CN109835949A - A kind of system and method for vanadium slag cleaning chlorination production high purity vanadic anhydride - Google Patents
A kind of system and method for vanadium slag cleaning chlorination production high purity vanadic anhydride Download PDFInfo
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Abstract
The invention discloses a kind of system and method for vanadium slag cleaning chlorination production high purity vanadic anhydride.Granulation processing is aoxidized by fluidized bed, realizes that vanadium slag mine is mutually reformed and ore particle is grown up；Gaseous state vanadium oxytrichloride is converted by the vanadium in vanadium slag by selective chlorination, most of impurity such as chromium, iron, calcium, phosphorus, manganese, titanium, silicon in vanadium slag is stayed in chloride residue, realizes efficiently separating for vanadium and chromium and other impurities.Gaseous vanadium oxytrichloride successively passes through the processes such as dedusting-elution-sedimentation-rectifying purifying-catalysis oxidation and high purity vanadic anhydride is prepared.Chloride residue is handled by vapor phase hydrolysis dechlorination, and processing slag returns to refining ferrochrome.The present invention realizes the cleaning comprehensive utilization of vanadium slag, while being effectively utilized the sensible heat of chlorination furnace high-temperature flue gas, achievees the purpose that energy-saving.
Description
Technical field
The invention belongs to metallurgy, chemical field, in particular to a kind of vanadium slag cleaning chlorination production high purity vanadic anhydride
System and method.
Background technique
Vanadic anhydride is a kind of important chemical metallurgy material, is mainly used for ferrous alloy additive all the time, raw
Produce steel alloy.Recently as the fast development of industrial technology, vanadic anhydride is in aerometal, energy storage material, petrochemical industry
The application percentage in the fields such as catalyst gradually rises.Especially energy storage material (all-vanadium redox flow battery electrolyte, lithium vanadate anode material
Material) and high performance turbine alloy (vanadium aluminium system, vanadium titanium alloy) industry fast-developing five oxidations two to high-quality high-purity
Vanadium produces huge demand.
Vanadium titano-magnetite is the primary raw material for producing vanadic anhydride.Currently, industrial obtained by reduction melting containing vanadium
Molten iron, further blowing obtains vanadium slag；Vanadium slag prepares technical grade five by " sodium roasting-leaching-precipitation-calcining and decomposing " process
V 2 O；By dissolution precipitating repeatedly, further removal impurity promotes purity to technical grade vanadic anhydride.But the extraction work
Skill is influenced compared with vulnerable to vanadium titano-magnetite raw material, for example the vanadium titano-magnetite chromium content in the red lattice area of Panzhihua is higher, suitable with vanadium.
During reduction melting, chromium and vanadium enter molten iron together, further blow red lattice vanadium titano-magnetite because property is close,
Obtain high chrome alum slag.If high chrome alum slag is using the process of " sodium roasting-leaching-precipitation-calcining and decomposing ", there are following
Two main problems: (1) vanadium recovery is low.In high chrome alum slag, picotite and vanadic spinel are dissolved together, and chromium point is brilliant
Stone is a kind of a kind of ore that oxygenolysis is more difficult to than vanadic spinel, and using common vanadium slag extracting method, vanadium recovery is very
It is low.(2) vanadium chrome liquor is mutually mixed, and separation is difficult.In order to improve the rate of recovery of vanadium, sodium roasting needs to increase sodium salt amount in the process,
Then it leaches again.Under the conditions of this, vanadium, chromium enter liquid phase simultaneously, it is difficult to and it efficiently separates, and generates a large amount of chromate waste water, it is dirty
Contaminate environment.And there is also following outstanding problems for sodium roasting technique itself: (1) process is tediously long, and energy consumption is high, high production cost；
(2) vanadium recovery is low, from vanadium slag to the rate of recovery of vanadium oxide product less than 80%；(3) vanadium-extracted residues are difficult to handle, sodium roasting
A large amount of sodium salt is introduced, residue is limited and directly returns to blast furnace ironmaking；(4) environmental problem is prominent, and leaching-precipitation process generates
The ammonia nitrogen waste water of a large amount of harmful metal ion, sodium sulphate containing there are many, causes serious influence to ecological environment.Therefore, it develops
The stronger technology of versatility can utilize common vanadium slag, high chrome alum slag to produce having for high purity vanadic anhydride important simultaneously
Meaning.
Chlorination process for extracting vanadium causes the extensive of people because of its stronger chlorination selectivity and the characteristics of being easy to rectification and purification
Concern.Some technical staff start to handle vanadium slag using chloridization process, and have applied for technical patent.Such as Chinese patent
CN101709388B discloses a kind of technique of separating vanadium by chloridizing and roasting vanadium slag, by vanadium slag oxidizing roasting material, solid chlorinating agent with
Carbonaceous reducing agent is mixed in a certain ratio pelletizing, and being sent into rotary kiln baking evaporates vanadium in the form of chloride, to reach
To the purpose of separation and Extraction vanadium.This technique using solid chlorinating agent combination rotary kiln baking is there are low efficiency and is unfavorable for big
The problem of scale operations.And the technique is not directed to the method that vanadium oxytrichloride prepares vanadic anhydride, is not one complete
Prepare the technology of vanadic anhydride.Chinese patent CN101845552B discloses a kind of reclaiming valuable element through gradient chlorination of vanadium slag
Vanadium slag, solid salt, simple substance carbon are uniformly mixed and are passed through chlorine at different temperature and successively carry out vanadium, iron, chromium and silicon by method
Chlorination, to achieve the purpose that these elements of separation and concentration.The technique uses solid chlorinating agent and gas chlorinating agent, process simultaneously
It is complicated.And the technique is not directed to the method that vanadium oxytrichloride or vanadium tetrachloride prepare vanadic anhydride, is not one complete
Prepare the technology of vanadic anhydride.Iron chloride, chromium chloride, silicon chloride for supervening etc. are difficult to efficiently use.Chinese patent
CN103130279B discloses one kind using substances containing vanadium such as vanadium slags as raw material, and the side of vanadic anhydride is prepared using chloridising extraction
Method, it is heavy with carbon chlorination (using solid chlorinating agent or gas chlorination agent), rectification and purification, liquid-phase hydrolysis or ammonium salt by substance containing vanadium
It forms sediment, vanadic anhydride is prepared in drying or calcining.The technique has been merely given as a kind of principle process flow of chlorination vanadium extraction, closes
It is strong that implementation is not provided in vanadium slag selective chlorination and key issues of by chloride efficiently preparing vanadic anhydride
Technical solution.And this technique for preparing vanadic anhydride " with carbon chlorination-purification-liquid-phase hydrolysis or ammonium salt precipitating-calcining "
Process, early in the 1960s, just proposing (Journal of the by the researcher of Iowa State University, the U.S.
Less-Common Metals,1960,2:29-35).Chinese patent CN105986126B discloses a kind of efficient chlorination of vanadium slag and mentions
The system and method for vanadium prepares vanadic anhydride with carbon chlorination-distilation-vapor phase hydrolysis process flow by vanadium slag.It should
Technique uses fluidizing chlorination technology, shows biggish technical advantage relative to solid chlorinating agent chlorination.And use gas phase water
The technique of solution prepares vanadic anhydride by vanadium oxytrichloride, and compare liquid-phase hydrolysis or ammonium salt precipitating, and wastewater flow rate is greatly lowered, and is in
Reveal significant technical advantage.But the vanadium slag in the technique does not pass through pre-treatment and is directly entered chlorination furnace, it will leads to vanadium
The selectivity of chlorination reduces, and a large amount of harmful cycling of elements are chloride, greatly improves at subsequent distilation and chloride residue
The cost of reason.The chlorination flue gas that chlorination furnace evaporates does not pass through dust removal process and directly exchanges heat, it will causes pipeline stifled
Plug, seriously affects production.Vapor phase hydrolysis technique will generate largely containing vanadic salts acid, increase environmentally friendly cost.And chlorination furnace
The sensible heat of heat balance, high-temp chlorination flue gas and chloride residue does not utilize well.
In conclusion existing chlorination process for extracting vanadium presents significant technological merit, but there is also many protrusions
The problem of: (1) chlorination selectively poor, in vanadium resource when vanadium chlorination, will lead to the chlorine of other iron, titanium, chromium, calcium, phosphorus, silicon
Change, causes rectification and purification and chloride residue to handle more difficult；(2) vanadium resource chloridising roasting belongs to strongly exothermic process, and chlorination is anti-
The heat that should be generated is other than it can meet the preheating of solid and gas reaction material, it is still necessary to the cooling that exchanges heat processing.And distill and
Waste water crystallization then needs to consume a large amount of energy.The energy of front and back process is unable to effective coordination utilization, will greatly improve the energy and disappears
Consumption increases production cost；(3) industrial vanadium product vanadic anhydride is prepared by vanadium chloride (vanadium oxytrichloride) and lacks high-efficiency cleaning
Technology path, due to vanadium in hydrochloric acid solution solubility with higher, the rate of recovery that direct liquid-phase hydrolysis will cause vanadium is too low,
Although and the rate of deposition of vanadium can be improved in use ammonium salt precipitating, can generate a large amount of ammonia nitrogen waste water；Though the technique of vapor phase hydrolysis
It so avoids generation ammonia nitrogen from dividing water, but will bring largely containing vanadic salts acid, environmental problem is prominent；(4) existing chlorination vanadium extraction work
Skill does not have practicability mainly for common vanadium slag, for vanadium slag containing chromium type.
Therefore, it is innovated by technology, the temperature for improving chlorination selectivity for polymorphic type vanadium slag, realizing chlorination process
Regulation and whole process heat integration utilize, solve the problems, such as that vanadium oxytrichloride efficiently prepares vanadic anhydride, realizes the comprehensive benefit of tailings
With being the key point of vanadium slag chlorination process scale application.
Summary of the invention
In view of the above-mentioned problems, the invention proposes a kind of system of vanadium slag cleaning chlorination production high purity vanadic anhydride and sides
Method, to realize the selective chlorination of vanadium slag, the regulation of chlorination process temperature and whole process heat integration are utilized, chlorination tailings it is harmless
Change processing, vanadium oxytrichloride efficiently prepare vanadic anhydride.
In order to reach these purposes, present invention employs following technical solutions:
The system of vanadium slag cleaning chlorination production high purity vanadic anhydride of the invention, including material papering section 1, mixing workshop section 2,
Chloridized dust collection workshop section 3, elution sedimentation workshop section 4, refinement 5, Zhi Fen workshop section 6 and chloride residue processing section 7；
The material papering section 1 includes vanadium slag feed bin 1-1, vanadium slag screw(-type) feeder 1-2, the granulating fluidized bed 1-3 of oxidation and rotation
Wind deduster 1-4；
The mixing workshop section 2 includes being granulated vanadium slag feed bin 2-1, being granulated vanadium slag screw feeder 2-2, carbon source feed bin 2-3, carbon
Source screw feeder 2-4 and fluidized bed blender 2-5；
The chloridized dust collection workshop section 3 includes chlorination furnace 3-1, chlorination furnace heat exchanger 3-2, gather dust tower 3-3 and the tower that gathers dust heat exchange
Device 3-4；
Elution sedimentation workshop section 4 include eluting column 4-1, mashing pump 4-2, eluting column heat exchanger 4-3, drop catcher 4-4 and
Elute slurry subsider 4-5；
The refinement 5 includes reboiler 5-1, reboiler heat exchanger 5-2, rectifying column 5-3, the condensation of high-purity vanadium oxytrichloride
Device 5-4 and high-purity vanadium oxytrichloride storage tank 5-5；
The Zhi Fen workshop section 6 includes powder reactor 6-1 processed, ultrapure water vaporizer 6-2, powder heat exchanger 6-3 processed, powder soft water processed
Storage tank 6-4, powder water circulating pump 6-5 processed, high purity vanadium feed bin 6-6 and high purity vanadium screw(-type) feeder 6-7；
The chloride residue processing section 7 includes technique water vaporizer 7-1, hydrolysis dechlorination fluidized bed 7-2, cyclone separator
7-3 and bag filter 7-4；
The discharge port of the bottom vanadium slag feed bin 1-1 is connected with the feed inlet of the vanadium slag screw(-type) feeder 1-2；It is described
The discharge port of vanadium slag screw(-type) feeder 1-2 is connected with the feed inlet of the granulating fluidized bed 1-3 of oxidation by pipeline；The oxygen
The air inlet for changing granulating fluidized bed 1-3 is connected with pneumatic manifold by pipeline；The tail of the granulating fluidized bed 1-3 of oxidation
Gas outlet is connected with the air inlet of the cyclone dust collectors 1-4 by pipeline；The gas outlet of the cyclone dust collectors 1-4 and tail
The air inlet of gas processing system is connected by pipeline；The dust outlet of the cyclone dust collectors 1-4 and the oxidation, which are granulated, flows
The dust inlet for changing bed 1-3 is connected by pipeline；The discharge gate and the granulation vanadium slag material of the granulating fluidized bed 1-3 of oxidation
The feed inlet of storehouse 2-1 is connected by pipeline；The discharge port and the granulation vanadium slag screw feeder for being granulated vanadium slag feed bin 2-1
The feed inlet of device 2-2 is connected；The discharge port for being granulated vanadium slag screw feeder 2-2 is with the fluidized bed blender 2-5's
Feed inlet is connected by pipeline；The feed inlet phase of the discharge port of the carbon source feed bin 2-3 and the carbon source screw feeder 2-4
Connection；The discharge port of the carbon source screw feeder 2-4 is connected with the feed inlet of the fluidized bed blender 2-5 by pipeline
It connects；The fluidisation gas inlet of the fluidized bed blender 2-5 is connected with nitrogen header pipe；The fluidized bed blender 2-5's goes out
Material mouth is connected with the feed inlet of the chlorination furnace 3-1 by pipeline；
The air inlet of the chlorination furnace 3-1 is connected with nitrogen header pipe, circulating chlorine gas general pipeline, chlorine general pipeline by pipeline respectively
It connects；The chlorination exhanst gas outlet of the chlorination furnace 3-1 is connected with the gas access for gathering dust tower 3-3 by pipeline；The chlorine
The chloride residue outlet for changing furnace 3-1 is connected with the feed inlet of the hydrolysis dechlorination fluidized bed 7-2 by pipeline；The chlorination furnace
Slurry inlet at the top of the 3-1 kettle base solution with the slurry outlet of the elution slurry subsider 4-5 and the reboiler 5-1 respectively
Outlet is connected by pipeline；The chlorination furnace heat exchanger 3-2 is set in the middle part of the chlorination furnace 3-1；It is described to gather dust tower 3-3's
Gas vent is connected with the air inlet of the eluting column 4-1 by pipeline；Slurry inlet difference at the top of the tower 3-3 that gathers dust
It exports with the kettle base solution of the slurry outlet of the elution slurry subsider 4-5 and the reboiler 5-1 and is connected by pipeline；Institute
The discharge gate for stating the tower 3-3 that gathers dust is connected with the feed inlet of the hydrolysis dechlorination fluidized bed 7-2 by pipeline；The tower that gathers dust changes
Hot device 3-4 is set to the middle part of the tower 3-3 that gathers dust；The tower heat exchanger 3-4 hot fluid outlet ports that gather dust are changed with the reboiler
The hot inlet of hot device 5-2 is connected by pipeline；The thermal fluid inlet of the tower heat exchanger 3-4 that gathers dust and the powder processed recycle
The fluid outlet of water pump 6-5 is connected by pipeline；The mashing pump 4-2 is set to the bottom of the eluting column 4-1；The leaching
Wash the top that tower heat exchanger 4-3 is set to the eluting column 4-1；Tower bottom liquid outlet and the elution of the eluting column 4-1 is starched
The entrance of material subsider 4-5 is connected by pipeline；The gas of the eluting column 4-1 offgas outlet and the drop catcher 4-4 enters
Mouth is connected by pipeline；The gas vent of the drop catcher 4-4 is connected with the gas access of exhaust treatment system by pipeline
It connects；The liquid outlet of the drop catcher 4-4 is connected with the entrance of the elution slurry subsider 4-5 by pipeline；The leaching
The supernatant outlet of pulp washing material subsider 4-5 is connected with the inlet of the rectifying column 5-3 by pipeline；
The refluxing opening of the rectifying column 5-3 is connected with the inlet of the reboiler 5-1 by pipeline；The reboiler
The gas outlet of 5-1 is connected with the air inlet of the rectifying column 5-3 by pipeline；The reboiler heat exchanger 5-2 is set to institute
State the inside of reboiler 5-1；The hot fluid of the reboiler heat exchanger 5-2 hot fluid outlet ports and the powder heat exchanger 6-3 processed enters
Mouth is connected by pipeline；High-purity vanadium oxytrichloride gas vent of the rectifying column 5-3 and high-purity vanadium oxytrichloride condenser
The gas access of 5-4 is connected by pipeline；The liquid outlet of high-purity vanadium oxytrichloride condenser 5-4 and high-purity trichlorine
The liquid inlet of vanadyl storage tank 5-5 is connected by pipeline；The liquid outlet and the powder processed of high-purity vanadium oxytrichloride storage tank 5-5
The vanadium oxytrichloride entrance of reactor 6-1 is connected by pipeline；The powder heat exchanger 6-3 processed is set to the powder reactor 6- processed
1 middle part；The thermal fluid inlet of the hot fluid outlet ports of the powder heat exchanger 6-3 processed and the powder soft water storage tank 6-4 processed pass through pipeline
It is connected；The fluid inlet of the hot fluid outlet ports of the powder soft water storage tank 6-4 processed and the powder water circulating pump 6-5 processed pass through pipeline
It is connected；The offgas outlet of the powder reactor 6-1 processed is connected with chlorine circulatory system entrance by pipeline；The ultrapure water
The feed inlet of vaporizer 6-2 is connected with purification oxygen-enriched air general pipeline, ultrapure supply mains respectively；The ultrapure water vaporizer 6-2's
Gas outlet is connected with the air inlet of the powder reactor 6-1 processed by pipeline；The discharge gate of the powder reactor 6-1 processed and institute
The feed inlet for stating high purity vanadium feed bin 6-6 is connected by pipeline；The discharge gate and the high purity vanadium spiral shell of the high purity vanadium feed bin 6-6
The feed inlet of rotation batcher 6-7 is connected by pipeline；
The water inlet of the technique water vaporizer 7-1 is connected with technique supply mains；The technique water vaporizer 7-1's goes out
Port is connected with the air inlet of the hydrolysis dechlorination fluidized bed 7-2 by pipeline；The air inlet of the hydrolysis dechlorination fluidized bed 7-2
Mouth is connected with air header simultaneously；The fuel inlet of the hydrolysis dechlorination fluidized bed 7-2 is connected with fuel manifold；The water
It solves and is equipped with processing slag discharge gate in the middle part of dechlorination fluidized bed 7-2；The offgas outlet and the whirlwind of the hydrolysis dechlorination fluidized bed 7-2
The air inlet of separator 7-3 is connected by pipeline；The gas vent of the cyclone separator 7-3 and the bag filter 7-
4 gas access is connected by pipeline；The dust outlet of the cyclone separator 7-3 and the hydrolysis dechlorination fluidized bed 7-2
Feed inlet be connected by pipeline；The air inlet of the dust outlet of the bag filter 7-4 and the cyclone separator 7-3
It is connected by pipeline；The offgas outlet of the bag filter 7-4 is connected with the air inlet of exhaust treatment system by pipeline
It connects.
The method of vanadium slag cleaning chlorination production high purity vanadic anhydride of the present invention based on above system is specific to wrap
Include following steps:
Vanadium slag in the vanadium slag feed bin 1-1 enters the chlorination by the vanadium slag screw(-type) feeder 1-2 and is granulated fluidisation
In bed 1-3, oxidation reaction occurs with the air from pneumatic manifold, while with particle growth；The oxidation is granulated
The operation temperature of fluidized bed 1-3 is 400 DEG C~1000 DEG C；Reaction end gas send tail after the cyclone dust collectors 1-4 removes dust
Gas processing system；Oxidation clinker successively enters institute through the granulation vanadium slag feed bin 2-1, the granulation vanadium slag screw feeder 2-2
It states in fluidized bed blender 2-5；Carbon source in the carbon source feed bin 2-3 enters the stream through the carbon source screw feeder 2-4
Change in bed blender 2-5；Carbon source quality is be granulated vanadium slag quality 5%~25% in the fluidized bed blender 2-5；It is fluidizing
It is uniformly mixed under the action of nitrogen with vanadium slag and enters in the chlorination furnace 3-1 together；Nitrogen, circulation chlorine from nitrogen header pipe
The chlorine of gas general pipeline, the chlorine of chlorine general pipeline enter from the air inlet of the bottom the chlorination furnace 3-1；Maintain vanadium slag and carbon source fluidised form
While change, chlorination reaction occurs therewith；Chlorination operation temperature is 280~950 DEG C；The vanadium oxytrichloride flue gas generated is reacted through institute
It states and the eluting column 4-1 is sent to elute after gathering dust tower 3-3 dedusting；Chlorination tailings send the hydrolysis dechlorination fluidized bed 7-2 dechlorination to handle；
From the slurry of the elution slurry subsider 4-5 and the low liquid of kettle of the reboiler 5-1 from the top of the chlorination furnace 3-1
It sprays into, to adjust reaction temperature；Waste heat of the chlorination furnace heat exchanger 3-2 to assist removing chlorination reaction, prevents
Furnace temperature is excessively high；From the slurry of the elution slurry subsider 4-5 and the kettle base solution of the reboiler 5-1 from the tower that gathers dust
The top of 3-3 sprays into, and to evaporate the solid dust of slurry and kettle base solution, while reducing the temperature of chlorination flue gas；It is described to gather dust
Dust-slag collection in tower 3-3 send the hydrolysis dechlorination fluidized bed 7-2 dechlorination to handle；The tower heat exchanger 3-4 that gathers dust gathers dust from described
The sensible heat of high-temp chlorination flue gas is recycled in tower 3-3, and provides heat for the reboiler 5-1 and powder reactor 6-1 processed, realizes section
It can consumption reduction；
The elution tail gas of the eluting column 4-1 send exhaust treatment system after the drop catcher 4-4 recycles drop；The leaching
The vanadium oxytrichloride liquid for washing the vanadium oxytrichloride slurry that tower 4-1 is eluted and drop catcher 4-4 recycling send the elution slurry
Subsider 4-5 settlement treatment；Obtained supernatant is passed through in the powder reactor 6-1 processed after rectifying column 5-3 purification；
Air from purification oxygen-enriched air general pipeline and the ultrapure water from ultrapure supply mains pass through the ultrapure water vaporizer 6-2
It is sent in the powder reactor 6-1 processed after preheating vaporization, catalytic oxidation occurs with vanadium oxytrichloride, obtains rich chlorine flue gas and high-purity
Vanadic anhydride；The reaction temperature of catalytic oxidation process is 120 DEG C~620 DEG C；Rich chlorine flue gas send the chlorine circulatory system；High-purity five
V 2 O send the high purity vanadium feed bin 6-6；Process water from technique supply mains gasifies through the technique water vaporizer 7-1
Afterwards be sent into together with the air of air header in the hydrolysis dechlorination fluidized bed 7-2, maintain the fluidization of chloride residue,
And hydrolysis dechlorination reaction occurs therewith；Fuel from fuel manifold is from the fuel of the bottom hydrolysis dechlorination fluidized bed 7-2
Entrance enters, and provides heat for reaction；Reaction temperature is 500 DEG C~900 DEG C；The mean residence time of powder is 30~80 points
Clock；Dechlorination tailings chlorinty is within 2%；Dechlorination tailings send refining ferrochrome；Dechlorination tail gas successively through the cyclone separator 7-3,
Exhaust treatment system is sent after bag filter 7-4 removing dust；The dust of the bag filter 7-4 recycling returns to the whirlwind
In separator 7-3, enter in the hydrolysis dechlorination fluidized bed 7-2 together with the dust of cyclone separator 7-3 recycling.
As preferred: the mass fraction of vanadic anhydride is 8%~28% in vanadium slag, and the mass fraction of chromium oxide is
0.5%~16%.
As preferred: the operating gas velocity in the granulating fluidized bed 1-3 of oxidation is 0.05m~4.00m/s, and vanadium slag is averaged
Residence time is 30~120min.
As preferred: the carbon source in the carbon source feed bin 2-3 refer to metallurgical coke, petroleum coke and coal dust etc. it is one such or
It is several.
As preferred: in the chlorination furnace 3-1, operating gas velocity is 0.04m~4.00m/s, into the indoor chlorine nitrogen of wind
The molar fraction of chlorine is 15%~100% in gas gaseous mixture；The chlorination rate of vanadic anhydride is 95% or more, the chlorine of chromium oxide
Rate is within 5%.
As preferred: in the powder reactor 6-1 processed, be passed through vapor be passed through vanadium oxytrichloride quality 0.05%~
12%, being passed through oxygen content volume fraction in clean oxygen-enriched air is 29%~97%, and the purity of high purity vanadic anhydride is
99.5% or more.
The present invention aoxidizes granulation processing by fluidized bed, realizes that vanadium slag mine is mutually reformed and ore particle is grown up；Pass through selective chlorine
Change and by the vanadium in vanadium slag convert gaseous state vanadium oxytrichloride, most of impurity such as chromium, iron, calcium, phosphorus, manganese, titanium, silicon in vanadium slag are stayed
In chloride residue, efficiently separating for vanadium and chromium and other impurities is realized.Gaseous vanadium oxytrichloride successively passes through dedusting-elution-
High purity vanadic anhydride is prepared in the processes such as sedimentation-rectifying purifying-catalysis oxidation.Chloride residue passes through at vapor phase hydrolysis dechlorination
Reason, processing slag return to refining ferrochrome.
Compared with the existing technology, the present invention has the advantages that protrude as follows:
(1) vanadium slag is handled through peroxidating granulation, is carried out mine and is mutually reformed, and is realized vanadium chromium, vanadium iron separation, is greatly improved the chlorine of vanadium
Change selectivity, realization is efficiently separated with other impurities；It grows up simultaneously with ore particle, is conducive to improve fluidization quality, realize
Efficient chlorination；
(2) vanadium slag is sufficiently mixed in fluidized bed blender by predetermined ratio first with carbon source, then enters back into chlorination furnace
Reaction ensure that the consistency and mixed uniformity of reaction raw materials proportion, to realize the chlorination of efficient stable；
(3) vanadium slag is strong exothermal reaction with carbon chlorination, and the chlorination furnace heat exchanger that is arranged can will be extra in the present invention
Heat removes, and prevents chlorination furnace from overheating；
(4) it is equipped with the tower heat exchanger that gathers dust in the present invention for recycling the part sensible heat of high-temp chlorination flue gas, and is reboiler
And powder reactor processed provides heat, realizes energy-saving, reduction production cost；
(5) chloride residue in the present invention is handled using the dechlorination of hydrolysis dechlorination fluidized bed, and treated, and tailings can refine chromium
Iron realizes tailings comprehensive utilization；
(6) catalysis oxidation for realizing vanadium oxytrichloride in the present invention with addition of a small amount of water by oxygen-enriched air, obtains high-purity five oxygen
Change two vanadium and rich chlorine tail gas, realize chlorine recycling, substantially reduces production and environmentally friendly cost.
The technology for preparing high purity vanadic anhydride using vanadium slag chloridising using the present invention can effectively improve chlorination selection
Property, realization is efficiently separated with other impurities, while realizing the integrated treatment of chloride slag and the Efficient Cycle of chlorine, and is realized high
The Exposure degree of warm chlorination flue gas utilizes, and has many advantages, such as that high-efficient, low energy consumption, pollution-free, product quality is good, can effectively mention
Vanadium-rich slag chloridising prepares the economic benefit and social benefit of vanadic anhydride technology.
Detailed description of the invention
Fig. 1 is the configuration schematic diagram that vanadium slag of the invention cleans chlorination production high purity vanadic anhydride system.
Appended drawing reference:
1 material papering section；
1-1 vanadium slag feed bin 1-2 vanadium slag screw(-type) feeder
1-3 aoxidizes granulating fluidized bed 1-4 cyclone dust collectors；
2 mixing workshop sections；
2-1 is granulated vanadium slag feed bin 2-2 and is granulated vanadium slag screw feeder
2-3 carbon source feed bin 2-4 carbon source screw feeder
2-5 fluidized bed blender；
3 chloridized dust collection workshop sections；
3-1 chlorination furnace 3-2 chlorination furnace heat exchanger
The 3-3 tower 3-4 that gathers dust gathers dust tower heat exchanger；
4 elution sedimentation workshop sections；
4-1 eluting column 4-2 mashing pump
4-3 eluting column heat exchanger 4-4 drop catcher
4-5 elutes slurry subsider；
5 refinements；
5-1 reboiler 5-2 reboiler heat exchanger
The high-purity vanadium oxytrichloride condenser of 5-3 rectifying column 5-4
The high-purity vanadium oxytrichloride storage tank of 5-5；
6 Zhi Fen workshop sections；
The ultrapure water vaporizer of 6-1 powder reactor 6-2
6-3 powder heat exchanger 6-4 powder soft water storage tank
6-5 powder water circulating pump 6-6 high purity vanadium feed bin
6-7 high purity vanadium screw(-type) feeder；
7 chloride residue processing sections；
7-1 technique water vaporizer 7-2 hydrolysis dechlorination fluidized bed
7-3 cyclone separator 7-4 bag filter.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached in the embodiment of the present invention
Figure, the technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is the present invention
A part of the embodiment, instead of all the embodiments.It is worth noting that embodiment is only to illustrate technical side of the invention
Case, rather than its limitations.Fig. 1 is that the system and method that a kind of vanadium slag of the invention cleans chlorination production high purity vanadic anhydride are shown
It is intended to.
Embodiment 1
In conjunction with Fig. 1, a kind of system of vanadium slag cleaning chlorination production high purity vanadic anhydride used in the present embodiment, including
Material papering section 1, mixing workshop section 2, chloridized dust collection workshop section 3, elution sedimentation workshop section 4, refinement 5, Zhi Fen workshop section 6 and chloride residue
Processing section 7；
Material papering section 1 includes that vanadium slag feed bin 1-1, vanadium slag screw(-type) feeder 1-2, the granulating fluidized bed 1-3 of oxidation and whirlwind remove
Dirt device 1-4；
Mixing workshop section 2 includes being granulated vanadium slag feed bin 2-1, being granulated vanadium slag screw feeder 2-2, carbon source feed bin 2-3, carbon source spiral shell
Revolve dispenser 2-4 and fluidized bed blender 2-5；
Chloridized dust collection workshop section 3 includes chlorination furnace 3-1, chlorination furnace heat exchanger 3-2, gather dust the tower 3-3 and tower heat exchanger 3- that gathers dust
4；
Elution sedimentation workshop section 4 includes eluting column 4-1, mashing pump 4-2, eluting column heat exchanger 4-3, drop catcher 4-4 and elution
Slurry subsider 4-5；
Refinement 5 includes reboiler 5-1, reboiler heat exchanger 5-2, rectifying column 5-3, high-purity vanadium oxytrichloride condenser 5-
4 and high-purity vanadium oxytrichloride storage tank 5-5；
Zhi Fen workshop section 6 includes powder reactor 6-1 processed, ultrapure water vaporizer 6-2, powder heat exchanger 6-3 processed, powder soft water storage tank processed
6-4, powder water circulating pump 6-5 processed, high purity vanadium feed bin 6-6 and high purity vanadium screw(-type) feeder 6-7；
Chloride residue processing section 7 includes technique water vaporizer 7-1, hydrolysis dechlorination fluidized bed 7-2, cyclone separator 7-3
With bag filter 7-4；
The discharge port of the bottom vanadium slag feed bin 1-1 is connected with the feed inlet of vanadium slag screw(-type) feeder 1-2；Vanadium slag screw feeder
The discharge port of machine 1-2 is connected with the feed inlet for aoxidizing granulating fluidized bed 1-3 by pipeline；Aoxidize granulating fluidized bed 1-3 into
Port is connected with pneumatic manifold by pipeline；The offgas outlet of granulating fluidized bed 1-3 is aoxidized with cyclone dust collectors 1-4's
Air inlet is connected by pipeline；The gas outlet of cyclone dust collectors 1-4 is connected with the air inlet of exhaust treatment system by pipeline
It connects；The dust outlet of cyclone dust collectors 1-4 is connected with the dust inlet for aoxidizing granulating fluidized bed 1-3 by pipeline；Oxidation is made
The discharge gate of grain fluidized bed 1-3 is connected with the feed inlet for being granulated vanadium slag feed bin 2-1 by pipeline；It is granulated vanadium slag feed bin 2-1's
Discharge port is connected with the feed inlet for being granulated vanadium slag screw feeder 2-2；It is granulated the discharge port and stream of vanadium slag screw feeder 2-2
The feed inlet for changing bed blender 2-5 is connected by pipeline；The discharge port of carbon source feed bin 2-3 is with carbon source screw feeder 2-4's
Feed inlet is connected；The discharge port of carbon source screw feeder 2-4 is connected with the feed inlet of fluidized bed blender 2-5 by pipeline
It connects；The fluidisation gas inlet of fluidized bed blender 2-5 is connected with nitrogen header pipe；The discharge port and chlorine of fluidized bed blender 2-5
The feed inlet for changing furnace 3-1 is connected by pipeline；
The air inlet of chlorination furnace 3-1 is connected with nitrogen header pipe, circulating chlorine gas general pipeline, chlorine general pipeline by pipeline respectively；
The chlorination exhanst gas outlet of chlorination furnace 3-1 is connected with the gas access for the tower 3-3 that gathers dust by pipeline；The chlorination of chlorination furnace 3-1 is residual
Slag outlet is connected with the feed inlet of hydrolysis dechlorination fluidized bed 7-2 by pipeline；Slurry inlet at the top of chlorination furnace 3-1 respectively with
The kettle base solution outlet for eluting the slurry outlet and reboiler 5-1 of slurry subsider 4-5 is connected by pipeline；Chlorination furnace heat exchanger
3-2 is set in the middle part of the chlorination furnace 3-1；The gas vent of tower 3-3 of gathering dust is connected with the air inlet of eluting column 4-1 by pipeline
It connects；The slurry inlet to gather dust at the top of tower 3-3 the bottom with the slurry outlet of elution slurry subsider 4-5 and reboiler 5-1 respectively
Liquid mouth goes out to be connected by pipeline；The discharge gate of tower 3-3 of gathering dust is connected with the feed inlet of hydrolysis dechlorination fluidized bed 7-2 by pipeline
It connects；The tower heat exchanger 3-4 that gathers dust is set to the middle part for the tower 3-3 that gathers dust；The tower heat exchanger 3-4 hot fluid outlet ports that gather dust exchange heat with reboiler
The hot inlet of device 5-2 is connected by pipeline；Gather dust the thermal fluid inlet and powder water circulating pump 6-5 processed of tower heat exchanger 3-4
Fluid outlet is connected by pipeline；Mashing pump 4-2 is set to the bottom of eluting column 4-1；Eluting column heat exchanger 4-3 is set to leaching
Wash the top of tower 4-1；The tower bottom liquid outlet of eluting column 4-1 is connected with the entrance of elution slurry subsider 4-5 by pipeline；Leaching
Tower 4-1 offgas outlet is washed to be connected with the gas access of drop catcher 4-4 by pipeline；The gas vent and tail gas of drop catcher 4-4
The gas access of processing system is connected by pipeline；The liquid outlet of drop catcher 4-4 and the entrance of elution slurry subsider 4-5
It is connected by pipeline；The supernatant outlet of elution slurry subsider 4-5 is connected with the inlet of rectifying column 5-3 by pipeline
It connects；
The refluxing opening of rectifying column 5-3 is connected with the inlet of reboiler 5-1 by pipeline；The gas outlet of reboiler 5-1
It is connected with the air inlet of rectifying column 5-3 by pipeline；Reboiler heat exchanger 5-2 is set to the inside of reboiler 5-1；Reboiler
Heat exchanger 5-2 hot fluid outlet ports are connected with the thermal fluid inlet of powder heat exchanger 6-3 processed by pipeline；Rectifying column 5-3's is high-purity
Vanadium oxytrichloride gas vent is connected with the gas access of high-purity vanadium oxytrichloride condenser 5-4 by pipeline；High-purity vanadium oxytrichloride
The liquid outlet of condenser 5-4 is connected with the liquid inlet of high-purity vanadium oxytrichloride storage tank 5-5 by pipeline；High-purity vanadium oxytrichloride
The liquid outlet of storage tank 5-5 is connected with the vanadium oxytrichloride entrance of powder reactor 6-1 processed by pipeline；Powder heat exchanger 6-3 setting processed
In the middle part of powder reactor 6-1 processed；The thermal fluid inlet of the hot fluid outlet ports of powder heat exchanger 6-3 processed and powder soft water storage tank 6-4 processed are logical
Piping is connected；The hot fluid outlet ports of powder soft water storage tank 6-4 processed and the fluid inlet of powder water circulating pump 6-5 processed pass through pipeline phase
Connection；The offgas outlet of powder reactor 6-1 processed is connected with chlorine circulatory system entrance by pipeline；Ultrapure water vaporizer 6-2
Feed inlet be connected respectively with purification oxygen-enriched air general pipeline, ultrapure supply mains；The gas outlet of ultrapure water vaporizer 6-2 and powder processed are anti-
The air inlet of device 6-1 is answered to be connected by pipeline；The discharge gate of powder reactor 6-1 processed and the feed inlet of high purity vanadium feed bin 6-6 are logical
Piping is connected；The discharge gate of high purity vanadium feed bin 6-6 is connected with the feed inlet of high purity vanadium screw(-type) feeder 6-7 by pipeline
It connects；
The water inlet of technique water vaporizer 7-1 is connected with technique supply mains；The gas outlet of technique water vaporizer 7-1 and water
The air inlet of solution dechlorination fluidized bed 7-2 is connected by pipeline；The air inlet of hydrolysis dechlorination fluidized bed 7-2 while and air header
It is connected；The fuel inlet of hydrolysis dechlorination fluidized bed 7-2 is connected with fuel manifold；It is equipped in the middle part of hydrolysis dechlorination fluidized bed 7-2
Handle slag discharge gate；The offgas outlet of hydrolysis dechlorination fluidized bed 7-2 is connected with the air inlet of cyclone separator 7-3 by pipeline
It connects；The gas vent of cyclone separator 7-3 is connected with the gas access of bag filter 7-4 by pipeline；Cyclone separator
The dust outlet of 7-3 is connected with the feed inlet of hydrolysis dechlorination fluidized bed 7-2 by pipeline；The dust of bag filter 7-4 goes out
Mouth is connected with the air inlet of cyclone separator 7-3 by pipeline；The offgas outlet and exhaust treatment system of bag filter 7-4
Air inlet be connected by pipeline.
Embodiment 2
Using system described in embodiment 1, the present embodiment provides a kind of methods for preparing high purity vanadic anhydride powder, including
Following steps:
Vanadium slag in vanadium slag feed bin 1-1 enters in the granulating fluidized bed 1-3 of chlorination by vanadium slag screw(-type) feeder 1-2, with
Oxidation reaction occurs from the air in pneumatic manifold, while with particle growth；Aoxidize the operation temperature of granulating fluidized bed 1-3
Degree is 400 DEG C~1000 DEG C；Reaction end gas send exhaust treatment system after cyclone dust collectors 1-4 removes dust；Aoxidize clinker according to
It is secondary to enter in fluidized bed blender 2-5 through granulation vanadium slag feed bin 2-1, granulation vanadium slag screw feeder 2-2；In carbon source feed bin 2-3
Carbon source enter in fluidized bed blender 2-5 through carbon source screw feeder 2-4；Carbon source quality is to make in fluidized bed blender 2-5
The 5%~25% of grain vanadium slag quality；It is uniformly mixed under the action of fluidizing nitrogen with vanadium slag and enters in chlorination furnace 3-1 together；Come
From in the nitrogen of nitrogen header pipe, the chlorine of circulating chlorine gas general pipeline, chlorine general pipeline chlorine from the air inlet of the bottom chlorination furnace 3-1 into
Enter；It maintains vanadium slag and carbon source fluidised simultaneously, chlorination reaction occurs therewith；Chlorination operation temperature is 280~950 DEG C；Reaction
The vanadium oxytrichloride flue gas of generation, which is gathered dust, send after tower 3-3 dedusting eluting column 4-1 to elute；Chlorination tailings send hydrolysis dechlorination fluidized bed 7-
2 dechlorinations processing；It is sprayed from the slurry of elution slurry subsider 4-5 and the kettle base solution of reboiler 5-1 from the top of chlorination furnace 3-1
Enter, to adjust reaction temperature；Waste heat of the chlorination furnace heat exchanger 3-2 to assist removing chlorination reaction, prevents furnace temperature mistake
It is high；It is sprayed into from the slurry of elution slurry subsider 4-5 and the kettle base solution of reboiler 5-1 from the top for the tower 3-3 that gathers dust, to
The solid dust of slurry and kettle base solution is evaporated, while reducing the temperature of chlorination flue gas；The dust-slag collection in tower 3-3 that gathers dust send hydrolysis de-
Chlorine fluidized bed 7-2 dechlorination processing；The tower heat exchanger 3-4 that gathers dust recycles the sensible heat of high-temp chlorination flue gas from the tower 3-3 that gathers dust, and for again
It boils device 5-1 and powder reactor 6-1 processed and heat is provided, realize energy-saving；
The elution tail gas of eluting column 4-1 send exhaust treatment system after drop catcher 4-4 recycles drop；Eluting column 4-1 elution
The vanadium oxytrichloride liquid of obtained vanadium oxytrichloride slurry and drop catcher 4-4 recycling send elution slurry subsider 4-5 settlement treatment；?
The supernatant arrived is passed through in powder reactor 6-1 processed after rectifying column 5-3 purification；From the air of purification oxygen-enriched air general pipeline
And from ultrapure supply mains ultrapure water by ultrapure water vaporizer 6-2 preheating vaporization after send in powder reactor 6-1 processed, with three
Catalytic oxidation occurs for chlorine vanadyl, obtains rich chlorine flue gas and high purity vanadic anhydride；The reaction temperature of catalytic oxidation process is
120 DEG C~620 DEG C；Rich chlorine flue gas send the chlorine circulatory system；High purity vanadic anhydride send high purity vanadium feed bin 6-6；From technique
The process water of supply mains is sent into hydrolysis dechlorination stream after technique water vaporizer 7-1 gasification together with from the air of air header
Change in bed 7-2, maintain the fluidization of chloride residue, and hydrolysis dechlorination reaction occurs therewith；From fuel manifold fuel from
The fuel inlet of the bottom hydrolysis dechlorination fluidized bed 7-2 enters, and provides heat for reaction；Reaction temperature is 500 DEG C~900 DEG C；Powder
The mean residence time of material is 30~80 minutes；Dechlorination tailings chlorinty is within 2%；Dechlorination tailings send refining ferrochrome；Dechlorination tail
Gas successively send exhaust treatment system after cyclone separator 7-3, bag filter 7-4 remove dust；Bag filter 7-4 recycling
Dust return cyclone separator 7-3 in, with cyclone separator 7-3 recycling dust together with enter hydrolysis dechlorination fluidized bed 7-2
In.
Embodiment 3
The present embodiment is using vanadium slag as raw material, and wherein the mass fraction of vanadic anhydride is 8%, and the mass fraction of chromium oxide is
0.5%, treating capacity 300kg/h, through oxidation granulations, mixing, chloridized dust collection, elute settle, refine, the processes such as powder processed are prepared into
Industrial surplus energy utility and residue dechlorination processing are realized to high purity vanadic anhydride product, and by UTILIZATION OF VESIDUAL HEAT IN, residue treatment.
In the granulating fluidized bed 1-3 of oxidation, oxidizing roasting temperature is 400 DEG C, operating gas velocity 0.05m/s, vanadium slag
Mean residence time be 30min；In the fluidized bed blender 2-5, metallurgical coke is with 5% that dosage is vanadium slag quality；Chlorine
Changing furnace chlorination temperature is 280 DEG C, and chlorination furnace operating gas velocity is 0.04m/s, into chlorine in the indoor chlorine nitrogen mixture of wind
Molar fraction be 15%, the chlorination rate 95% of vanadic anhydride, the chlorination rate of chromium oxide is 5%；In powder reactor processed, urge
Change oxidation process and be passed through vapor is vanadium oxytrichloride quality 0.05%, reaction temperature is 120 DEG C, oxygen in the oxygen-enriched air being passed through
The mass fraction of gas is 29%, and for the direct yield of vanadium up to 94%, the purity of high purity vanadic anhydride product reaches 99.5wt% (2N5)；
In the hydrolysis dechlorination fluidized bed, reaction temperature is 500 DEG C, and the residence time of powder is 30min, and dechlorination tailings chlorinty exists
2%.
Embodiment 4
The present embodiment is using chromium type high vanadium slag as raw material, and wherein the mass fraction of vanadic anhydride is 28%, the matter of chromium oxide
Measuring score is 16%, treating capacity 800kg/h, through oxidation granulations, mixing, chloridized dust collection, elute settle, refine, the works such as powder processed
High purity vanadic anhydride product is prepared in sequence, and realizes that industrial surplus energy utility and residue are de- by UTILIZATION OF VESIDUAL HEAT IN, residue treatment
Chlorine processing.
In the granulating fluidized bed 1-3 of oxidation, oxidizing roasting temperature is 1000 DEG C, operating gas velocity 4.00m/s, vanadium slag
Mean residence time be 120min；In the fluidized bed blender 2-5, petroleum coke is with 25% that dosage is vanadium slag quality；
Chlorination furnace chlorination temperature is 950 DEG C, and chlorination furnace operating gas velocity is 4.00m/s, and chloridric medium is pure chlorine；The chlorine of vanadic anhydride
Rate 98%, the chlorination rate 2% of chromium oxide；In powder reactor processed, it is vanadium oxytrichloride matter that catalytic oxidation process, which is passed through vapor,
The 12% of amount, reaction temperature are 620 DEG C, and the mass fraction of oxygen is 97% in the oxygen-enriched air being passed through, and the direct yield of vanadium reaches
96%, the purity of high purity vanadic anhydride product reaches 99.95wt% (3N5)；In the hydrolysis dechlorination fluidized bed, reaction temperature
It is 900 DEG C, the residence time of powder is 80min, and dechlorination tailings chlorinty is 1%.
Embodiment 5
The present embodiment is using chromium type high vanadium slag as raw material, and wherein the mass fraction of vanadic anhydride is 20%, the matter of chromium oxide
Measuring score is 12%, treating capacity 600kg/h, through oxidation granulations, mixing, chloridized dust collection, elute settle, refine, the works such as powder processed
High purity vanadic anhydride product is prepared in sequence, and realizes that industrial surplus energy utility and residue are de- by UTILIZATION OF VESIDUAL HEAT IN, residue treatment
Chlorine processing.
In the granulating fluidized bed 1-3 of oxidation, oxidizing roasting temperature is 800 DEG C, operating gas velocity 2.00m/s, vanadium slag
Mean residence time be 60min；In the fluidized bed blender 2-5, coal dust is with 20% that dosage is vanadium slag quality；Chlorination
Furnace chlorination temperature is 650 DEG C, and chlorination furnace operating gas velocity is 2.00m/s, into chlorine in the indoor chlorine nitrogen mixture of wind
Molar fraction is 75%；The chlorination rate 97% of vanadic anhydride, the chlorination rate 1% of chromium oxide；In powder reactor processed, it is catalyzed oxygen
Change process is passed through 6% that vapor is vanadium oxytrichloride quality, and reaction temperature is 300 DEG C, the matter of oxygen in the oxygen-enriched air being passed through
Measuring score is 90%, and for the direct yield of vanadium up to 95%, the purity of high purity vanadic anhydride product reaches 99.995wt% (4N5)；Institute
It states in hydrolysis dechlorination fluidized bed, reaction temperature is 700 DEG C, and the residence time of powder is 50min, and dechlorination tailings chlorinty exists
0.5%.
Non-elaborated part of the present invention belongs to techniques well known.
Certainly, the present invention can also there are many embodiments, without deviating from the spirit and substance of the present invention, are familiar with
Those skilled in the art can disclosure according to the present invention make various corresponding changes and modifications, but these it is corresponding change and
Deformation all should belong to scope of protection of the claims of the invention.
Claims (7)
1. a kind of system of vanadium slag cleaning chlorination production high purity vanadic anhydride, which is characterized in that the system comprises stock works
Section (1), mixing workshop section (2), chloridized dust collection workshop section (3), elution sedimentation workshop section (4), refinement (5), Zhi Fen workshop section (6) and chlorine
Change residue treatment workshop section (7)；
The material papering section (1) includes vanadium slag feed bin (1-1), vanadium slag screw(-type) feeder (1-2), aoxidizes granulating fluidized bed (1-3)
With cyclone dust collectors (1-4)；
The mixing workshop section (2) includes being granulated vanadium slag feed bin (2-1), being granulated vanadium slag screw feeder (2-2), carbon source feed bin (2-
3), carbon source screw feeder (2-4) and fluidized bed blender (2-5)；
The chloridized dust collection workshop section (3) includes chlorination furnace (3-1), chlorination furnace heat exchanger (3-2), the tower that gathers dust (3-3) and the tower that gathers dust
Heat exchanger (3-4)；
Elution sedimentation workshop section (4) includes eluting column (4-1), mashing pump (4-2), eluting column heat exchanger (4-3), drop catcher
(4-4) and elution slurry subsider (4-5)；
The refinement (5) includes reboiler (5-1), reboiler heat exchanger (5-2), rectifying column (5-3), high-purity vanadium oxytrichloride
Condenser (5-4) and high-purity vanadium oxytrichloride storage tank (5-5)；
The Zhi Fen workshop section (6) includes powder reactor (6-1) processed, ultrapure water vaporizer (6-2), powder heat exchanger processed (6-3), powder processed
Soft water storage tank (6-4), powder water circulating pump processed (6-5), high purity vanadium feed bin (6-6) and high purity vanadium screw(-type) feeder (6-7)；
The chloride residue processing section (7) includes technique water vaporizer (7-1), hydrolysis dechlorination fluidized bed (7-2), cyclonic separation
Device (7-3) and bag filter (7-4)；
The discharge port of vanadium slag feed bin (1-1) bottom is connected with the feed inlet of the vanadium slag screw(-type) feeder (1-2)；It is described
The discharge port of vanadium slag screw(-type) feeder (1-2) is connected with the feed inlet for aoxidizing granulating fluidized bed (1-3) by pipeline；Institute
It states and aoxidizes the air inlet of granulating fluidized bed (1-3) and be connected with pneumatic manifold by pipeline；The oxidation is granulating fluidized bed
The offgas outlet of (1-3) is connected with the air inlet of the cyclone dust collectors (1-4) by pipeline；Cyclone dust collectors (the 1-
4) gas outlet is connected with the air inlet of exhaust treatment system by pipeline；The dust outlet of the cyclone dust collectors (1-4)
It is connected with the dust inlet for aoxidizing granulating fluidized bed (1-3) by pipeline；The row for aoxidizing granulating fluidized bed (1-3)
Material mouth is connected with the feed inlet for being granulated vanadium slag feed bin (2-1) by pipeline；The discharging for being granulated vanadium slag feed bin (2-1)
Mouth is connected with the feed inlet for being granulated vanadium slag screw feeder (2-2)；It is described to be granulated going out for vanadium slag screw feeder (2-2)
Material mouth is connected with the feed inlet of the fluidized bed blender (2-5) by pipeline；The discharge port of the carbon source feed bin (2-3) with
The feed inlet of the carbon source screw feeder (2-4) is connected；The discharge port and the stream of the carbon source screw feeder (2-4)
The feed inlet for changing bed blender (2-5) is connected by pipeline；The fluidisation gas inlet and nitrogen of the fluidized bed blender (2-5)
Gas general pipeline is connected；The discharge port of the fluidized bed blender (2-5) and the feed inlet of the chlorination furnace (3-1) pass through pipeline phase
Connection；
The air inlet of the chlorination furnace (3-1) is connected with nitrogen header pipe, circulating chlorine gas general pipeline, chlorine general pipeline by pipeline respectively
It connects；The chlorination exhanst gas outlet of the chlorination furnace (3-1) is connected with the gas access of the tower that gathers dust (3-3) by pipeline；Institute
The chloride residue outlet for stating chlorination furnace (3-1) is connected with the feed inlet of the hydrolysis dechlorination fluidized bed (7-2) by pipeline；Institute
State the slurry inlet at the top of chlorination furnace (3-1) respectively with the slurry outlet of elution slurry subsider (4-5) and described boil again
The kettle base solution outlet of device (5-1) is connected by pipeline；The chlorination furnace heat exchanger (3-2) is set to the chlorination furnace (3-1)
Middle part；The gas vent of the tower that gathers dust (3-3) is connected with the air inlet of the eluting column (4-1) by pipeline；The receipts
Slurry inlet at the top of chimney (3-3) slurry outlet and the reboiler (5- with elution slurry subsider (4-5) respectively
1) kettle base solution goes out-and mouth is connected by pipeline；The discharge gate of the tower that gathers dust (3-3) and the hydrolysis dechlorination fluidized bed (7-
2) feed inlet is connected by pipeline；The tower heat exchanger (3-4) that gathers dust is set to the middle part of tower (3-3) that gather dust；Institute
Tower heat exchanger (3-4) hot fluid outlet ports that gather dust are stated to be connected with the hot inlet of the reboiler heat exchanger (5-2) by pipeline；
The thermal fluid inlet of the tower heat exchanger (3-4) that gathers dust and the fluid outlet of the powder water circulating pump (6-5) processed pass through pipeline phase
Connection；The mashing pump (4-2) is set to the bottom of the eluting column (4-1)；The eluting column heat exchanger (4-3) is set to institute
State the top of eluting column (4-1)；The tower bottom liquid outlet of the eluting column (4-1) and entering for elution slurry subsider (4-5)
Mouth is connected by pipeline；The gas access of eluting column (4-1) offgas outlet and the drop catcher (4-4) passes through pipeline phase
Connection；The gas vent of the drop catcher (4-4) is connected with the gas access of exhaust treatment system by pipeline；It is described to catch drop
The liquid outlet of device (4-4) is connected with the entrance of elution slurry subsider (4-5) by pipeline；The elution slurry is heavy
The supernatant outlet of drop slot (4-5) is connected with the inlet of the rectifying column (5-3) by pipeline；
The refluxing opening of the rectifying column (5-3) is connected with the inlet of the reboiler (5-1) by pipeline；The reboiler
The gas outlet of (5-1) is connected with the air inlet of the rectifying column (5-3) by pipeline；The reboiler heat exchanger (5-2) sets
It is placed in the inside of the reboiler (5-1)；Reboiler heat exchanger (5-2) hot fluid outlet ports and the powder heat exchanger (6- processed
3) thermal fluid inlet is connected by pipeline；High-purity vanadium oxytrichloride gas vent of the rectifying column (5-3) with it is described high-purity
The gas access of vanadium oxytrichloride condenser (5-4) is connected by pipeline；The liquid of high-purity vanadium oxytrichloride condenser (5-4)
Outlet is connected with the liquid inlet of high-purity vanadium oxytrichloride storage tank (5-5) by pipeline；High-purity vanadium oxytrichloride storage tank
The liquid outlet of (5-5) is connected with the vanadium oxytrichloride entrance of the powder reactor (6-1) processed by pipeline；The powder heat exchanger processed
(6-3) is set in the middle part of the powder reactor (6-1) processed；The hot fluid outlet ports and the powder processed of the powder heat exchanger (6-3) processed
The thermal fluid inlet of soft water storage tank (6-4) is connected by pipeline；The hot fluid outlet ports of the powder soft water storage tank (6-4) processed and institute
The fluid inlet for stating powder water circulating pump (6-5) processed is connected by pipeline；The offgas outlet and chlorine of the powder reactor (6-1) processed
Gas circulatory system entrance is connected by pipeline；The feed inlet of the ultrapure water vaporizer (6-2) respectively with purification oxygen-enriched air
General pipeline, ultrapure supply mains are connected；The air inlet of the gas outlet of the ultrapure water vaporizer (6-2) and the powder reactor (6-1) processed
Mouth is connected by pipeline；The discharge gate of the powder reactor (6-1) processed and the feed inlet of the high purity vanadium feed bin (6-6) pass through
Pipeline is connected；The discharge gate of the high purity vanadium feed bin (6-6) and the feed inlet of the high purity vanadium screw(-type) feeder (6-7) pass through
Pipeline is connected；
The water inlet of the technique water vaporizer (7-1) is connected with technique supply mains；The technique water vaporizer (7-1) goes out
Port is connected with the air inlet of the hydrolysis dechlorination fluidized bed (7-2) by pipeline；The hydrolysis dechlorination fluidized bed (7-2)
Air inlet is connected with air header simultaneously；The fuel inlet of the hydrolysis dechlorination fluidized bed (7-2) is connected with fuel manifold；
Processing slag discharge gate is equipped in the middle part of the hydrolysis dechlorination fluidized bed (7-2)；The offgas outlet of the hydrolysis dechlorination fluidized bed (7-2)
It is connected with the air inlet of the cyclone separator (7-3) by pipeline；The gas vent of the cyclone separator (7-3) and institute
The gas access for stating bag filter (7-4) is connected by pipeline；The dust outlet of the cyclone separator (7-3) with it is described
The feed inlet of hydrolysis dechlorination fluidized bed (7-2) is connected by pipeline；The dust outlet of the bag filter (7-4) with it is described
The air inlet of cyclone separator (7-3) is connected by pipeline；The offgas outlet and vent gas treatment of the bag filter (7-4)
The air inlet of system is connected by pipeline.
2. a kind of method of the vanadium slag cleaning chlorination production high purity vanadic anhydride based on system described in claim 1, the side
Method the following steps are included:
Vanadium slag in the vanadium slag feed bin (1-1) enters the chlorination by the vanadium slag screw(-type) feeder (1-2) and is granulated fluidisation
In bed (1-3), oxidation reaction occurs with the air from pneumatic manifold, while with particle growth；The oxidation is made
The operation temperature of grain fluidized bed (1-3) is 400 DEG C~1000 DEG C；Reaction end gas removes dust through the cyclone dust collectors (1-4)
After send exhaust treatment system；Clinker is aoxidized successively through the granulation vanadium slag feed bin (2-1), the granulation vanadium slag screw feeder
(2-2) enters in the fluidized bed blender (2-5)；Carbon source in the carbon source feed bin (2-3) is through the carbon source screw feeder
Device (2-4) enters in the fluidized bed blender (2-5)；Carbon source quality is to be granulated vanadium slag in the fluidized bed blender (2-5)
The 5%~25% of quality；It is uniformly mixed under the action of fluidizing nitrogen with vanadium slag and enters in the chlorination furnace (3-1) together；Come
From in the nitrogen of nitrogen header pipe, the chlorine of circulating chlorine gas general pipeline, chlorine general pipeline chlorine from the chlorination furnace (3-1) bottom into
Air port enters；It maintains vanadium slag and carbon source fluidised simultaneously, chlorination reaction occurs therewith；Chlorination operation temperature is 280~950
℃；The vanadium oxytrichloride flue gas that reaction generates gathers dust described in through send the eluting column (4-1) elution after tower (3-3) dedusting；Chlorination tail
Slag send hydrolysis dechlorination fluidized bed (7-2) dechlorination to handle；From the elution slurry of slurry subsider (4-5) and described
The kettle base solution of reboiler (5-1) is sprayed into from the top of the chlorination furnace (3-1), to adjust reaction temperature；The chlorination furnace changes
Waste heat of the hot device (3-2) to assist removing chlorination reaction, prevents furnace temperature excessively high；From the elution slurry subsider
The kettle base solution of the slurry of (4-5) and the reboiler (5-1) is sprayed into from the top of the tower that gathers dust (3-3), to evaporate slurry
And the solid dust of kettle base solution, while reducing the temperature of chlorination flue gas；Dust-slag collection in the tower that gathers dust (3-3) send the hydrolysis
Dechlorination fluidized bed (7-2) dechlorination processing；The tower heat exchanger (3-4) that gathers dust recycles high-temp chlorination from the tower that gathers dust (3-3)
The sensible heat of flue gas, and heat is provided for the reboiler (5-1) and powder reactor processed (6-1), it realizes energy-saving；
The elution tail gas of the eluting column (4-1) send exhaust treatment system after the drop catcher (4-4) recycles drop；The leaching
The vanadium oxytrichloride liquid for washing the vanadium oxytrichloride slurry that tower (4-1) elution obtains and the drop catcher (4-4) recycling send the elution
Slurry subsider (4-5) settlement treatment；Obtained supernatant is passed through the powder reaction processed after the rectifying column (5-3) purification
In device (6-1)；Air from purification oxygen-enriched air general pipeline and the ultrapure water from ultrapure supply mains pass through described ultrapure
It is sent in the powder reactor (6-1) processed after water vaporizer (6-2) preheating vaporization, catalytic oxidation occurs with vanadium oxytrichloride, obtains
To rich chlorine flue gas and high purity vanadic anhydride；The reaction temperature of catalytic oxidation process is 120 DEG C~620 DEG C；Rich chlorine flue gas send chlorine
The gas circulatory system；High purity vanadic anhydride send the high purity vanadium feed bin (6-6)；Described in process water warp from technique supply mains
The hydrolysis dechlorination fluidized bed (7-2) is sent into together with from the air of air header after technique water vaporizer (7-1) gasification
In, the fluidization of chloride residue is maintained, and hydrolysis dechlorination reaction occurs therewith；Fuel from fuel manifold is from the hydrolysis
The fuel inlet of the bottom dechlorination fluidized bed (7-2) enters, and provides heat for reaction；Reaction temperature is 500 DEG C~900 DEG C；Powder
Mean residence time be 30~80 minutes；Dechlorination tailings chlorinty is within 2%；Dechlorination tailings send refining ferrochrome；Dechlorination tail gas
Successively exhaust treatment system is sent after the cyclone separator (7-3), bag filter (7-4) removing dust；The cloth bag removes
The dust of dirt device (7-4) recycling returns in the cyclone separator (7-3), the dust with the cyclone separator (7-3) recycling
Enter in the hydrolysis dechlorination fluidized bed (7-2) together.
3. the method for vanadium slag cleaning chlorination production high purity vanadic anhydride according to claim 2, which is characterized in that vanadium slag
The mass fraction of middle vanadic anhydride is 8%~28%, and the mass fraction of chromium oxide is 0.5%~16%.
4. the method for vanadium slag cleaning chlorination production high purity vanadic anhydride according to claim 2, which is characterized in that described
Aoxidizing operating gas velocity in granulating fluidized bed (1-3) is 0.05m~4.00m/s, the mean residence time of vanadium slag is 30~
120min。
5. the method for vanadium slag cleaning chlorination production high purity vanadic anhydride according to claim 2, which is characterized in that described
Carbon source in carbon source feed bin (2-3) refers to one or more of metallurgical coke, petroleum coke and coal dust.
6. the method for vanadium slag cleaning chlorination production high purity vanadic anhydride according to claim 2, which is characterized in that in institute
It states in chlorination furnace (3-1), operating gas velocity is 0.04m~4.00m/s, is rubbed into chlorine in the indoor chlorine nitrogen mixture of wind
Your score is 15%~100%, and the chlorination rate of vanadic anhydride is 95% or more, and the chlorination rate of chromium oxide is within 5%.
7. the method for vanadium slag cleaning chlorination production high purity vanadic anhydride according to claim 2, which is characterized in that in institute
It states in powder reactor (6-1) processed, being passed through vapor is be passed through vanadium oxytrichloride quality 0.05%~12%, is passed through clean oxygen-enriched sky
Oxygen content volume fraction is 29%~97% in gas, and the purity of high purity vanadic anhydride is 99.5% or more.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111411243A (en) * | 2020-05-29 | 2020-07-14 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for directly chloridizing and extracting vanadium from high-calcium high-phosphorus vanadium slag |
| CN117488104A (en) * | 2023-11-02 | 2024-02-02 | 聚挪机械科技(上海)有限公司 | Method for preparing high-vanadium slag by treating vanadium-containing slurry by fluidized bed |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010001669A1 (en) * | 2008-06-30 | 2010-01-07 | 独立行政法人産業技術総合研究所 | Thermochromic microparticles, dispersions thereof, and manufacturing method thereof, as well as light-modulating coatings, light-modulating films and light-modulating inks |
| CN101709388A (en) * | 2009-12-09 | 2010-05-19 | 攀钢集团攀枝花钢钒有限公司 | Process for separating vanadium by chloridizing and roasting vanadium slag |
| CN103130279A (en) * | 2011-11-29 | 2013-06-05 | 刘艳梅 | Method for producing high-purity vanadium pentoxide by chlorination |
| CN105986126A (en) * | 2015-01-30 | 2016-10-05 | 中国科学院过程工程研究所 | System and method for high-efficiency extraction of vanadium from vanadium slag through chlorination |
-
2017
- 2017-11-24 CN CN201711189973.4A patent/CN109835949B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010001669A1 (en) * | 2008-06-30 | 2010-01-07 | 独立行政法人産業技術総合研究所 | Thermochromic microparticles, dispersions thereof, and manufacturing method thereof, as well as light-modulating coatings, light-modulating films and light-modulating inks |
| CN101709388A (en) * | 2009-12-09 | 2010-05-19 | 攀钢集团攀枝花钢钒有限公司 | Process for separating vanadium by chloridizing and roasting vanadium slag |
| CN103130279A (en) * | 2011-11-29 | 2013-06-05 | 刘艳梅 | Method for producing high-purity vanadium pentoxide by chlorination |
| CN105986126A (en) * | 2015-01-30 | 2016-10-05 | 中国科学院过程工程研究所 | System and method for high-efficiency extraction of vanadium from vanadium slag through chlorination |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111411243A (en) * | 2020-05-29 | 2020-07-14 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for directly chloridizing and extracting vanadium from high-calcium high-phosphorus vanadium slag |
| CN111411243B (en) * | 2020-05-29 | 2022-08-05 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for directly chloridizing and extracting vanadium from high-calcium high-phosphorus vanadium slag |
| CN117488104A (en) * | 2023-11-02 | 2024-02-02 | 聚挪机械科技(上海)有限公司 | Method for preparing high-vanadium slag by treating vanadium-containing slurry by fluidized bed |
| CN117488104B (en) * | 2023-11-02 | 2024-04-30 | 聚挪机械科技(上海)有限公司 | Method for preparing high-vanadium slag by treating vanadium-containing slurry by fluidized bed |
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