exists in the form of Within Monominerals.Just because of existence form diversification of the vanadium in bone coal, so big to extracting vanadium from stone coal
Difficulty is increased greatly.
The technique rate of recovery of traditional sodium roasting and calcification baking extracting vanadium from stone coal is ideal not enough, the former has serious ring
Border pollution problem, requirement of the latter to bone coal original ore property are harsher.Although process for extracting vanadium by acid leaching can improve the leaching rate of vanadium
And the rate of recovery, it reduces environmental pollution, but sour dosage is larger, severe corrosion to equipment, foreign ion type and contains in pickle liquor
Amount is high, and subsequent processing 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 alkaline-leaching and vanadium extraction technique at present, 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 be the important development direction of extracting vanadium from stone coal using the method for alkali leaching.But
The main deficiency of alkali soaking technology is that alkali consumption is high, however, residual base utilization rate is low in leachate at present, and leachate concentration containing vanadium is low, after
Continuous treating capacity is big, increases production cost, and hardly possible, which is realized, to be promoted and applied.
Summary of the invention
Present invention aim to address high production cost present in original technique, and energy consumption is high, and environmental pollution is serious, subsequent
Complicated disadvantage is handled, a kind of clean and environmental protection is provided, had not only been able to achieve higher vanadium recovery, but also alkaline consumption can be reduced and be produced into
This vanadium extract technology.
To achieve the goals above, one aspect of the present invention provides a kind of method of vanadium extraction from bone coal, the method packet
It includes:
A, stone coal powder is roasted to obtain bone coal fired slags；
B, bone coal fired slags are impregnated with compound alkali leaching agent, obtains 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, return step B is used as compound alkali leaching agent after cleaning solution and part leachate being added compound alkali；
E, calcium compound reaction is added in Xiang Qiyu leachate, removal of impurities liquid is obtained after separation of solid and liquid；
F, it is passed through carbon dioxide progress carbon into removal of impurities liquid to divide, the carbonate of precipitated sodium, obtains the carbon of sodium after separation of solid and liquid
Hydrochlorate and rich vanadium solution.
Preferably, method of the invention can also include: to collect the flue gas of generation in step；The flue gas of collection is net
It is passed through in step F after change in removal of impurities liquid and carries out carbon point.
Preferably, method of the invention can also include preparing vanadium product, such as ammonium vanadate, five oxidations two with rich vanadium solution
Vanadium etc..In one embodiment, ammonium vanadate can be prepared with rich vanadium solution, then roasts ammonium vanadate to obtain five oxidations two
Vanadium.
In step, the partial size of stone coal powder is not specifically limited, as long as not influencing 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 will increase grinding cost, therefore generally in 300 mesh hereinafter, for example below 200 mesh.For example, stone coal powder can
To prepare as follows: ball mill will be used levigate after bone coal coarse crushing, sieved with 100 meshes, extracting screen underflow obtains stone coal powder.
In step, the purpose of roasting is the charcoal and volatile oxide removed 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, facilitates the leaching of vanadium.The temperature and time of roasting is not special
It limits, as long as can be realized above-mentioned purpose.Preferably, roasting can carry out at 800 DEG C~1000 DEG C, and the time can be
1~4h, preferably 2~3h.In addition, roasting can carry out in any suitable equipment, such as carried out in Muffle furnace.
In step, it is also preferable to include crush bone coal fired slags.Smashed granularity can be in 60 mesh to 300
Between mesh, preferably 100~200 mesh.For example, the pulverising step can prepare it is as follows: the bone coal after roasting is thin through ball mill
It is sieved after broken with 100 meshes, extracting screen underflow obtains bone coal fired slags powder.The crushing of bone coal fired slags can further be increased
Strong leaching effect.
In step, the flue gas of generation can also be collected spare.The main ingredient of flue gas is C, S, N oxide,
Such as CO2、SO3、SO2、NO、NO2Deng, thus can be used for the carbon point of step F.In this way, the flue gas on the one hand generated is recycled
It recycles, 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, acid amount needed for greatly reducing subsequent tune pH value when preparing ammonium vanadate.
In stepb, compound alkali with the aluminosilicate in bone coal for reacting, to dissolve out the vanadium wrapped up by alumino-silicate.It is multiple
Alkali is closed to be made of sodium hydroxide, sodium carbonate and optional sodium bicarbonate.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 influencing V leaching rate at
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 bicarbonate and sodium carbonate be respectively 40~80g/l, 0~60g/l and 10~
The compound alkali leaching agent of dosage preparation of 60g/l, preferably respectively 50~70g/l, 0~50g/l, 20~50g/l.
When being impregnated, the bone coal fired slags based on 1 parts by weight, the dosage of compound alkali leaching agent is preferably 1~4 weight
Part, more preferable 2~3 parts by weight.Dipping preferably carries out under stiring.Dipping temperature is not particularly limited, as long as being able to carry out anti-
Should, it is preferred that being 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 preferable 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.Washing is for by the residual alkali in leached mud
It is washed out with remaining solvable vanadium.Washing may be carried out batchwise or be carried out continuously.In the case where interval carries out, do not have to washing times
It is specifically limited, as long as realizing washing purpose.Such as 1~3 time, preferably 1~2 time can be washed.What is repeatedly washed
In the case of, rear washing gained cleaning solution is preferably recycled to previous washing.Such as in the case where wash twice, by the
The resulting cleaning solution of secondary washing is back to washing for the first time for washing leached mud.It, can in the case where being carried out continuously washing
To carry out countercurrent washing to leached mud with water.The dosage of water is not specifically limited, but the leached mud based on 1 parts by weight, preferably
The dosage of water is 1~3 parts by weight, more preferably 1~2 parts by weight.
Washing residue is mainly silicate and alumino-silicate, may be used as preparing cement building material.
In step D, return step B is used as after cleaning solution obtained by step C and part leachate being added compound alkali allotment
Compound alkali leaching agent.The amount of the leachate of return step B 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 stable.Using leachate
Vanadium concentration increases in the final leachate that alkali and water consumption can be substantially reduced after reflux cycle extract technology, and obtained, and has
Conducive to subsequent vanadium extraction everything goes well with your work carry out.The compound alkali number added is not particularly limited, it is preferred that mend to 60~250g/l
(basicity is in terms of sodium hydroxide in the present invention), more preferably 80~150g/l.
Calcium compound reaction is added in step E, in Xiang Qiyu leachate, removal of impurities liquid is obtained after separation of solid and liquid.It is soaked in alkali
In the process, the metal ions such as Fe, Ca, Mg in bone coal fired slags are not leached under basic conditions, main in leachate
Impurity is Si, P, with SiO3 2-、PO4 3-Form exists.Leachate is strong basicity, pH > 14.Calcium directly 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.Reaction temperature and time are not particularly limited, as long as enabling to Si in leachate and P and calcium
Compound reaction.Preferable reaction temperature is between 60~100 DEG C, more preferably between 70~95 DEG C, for example, about 90 DEG C.
Reaction time can be about 10 minutes or more, and about 30 minutes or more, for example, about 1h.It is separated by solid-liquid separation after reaction and obtains removal of impurities liquid.
Solid is calcium-silicon slag, can be used for preparing cement building material.
In step F, it is passed through carbon dioxide into removal of impurities liquid and carries out carbon point, the carbonate of precipitated sodium, after 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 the flue gas that step A can be made to generate in this way obtains recycling and reusing, air pollution is prevented, moreover, S, N in flue gas
Oxide can neutralize removal of impurities liquid basicity, so as to greatly reduce it is subsequent prepare ammonium vanadate when tune pH value needed for acid amount.
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 bicarbonate, be mingled with the sodium carbonate of sub-fraction.The carbonate of sodium can be used for preparing compound alkali and leach
Agent returns to leaching section and recycles, reduces production cost.Therefore, step F may further include obtained sodium
Carbonate is for the step of preparing compound alkali leaching agent.
Gained richness vanadium solution can be further used for preparing vanadium product, such as ammonium vanadate, vanadic anhydride etc..For example, first
First by rich vanadium solution adjust pH to 2~3, then through D201 resin carry out ion exchange with remove the impurity sun in rich vanadium solution 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 resin
It is small compared with ammonium metavanadate to lead to that a large amount of potassium metavanadate is mixed in the ammonium metavanadate obtained in the case where not removing, it influences
The problem of product purity.Loaded resin obtains the vanadium solution of high concentration after elution, and high concentration vanadium liquid is adjusted pH to 2
Acid ammonium salt precipitation vanadium is added after~3 thereto and obtains ammonium vanadate solid.The acid ammonium salt can be ammonium chloride, sulfuric acid
Ammonium, ammonium nitrate etc..The eluent can be one or both of sodium hydroxide or sodium chloride solution, wherein sodium hydroxide
With the mass fraction of sodium chloride all can be 1%~14%, preferably 3%~10%.Ammonium vanadate is roasted 2 at 500~600 DEG C
Impurity component is obtained after~3h and content meets the vanadic anhydride product of 87 quality standard of GB3283-.
Another aspect of the present invention provides the system of the vanadium extraction from bone coal, the system comprises:
First calciner is used to roast stone coal powder to obtain bone coal fired slags；
Compound alkali leaching agent storing apparatus is used to store compound alkali leaching agent；
Leaching device receives the bone coal fired slags from the first calciner and comes from compound alkali leaching agent storing apparatus
Compound alkali leaching agent, for compound alkali leaching agent dipping bone coal fired slags；
First equipment for separating liquid from solid receives the mixing of compound alkali leaching agent and bone coal fired slags from leaching device
Object obtains leachate and leached mud after separation of solid and liquid；
Wash mill receives the leached mud from the first equipment for separating liquid from solid of connection, for leached mud to be washed with water；
Second equipment for separating liquid from solid receives the mixture of leached mud and water from wash mill, after separation of solid and liquid
To cleaning solution and washing residue；
Liquid conveyer receives the cleaning solution from the second equipment for separating liquid from solid and comes 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 receives the leachate from the first equipment for separating liquid from solid, in the first reaction unit, leaches
Liquid is reacted with the calcium compound of addition；
Third equipment for separating liquid from solid receives the reaction mixture from the first reaction unit, is removed after separation of solid and liquid
Miscellaneous liquid and calcium-silicon slag；
Carbon dioxide storing apparatus is used to store carbon dioxide；
Carbon divides reaction unit, receives the removal of impurities liquid from third equipment for separating liquid from solid and comes from carbon dioxide storing apparatus
Carbon dioxide, for carrying out carbon point reaction；
4th equipment for separating liquid from solid receives the reaction mixture for dividing reaction unit from carbon, obtains sodium after separation of solid and liquid
Carbonate and rich vanadium solution；
Solid conveyer, 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 can also include smoke gas collecting apparatus in slave bone coal of the invention, receive and collect calciner
The flue gas generated in roasting process.
The system of vanadium extraction can also include flue gas purification device in slave bone coal of the invention, receive to fill from fume collection
The flue gas set, and purified.
Smoke gas collecting apparatus and flue gas purification device of the invention also may be integrally incorporated to realizes fume collection and purification together
Function, such as flue gas cleaner.
The system of vanadium extraction can also include gas transport device in slave bone coal of the invention, receive to fill from gas cleaning
The purified flue gas set, and be conveyed to carbon and reaction unit is divided to carry out carbon point for being passed through in removal of impurities liquid.
The system of vanadium extraction can also include: in slave bone coal of the invention
PH regulating device receives the rich vanadium solution from the 4th equipment for separating liquid from solid, by rich vanadium in pH regulating device
The pH of solution is adjusted to 2~3；
Pro-concentration with ion exchange process vanadium extraction device receives the rich vanadium solution after the pH from pH regulating device is adjusted, and carries out
Then ion exchange obtains vanadium solution after elution to remove the impurity cationic in rich vanadium solution；
Settler 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, and acid ammonium salt precipitation vanadium is then added；
5th equipment for separating liquid from solid, receives the precipitation reaction mixture from settler, and separation of solid and liquid obtains vanadic acid
Ammonium solid.
The system of vanadium extraction can also include: the second calciner in slave bone coal of the invention, receive to come from the 5th solid-liquid
The ammonium vanadate solid of separator is simultaneously roasted to vanadic anhydride.
The system of vanadium extraction can also include crushing device in slave bone coal of the invention, for bone coal to be crushed to suitable grain
Degree, such as crusher, ball mill etc..
Above-mentioned apparatus of the invention is not particularly limited, as long as can be realized the function, can use ability
The device conventionally used for realizing the function in domain.For example, calciner can be calcining kiln, roaster, calcining furnace, fusing
Furnace etc..Storing apparatus can be storage tank, storage tank etc..Leaching device, wash mill, the first reaction unit, carbon divide reaction unit, pH
Regulating device and settler can be slot type reaction unit (such as stirred tank), reaction kettle etc..Equipment for separating liquid from solid can be
Filter press (such as plate and frame filter press), centrifuge, nutsch filter etc..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 the above device inlet porting and/or
Outlet, to realize required connection, charging or discharging.In addition, as needed, in the visual field of those skilled in the art, may be used also
To increase auxiliary device, such as agitating device, drying device, pipeline, pump (such as metering pump, circulating pump, delivery pump etc.), valve
Door, heat exchanger (such as plate heat exchanger), condensing unit, heating device, conveyer, batcher etc..
In slave bone coal of the invention in the system of vanadium extraction, description and the foregoing teachings of the raw material and condition that are used for technique
Identical, details are not described herein.
Beneficial effect
1, the present invention uses alkaline matter preferable to ion selectivity as leaching agent vanadium extraction, Fe, Ca in bone coal fired slags,
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.
2, the present invention considers that sodium hydroxide concentration is big, high production cost, 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 influencing V leaching rate at
This.
3, using after part leachate reflux cycle extract technology, alkali and water consumption substantially reduce the present invention, and obtain
Leachate in vanadium concentration increase, be conducive to subsequent vanadium extraction everything goes well with your work carry out.
4, leachate is cleaned under the alkaline condition of pH > 14 using calcium compound in the present invention, first tune pH as compared with the past
It cleans again to alkalescent, without acid consumption, and it is thorough to clean.
5, the present invention carries out carbon point recycling sodium bicarbonate, the flue gas on the one hand generated using the flue gas generated after bone coal roasting
Obtaining recycling and reusing prevents air pollution, and another aspect sodium bicarbonate returns again to leaching section and recycles, and reduces production
Cost, while the basicity for the liquid that cleans also reduces, the amount of acid needed for adjusting pH value greatly reduces.
6, operation of the present invention simple process is easy to industrialization promotion, has certain economic effect under current technical conditions
Pollutant is not generated in benefit and production process, is had the advantages that environmental-friendly.
Specific embodiment
The present invention will be described in further detail with reference to the examples below.
Embodiment 1:
Raw material: Rock coal containing alum is derived from Anhui province, and vanadium grade is 0.71%.
It is levigate to 150 μm hereinafter, by bone coal through 850 DEG C in roaster by ball mill again after bone coal crusher coarse crushing
Fired slags are obtained after roasting 3.0h, it is spare to collect gas cleaning with flue gas cleaner.
Bone coal fired slags ball mill is levigate, it is sieved with 100 meshes, extracting screen underflow is added in leaching tanks, by liquid
Gu compound alkali leaching agent is added from compound alkali leaching agent storage tank than the ratio that (weight ratio) is 2:1, wherein in compound alkali leaching agent
Sodium hydroxide and concentration of sodium carbonate are respectively 70g/l and 40g/l, basicity 142g/l.It is stirred to react under 95 DEG C of waters bath with thermostatic control
2h。
It will be imported in plate and frame filter press from the mixture that leaching tanks are discharged, leachate and leached mud obtained after separation of solid and liquid,
Controlling water content in slag is 35% or so.
Leached mud is carried out to clear water washing, wash water adverse current reuse twice to be separated by solid-liquid separation through plate and frame filter press in sink
Cleaning solution and washing residue are obtained, controlling water content in slag is 35% or so.Wash residue stockpiling.
Cleaning solution and 1/2 volume leachate are returned after compound alkali leaching agent storage tank mends alkali and are formulated as compound alkali leaching agent,
Basicity is 148g/l after mending alkali.
With the content of vanadium in potassium permanganate-iron ammonium sulfate method measurement leached mud, the rate of recovery of vanadium is extrapolated, is once followed
Vanadium recovery is 89.06% after ring, and vanadium recovery is stablized 84.00% or so after repeatedly recycling.
Remaining leachate is imported in reaction kettle, calcium oxide is added into leachate and reacts 1h, reaction mixing at 90 DEG C
Object imports after plate and frame filter press is separated by solid-liquid separation and obtains removal of impurities liquid and calcium-silicon slag.Calcium-silicon slag stockpiling.
Removal of impurities liquid is imported in reaction kettle, the flue gas after being passed through collection and purification carries out carbon point, and sodium bicarbonate and carbonic acid is precipitated
The salt-mixture of sodium.Mixture after carbon point is imported in plate and frame filter press, sodium bicarbonate is obtained after separation of solid and liquid and (is wherein mingled with
Sodium carbonate) and rich vanadium solution.Solid mixture is transported to compound alkali leaching agent storage tank and is used to prepare compound alkali leaching agent.It will be rich
Vanadium liquid adds sulfuric acid tune pH to 2.0 again, crosses D201 ion exchange resin column Vanadium Concentrationin.Loaded resin mass fraction is 4%
The vanadium solution of high concentration is obtained after NaOH solution elution.
Brick-red vanadium is obtained by being added after ammonium sulfate precipitation thereto after the vanadium solution of high concentration sulphur acid for adjusting pH to 2.0
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 cake.By metavanadic acid
Ammonium obtains impurity component after 550 DEG C of roasting kiln roasting 2h and content meets the vanadic anhydride of 87 quality standard of GB3283-
Product.
Embodiment 2:
Raw material: Rock coal containing alum is derived from Anhui province, and vanadium grade is 0.71%.
It is levigate to 150 μm hereinafter, by bone coal through 850 DEG C in roaster by ball mill again after bone coal crusher coarse crushing
Fired slags are obtained after roasting 2.5h, it is spare to collect gas cleaning with flue gas cleaner.
Bone coal fired slags ball mill is levigate, it is sieved with 100 meshes, extracting screen underflow is added in leaching tanks, by liquid
Gu compound alkali leaching agent is added from compound alkali leaching agent storage tank than the ratio that (weight ratio) is 2:1, wherein in compound alkali leaching agent
Sodium hydroxide and sodium bicarbonate concentration are respectively 65g/l and 38g/l, basicity 132g/l.It is stirred under 90 DEG C of waters bath with thermostatic control anti-
Answer 2.0h.
It will be imported in plate and frame filter press from the mixture that leaching tanks are discharged, leachate and leached mud obtained after separation of solid and liquid.
Leached mud is carried out in sink twice clear water washing, wash water adverse current reuse, separation of solid and liquid obtain cleaning solution and
Wash residue.Wash residue stockpiling.
Cleaning solution and 1/2 volume leachate are returned after compound alkali leaching agent storage tank mends alkali and are formulated as compound alkali leaching agent,
Basicity is 136g/l after mending alkali.
With the content of vanadium in potassium permanganate-iron ammonium sulfate method measurement leached mud, the rate of recovery of vanadium is extrapolated, is once followed
Vanadium recovery is 87.83% after ring, and vanadium recovery is stablized 83.16% or so after repeatedly recycling.
Remaining leachate is imported in reaction kettle, calcium chloride is added into leachate and reacts 1.5h at 90 DEG C, reaction is mixed
It closes after object imports plate and frame filter press separation of solid and liquid and obtains removal of impurities liquid and calcium-silicon slag.Calcium-silicon slag stockpiling.
Removal of impurities liquid is imported in reaction kettle, the flue gas after being passed through collection and purification carries out carbon point, and sodium bicarbonate and carbonic acid is precipitated
The salt-mixture of sodium.Mixture after carbon point is imported in plate and frame filter press, sodium bicarbonate is obtained after separation of solid and liquid and (is wherein mingled with
Sodium carbonate) and rich vanadium solution.Solid mixture is transported to compound alkali leaching agent storage tank and is used to prepare compound alkali leaching agent.It will be rich
Vanadium liquid adds sulfuric acid tune pH to 2.1 again, crosses D201 ion exchange resin column Vanadium Concentrationin.Loaded resin is 3%NaOH+ with mass fraction
The vanadium solution of high concentration is obtained after the elution of 5%NaCl solution.
Brick-red vanadium is obtained by being added after ammonium sulfate precipitation thereto after the vanadium solution of high concentration sulphur acid for adjusting pH to 2.0
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 cake.By metavanadic acid
Ammonium obtains impurity component after 550 DEG C of roasting kiln roasting 2h and content meets the vanadic anhydride of 87 quality standard of GB3283-
Product.
Claims (33)
1. a kind of method of the vanadium extraction from bone coal, which comprises
A, stone coal powder is roasted to obtain bone coal fired slags, wherein the granularity of stone coal powder more than 60 mesh, roasting 800 DEG C~
It is carried out at 1000 DEG C；
B, bone coal fired slags are impregnated with compound alkali leaching agent, obtains leachate and leached mud after separation of solid and liquid, wherein described compound
Alkali leaching agent is the aqueous solution of compound alkali, and basicity is calculated as 60~250g/l with sodium hydroxide, and compound alkali is by sodium hydroxide and carbonic acid
Sodium is formed or is made of sodium hydroxide, sodium carbonate and sodium bicarbonate, when being impregnated, the bone coal fired slags based on 1 parts by weight,
The dosage of compound alkali leaching agent is 1~4 parts by weight；
C, leached mud is washed with water, separation of solid and liquid obtains cleaning solution and washing residue, wherein washing times are 1~5 time or use
Water carries out countercurrent washing, and the leached mud based on 1 parts by weight to leached mud, and the dosage of water is 1~3 parts by weight；
D, return step B is used as compound alkali leaching agent after cleaning solution and part leachate being added compound alkali, wherein return step
The amount of the leachate of B is the 1/4 to 3/4 of leachate total amount, and the compound alkali number added is to mend to basicity to be calculated as 60 with sodium hydroxide
~250g/l；
E, calcium compound reaction is added in Xiang Qiyu leachate, removal of impurities liquid is obtained after separation of solid and liquid, wherein the calcium compound choosing
From Ca (OH)2, CaO and CaCl2；
F, it is passed through carbon dioxide progress carbon into removal of impurities liquid to divide, the carbonate of precipitated sodium, obtains the carbonate of sodium after separation of solid and liquid
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 80 mesh；And/or roasting
Time is 1~4h.
3. according to the method described in claim 2, wherein, in step, the granularity of stone coal powder is more than 100 mesh and/or roasts
Time is 2~3h.
4. according to the method described in claim 1, wherein, in stepb, the compound alkali leaching agent basicity is in terms of sodium hydroxide
For 80~150g/l.
5. according to the method described in claim 1, wherein, in stepb, being distinguished with sodium hydroxide, sodium bicarbonate and sodium carbonate
Compound alkali leaching agent is prepared for the dosage of 40~80g/l, 0~60g/l and 10~60g/l.
6. according to the method described in claim 1, wherein, in stepb, being distinguished with sodium hydroxide, sodium bicarbonate and sodium carbonate
Compound alkali leaching agent is prepared for the dosage of 50~70g/l, 0~50g/l, 20~50g/l.
7. according to the method described in claim 1, wherein, in stepb, when being impregnated, the bone coal based on 1 parts by weight is roasted
Slag, the dosage of compound alkali leaching agent are 1~4 parts by weight；And/or dipping temperature is 70~100 DEG C；And/or dip time is 1
~4h.
8. according to the method described in claim 7, wherein, the bone coal fired slags based on 1 parts by weight, the dosage of compound alkali leaching agent
For 2~3 parts by weight；And/or dipping temperature is 80~95 DEG C；And/or dip time is 2~3h.
9. according to the method described in claim 1, wherein, in step C, washing times are 2~3 times；And/or it is carrying out repeatedly
In the case where washing, rear washing gained cleaning solution is recycled to previous washing；And/or the leached mud based on 1 parts by weight, water
Dosage is 1~2 parts by weight.
10. according to the method described in claim 1, wherein, in step D, the amount of the leachate of return step B is that leachate is total
The 1/2 of amount；And/or the compound alkali number added is to mend to basicity to be calculated as 80~150g/l with sodium hydroxide.
11. according to the method described in claim 1, wherein, in step E, the calcium compound is CaO.
12. according to the method described in claim 1, wherein, in step E, reaction temperature is and/or anti-between 60~100 DEG C
It is 10 minutes or more between seasonable.
13. according to the method for claim 11, wherein reaction temperature is between 70~95 DEG C and/or the reaction time is 30
Minute or more.
14. according to the method described in claim 1, further comprising: in step, collecting the flue gas of generation；By collection
It is passed through in step F after gas cleaning in removal of impurities liquid and carries out carbon point.
15. according to the method described in claim 1, further comprising: in step, bone coal fired slags are crushed.
16. according to the method for claim 15, wherein by the smashed granularity of bone coal fired slags 60 mesh to 300 mesh it
Between.
17. according to the method for claim 16, wherein by the smashed granularity of bone coal fired slags be 100~200 mesh.
18. according to the method described in claim 1, further comprising: washing residue being used as and prepares cement in step C
Building materials.
19. according to the method described in claim 1, further comprising: will be separated by solid-liquid separation obtained solid in step E and use
In preparing cement building material.
20. according to the method described in claim 1, further comprising: the carbonate of obtained sodium is used in step F
In the compound alkali leaching agent of preparation.
21. according to the method described in claim 1, further comprising: gained richness vanadium solution is used to prepare vanadium product.
22. according to the method for claim 21, wherein rich vanadium solution is adjusted pH to 2~3, then is carried out through D201 resin
For ion exchange to remove the impurity cationic in rich vanadium solution, the vanadium that loaded resin obtains high concentration after elution is molten
Liquid obtains ammonium vanadate solid for acid ammonium salt precipitation vanadium is added thereto after high concentration vanadium liquid adjusting pH to 2~3.
23. according to the method for claim 22, wherein the acid ammonium salt is selected from ammonium chloride, ammonium sulfate and ammonium nitrate；
And/or the eluent is selected from one or both of sodium hydroxide solution and sodium chloride solution.
24. according to the method for claim 23, wherein in the sodium hydroxide solution and sodium chloride solution, sodium hydroxide
Mass fraction with sodium chloride is 1%~14%.
25. according to the method for claim 24, wherein in the sodium hydroxide solution and sodium chloride solution, sodium hydroxide
Mass fraction with sodium chloride is 3%~10%.
26. according to the method for claim 22, wherein the method further includes roasting ammonium vanadate at 500~600 DEG C
Impurity component is obtained after burning 2~3h and content meets the vanadic anhydride product of 87 quality standard of GB3283-.
27. a kind of system of the vanadium extraction from bone coal, the system comprises:
First calciner is used to roast stone coal powder to obtain bone coal fired slags；
Compound alkali leaching agent storing apparatus is used to store compound alkali leaching agent；
Leaching device 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 receives the mixture of compound alkali leaching agent and bone coal fired slags from leaching device, Gu
Leachate and leached mud are obtained after liquid separation；
Wash mill receives the leached mud from the first equipment for separating liquid from solid of connection, for leached mud to be washed with water；
Second equipment for separating liquid from solid receives the mixture of leached mud and water from wash mill, is washed after separation of solid and liquid
Wash liquid and washing residue；
Liquid conveyer 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, receive the leachate from the first equipment for separating liquid from solid, in the first reaction unit, leachate with
The calcium compound of addition reacts；
Third equipment for separating liquid from solid receives the reaction mixture from the first reaction unit, and removal of impurities liquid is obtained after separation of solid and liquid
And calcium-silicon slag；
Carbon dioxide storing apparatus is used to store carbon dioxide；
Carbon divides reaction unit, receives the removal of impurities liquid from third 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 receives the reaction mixture for dividing reaction unit from carbon, obtains the carbon of sodium after separation of solid and liquid
Hydrochlorate and rich vanadium solution；
Solid conveyer, receives the carbonate of the sodium from the 4th equipment for separating liquid from solid, and carries it to compound alkali and soak
Agent storing apparatus out.
28. system according to claim 27, further include:
Smoke gas collecting apparatus receives and collects the flue gas that calciner generates in roasting process.
29. system according to claim 28, further include:
Flue gas purification device receives the flue gas from smoke gas collecting apparatus, and is purified.
30. system according to claim 29, further include:
Gas transport device receives the purified flue gas from flue gas purification device, and is conveyed to carbon point reaction dress
It sets and carries out carbon point for being passed through in removal of impurities liquid.
31. system according to claim 27, further include:
Crushing device, for bone coal to be crushed to suitable granularity.
32. system according to claim 27, further include:
PH regulating device receives the rich vanadium solution from the 4th equipment for separating liquid from solid, by rich vanadium solution in pH regulating device
PH be adjusted to 2~3；
Pro-concentration with ion exchange process vanadium extraction device receives the rich vanadium solution after the pH from pH regulating device is adjusted, and carries out ion
Then exchange obtains vanadium solution after elution to remove the impurity cationic in rich vanadium solution；
Settler receives the vanadium solution from Pro-concentration with ion exchange process vanadium extraction device, in settler, by vanadium solution pH tune
Then acid ammonium salt precipitation vanadium is added to 2~3 in section；
5th equipment for separating liquid from solid receives the precipitation reaction mixture from settler, and it is solid that separation of solid and liquid obtains ammonium vanadate
Body.
33. system according to claim 32, further include:
Second calciner receives the ammonium vanadate solid from the 5th equipment for separating liquid from solid and is roasted to five oxidations two
Vanadium.
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| CN108251661B (en) * | 2018-01-30 | 2020-10-09 | 长春师范大学 | Process for extracting vanadium from stone coal vanadium ore |
| CN109293203A (en) * | 2018-09-06 | 2019-02-01 | 贵州民族大学 | A kind of sludge heavy-metal recovery system and method |
| CN110218882A (en) * | 2019-05-31 | 2019-09-10 | 中国地质调查局武汉地质调查中心(中南地质科技创新中心) | Interior circulation second level counterflow leaching extraction vanadium method based on Rock coal containing alum |
| CN111500867A (en) * | 2020-06-09 | 2020-08-07 | 攀钢集团攀枝花钢铁研究院有限公司 | Recovery treatment and utilization method of vanadium precipitation wastewater and vanadium trioxide dedusting and leaching water |
| CN114262808A (en) * | 2021-12-16 | 2022-04-01 | 浙江鑫旺钒业控股有限公司 | Process for extracting high-purity vanadium pentoxide from stone coal vanadium ore |
| CN115232988B (en) * | 2022-07-29 | 2023-09-01 | 攀钢集团研究院有限公司 | Method for extracting vanadium from leached tailings by carbonation of blank vanadium slag or calcified roasting clinker |
| CN115725863B (en) * | 2022-11-22 | 2024-06-11 | 辽宁东大矿冶工程技术有限公司 | Method for extracting vanadium from vanadium shale by segmented microwave roasting-stepwise alkaline leaching |
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