CN103979604B - The inner circulation fluidized device and method preparing titanium tetrachloride of a kind of vibration type - Google Patents
The inner circulation fluidized device and method preparing titanium tetrachloride of a kind of vibration type Download PDFInfo
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- CN103979604B CN103979604B CN201410232400.5A CN201410232400A CN103979604B CN 103979604 B CN103979604 B CN 103979604B CN 201410232400 A CN201410232400 A CN 201410232400A CN 103979604 B CN103979604 B CN 103979604B
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Abstract
The inner circulation fluidized device and method preparing titanium tetrachloride of a kind of vibration type, belongs to titanium tetrachloride preparing technical field.Apparatus of the present invention, mainly include external circulation fluidized bed, interior fluidized-bed reactor, vibration distribution plate and vibrator, cyclone separator, gas buffer tank and gas distribution grid etc.；The inventive method, with the high high titanium slag of low-grade calcium-magnesium content and coke as solid material, with chlorine, oxygen and nitrogen as gas raw material, utilizes apparatus of the present invention, prepares finished product through chlorination reaction and cooling and gas solid separation.It is compact that apparatus of the present invention have structure of reactor, it is easy to operation maintenance, and granule is anti-stick effective, and product quality is high, beneficially continuous-stable long-term work, it is adaptable to the features such as large-scale industrial production；The utilization rate that the inventive method has material heat is high, and reaction temperature profile is uniform, easy to control, titanium conversion ratio high.The present invention is especially suitable for the high titanium slag with low-grade calcium-magnesium content is high and prepare titanium tetrachloride.
Description
Technical field
The invention belongs to titanium tetrachloride preparing technical field, be specifically related to prepare the device and method of titanium tetrachloride.
Background technology
Titanium tetrachloride is to manufacture titanium white (titanium dioxide), an important intermediate of Titanium.Titanium white is considered as the most in the world
A kind of Chinese white that performance is best, is widely used in coating, plastics, papermaking, printing-ink, chemical fibre, rubber, cosmetics
Deng industry.The titanium dioxide second largest after the most Shi Ji U.S. of China consumes state, and growth is swift and violent, and potentiality are the most very
Greatly.At present the purposes of titanium develops the most quickly, be widely used in aircraft, rocket, artificial satellite, spacecraft, naval vessels,
Light industry, chemical industry, weaving, medical treatment and field of petrochemical industry.China is titanium resource big country, and the titanium resource of China is mainly concentrated
In Panzhihua Region, the reserves of its titanium dioxide (TiO2) reach about 8.7 hundred million tons, account for more than the 90% of domestic titanium reserves.Existing
The preparation having titanium tetrachloride is at high temperature to react acquisition by essence titanium ore or rich-titanium material with chlorine, and its production technology mainly has two kinds:
(1) fused salt chlorimation method, is to insert titaniferous materials and coke mixture by KCl, NaCl, MgCl2In fused salt, it is passed through chlorine
Reacting, the shortcoming of this technique is that equipment capacity is low, reaction volume big, the most liquid and waste slag produced many, big for environment pollution,
It is unsatisfactory for the requirement of modern manufacturing industry, has the most progressively been eliminated.(2) fluidizing chlorination method, fluidizing chlorination is to be prepared by titaniferous materials
Becoming the granule of certain distribution, and put in reactor with coke granule, logical people's chlorine makes granule suspend to get up to react,
The method reactor efficiency is high, does not has waste liquid to produce, and waste residue is also little, and the impact on environment is the least, thus fluidizing chlorination is
Prepare the main method of titanium tetrachloride at present.The shortcoming of this technique is to require material quality the highest, and particularly calcium and magnesium oxides contains
Amount is less than 1%, and this is due to chlorination reaction temperature generally between 800～1000 DEG C, when containing more calcium in titanium slag
During magnesium oxide, will produce substantial amounts of calcium chloride, magnesium chloride, and the fusing point of calcium chloride is 714 DEG C, the fusing point of magnesium chloride is 772 DEG C,
In the chlorination reactor of 800-1000 DEG C, calcium chloride and magnesium chloride are all in a liquid state, and bonding granule around forms bigger agglomerate,
Destroy the stable operation of ebullated bed.But the grade of Flos Bombacis Malabarici titanium ore is relatively low, calcium and magnesium oxides content is high, with Flos Bombacis Malabarici ilmenite concentrate smelting
The high titanium slag CaO of refining, content of MgO are 7～11%, and existing fluidizing chlorination technique can't be by low-grade (calcium-magnesium content be high)
Titanium material be directly used as the raw material of fluidizing chlorination.Titanium tetrachloride prepared by the low-grade titanium ore how making full use of Panzhihua Region,
It it is a difficult problem anxious to be resolved.
The existing device and method preparing titanium tetrachloride with low-grade high titanium slag, as disclosed in 12 days November in 2003, publication number
For " preparing the apparatus and method of titanium tetrachloride for chlorination of titanium bearing ores " patent of CN1454849A, open is that one is multistage soon
The mode of speed fluid bed and turbulent fluidized bed series connection processes low-grade high titanium slag technique, i.e. former for solid with titaniferous ore and petroleum coke
Material, with chlorine and oxygen as gas raw material, use multistage (3-10 level) fast reaction fluid bed and turbulent fluidized bed as reaction
Device, first carries out high-temperature chlorination, by cooling, then carries out a solid and gas separation and prepares finished product.This patent mainly has following
Shortcoming: 1) structure of reactor complexity, the reactor quantity of needs is more, and between two class reactors, architectural difference is relatively big, if
Standby investment is big, and production cost is high.2) carried out reactor in order to avoid the coke granule that density is the least by gas, granule must be used
The coke granule that diameter is the biggest, or use less operating gas velocity, both of these case all can reduce the speed of reaction, and impact is anti-
Answering the efficiency of device, production efficiency is the highest.3) turbulent fluidized bed is relatively big with the different diameters of fast fluidized bed, has relatively between import and export
Big inclination angle, solid particle, there are magnesium chloride, calcium chloride and the bigger high titanium slag granule of viscosity especially for due to surface, hold
Easily importing and exporting bonding, causing that system operates and abnormal, affect yield and the quality of product；And for example Patent No.
" a kind of method of preparing titanic chloride by half cycle fluidization " of ZL200910103049.9, disclosed method is with low-grade high titanium
Slag and coke are solid material, with chlorine and nitrogen as gas raw material, use circulating fluidized bed device, through high-temperature chlorination,
Cooling and gas solid separation and by titanium tetrachloride product.The major defect of the method is: 1) circulating fluidized bed device is complex, institute
The fluidized-bed reactor comprised contains bringing-up section, the refrigerated separation section at pyroreaction section and top, and structure is complicated, and operation is not
Convenient, equipment investment is big；2) in order to promote agglomerate to crush, higher gas speed is needed, the highest for improving the low needs of conversion per pass
Reactor；3) there is liter gentleness cooling due to reactor at differing heights, energy efficiency is low.
Summary of the invention
It is an object of the invention to: for the deficiency of the existing device and method preparing titanium tetrachloride with low-grade high titanium slag, it is provided that one
Planting the inner circulation fluidized device and method preparing titanium tetrachloride of vibration type, apparatus of the present invention have compact conformation, and Btu utilization is high,
The features such as production efficiency is high, good product quality, easy to operate and effectively to process calcium-magnesium content high, tough low-grade titanium slag,
The inventive method is material heating and high-temperature chlorination to be coupled, and uses external circulation fluidized bed heating, and interior fluid bed is anti-
Answer the method that device reacts, there is reaction temperature profile uniform, easy to control, titanium conversion ratio high.
The mechanism of the present invention: the present invention uses the method that titanium tetrachloride is prepared in the inner circulation fluidized chlorination of vibration type, reactant chlorine and
Titanium slag granule and coke granule carry out fluidizing chlorination reaction, owing to this reaction belongs to condensation reaction: along with instead inside fluid bed
The carrying out answered, gas-solid mixture is during up, and the particle diameter of solid reaction composition granule is gradually reduced.Reactant is from interior fluid bed
Reactor head outlet exits into free spatial domain, and owing to free spatial domain diameter increases, the superficial velocity of gas reduces, and carries
Fine grained is shed on vibration distribution plate, and under the vibration of vibrator, fine grained enters outer following through the pore on vibration distribution plate
Ring fluid bed, dirty together with the coke granule being newly added, in the feedback outlet entrance from interior fluidized-bed reaction wall, fluid bed is anti-
Answer device, thus form inner circulation fluidized chlorination process.Superfine little powder will be carried from free spatial domain top discharge pipe effluent air
Dirt enters efficient cyclone separator by straight tube, and dust is discharged from cyclone separator bottom solid particle discharging opening.Device bottom sets
It is equipped with oxygen and nitrogen mixed gas feed pipe, the oxygen of input and coke granule and carries out reaction of making charcoal, release substantial amounts of heat,
Can be that whole response system provides sufficient heat, the nitrogen of input maintains outer circulation bed endoparticle to be in incipient fluidizing state,
It is easy to granule flow downward.Bottom interior fluidized-bed reactor, there is chlorine feed pipe, carry fluidized-bed reaction in titanium slag granule enters
Device, carries out high-temperature chlorination, prepares titanium tetrachloride product.
The technical scheme realizing the object of the invention is: the inner circulation fluidized device preparing titanium tetrachloride of a kind of vibration type, mainly includes
External circulation fluidized bed, interior fluidized-bed reactor, vibration distribution plate and vibrator, cyclone separator, gas buffer tank and gas divide
Fabric swatch etc..It is characterized in that:
Described external circulation fluidized bed, interior fluidized-bed reactor, vibration distribution plate, gas buffer tank, baffle plate, discharge nozzle, straight tube,
The material of feed pipe is stainless steel or titanium alloy material.
The cylindrical housings being shaped as top closure of described external circulation fluidized bed, the internal diameter of described cylindrical housings is
500～3000mm, a length of 1000～5000mm, thickness is 3～8mm.Upper height in described circular cylindrical shell body is
The space of 400～3000mm is free spatial domain, arranges free spatial domain in order to the charging of coke solids raw material and from described interior fluid bed
The sedimentation of the solid particle that reactor flows out.In the circumferential wall in described free spatial domain, being symmetrically arranged two apertures is
The through hole (i.e. coke solids feed(raw material)inlet) of 50～150mm, is respectively welded a root length degree outside described coke solids feed(raw material)inlet
Be 500～1500mm with the angle of the housing of described external circulation fluidized bed be 30 °～70 °, internal diameter enters with described coke solids raw material
The coke granule feed pipe that mouth matches, in order to coke solids raw material can successfully input in described external circulation fluidized bed, and leads to
Cross in the described internal circulation fluidized bed reactor described in the entrance of vibration distribution plate.The center of circle at the top end face of described cylindrical housings
Place's (being i.e. positioned at the top circle centre position in described free spatial domain) arranges the through hole (i.e. discharging opening) that an aperture is 50～200mm, in institute
The discharge outlet stated welds one a length of 1500～2000mm, the discharge nozzle that matches with described discharging opening of internal diameter, and described
The other end of discharge nozzle weld one a length of 1000～5000mm, external diameter be 50～200mm perpendicular with described discharge nozzle
Straight tube, the other end of described straight tube is affixed with the entrance of described cyclone separator to be connected, in order to the output of described external circulation fluidized bed
Mixed gas after chlorination reaction inputs described cyclone separator smoothly and carries out gas solid separation.At the bottom of described external circulation fluidized bed
Hold by the affixed gas distribution grid of flange 1, described gas distribution grid 1 for thickness be 1～10mm, external diameter and described outer circulation
The annular that the internal diameter of fluid bed housing matches, internal diameter matches with the internal diameter of described internal circulation fluidized bed reactor housing is ceramic
Plate, described gas distribution grid 1 is uniformly arranged percent opening be 1%～10%, aperture be 0.5～2.5mm through hole, in order to
Described nitrogen and the mixed gas of oxygen input in the housing of described external circulation fluidized bed equably, described gas distribution grid 1
It is uniformly distributed for oxygen and nitrogen mixed gas.The lower end in the free spatial domain in the circular cylindrical shell body of described external circulation fluidized bed
Place, welds a vibration distribution plate, in order to coke solids granule is by the external circulation fluidized bed described in the entrance of described vibration distribution plate
With in described interior fluidized-bed reactor.
The cylindrical housings being shaped as both ends open of described interior fluidized-bed reactor, the top of described interior fluidized-bed reactor housing
It is welded on the outer surface of described vibration distribution plate bottom.Described cylindrical housings internal diameter is 250～2500mm, a length of
800～2000mm, thickness is 3～8mm.The circumferential wall of the bottom of described cylindrical housings is also uniformly arranged 2～8, hole
Footpath is the through hole (i.e. granule feedback outlet) of 10～50mm, in order to enter institute smoothly through the coke solids raw material of described vibration distribution plate
Chlorination reaction is carried out in the interior fluidized-bed reactor stated.Set on the wall of fluidized-bed reactor lower housing portion side in described cylinder
Put the through hole (i.e. titanium slag solid feed inlet) that an aperture is 50～150mm, a length of in described through hole welding one
200～800mm with the angle of fluidized-bed reactor housing in described cylinder be 30 °～70 °, internal diameter former with described titanium slag solid
The titanium slag particulate charge pipe that material entrance matches, in order to titanium slag solid material enters in described internal circulation fluidized bed reactor smoothly.
In described cylinder, the affixed gas distribution grid of flange 2 is passed through in fluidized-bed reactor housing bottom, and described gas distribution grid 2 is thick
The disc ceramic wafer that degree is 1～10mm, the internal diameter of external diameter and described interior fluidized-bed reactor housing matches, at described gas
Be uniformly arranged on body distribution grid 2 percent opening be 1%～10%, aperture be 0.5～2.5mm through hole, in order to described chlorine gas
Raw material inputs in described cylinder in fluidized-bed reactor housing equably.
The truncated cone shape housing being shaped as both ends open of described vibration distribution plate, the internal diameter of the upper end face of described truncated cone shape housing with
The internal diameter of described external circulation fluidized bed housing matches, the internal diameter of bottom surface is 100～1000mm, height is 300～1200mm,
Thickness is 100～400mm.Described truncated cone shape housing is divided into upper and lower, (i.e. accounts for whole on the top of described truncated cone shape housing
The 2/3 of vibration distribution plate length) be uniformly arranged aperture be 0.5～2mm, pitch of holes be 2～6mm aperture (i.e. vibration distribution plate
Top aperture), in order to less coke solids granule carries out Matter Transfer in described aperture enters described external circulation fluidized bed；
Described truncated cone shape lower housing portion (i.e. accounting for the 1/3 of whole vibration distribution plate length) be uniformly arranged aperture be 1～3mm, pitch of holes
It is the macropore (i.e. vibration distribution plate bottom macropore) of 3～10mm, in order to bigger coke solids granule enters through described macropore
Chlorination reaction is carried out in described interior fluidized-bed reactor.On bottom face in described truncated cone shape housing, both ends of the surface are set the most unlimited
The baffle plate of cylindrical housings, the height of described baffle plate is 20～50mm, thickness is 5～8mm, internal diameter and described truncated cone shape shell
The bottom surface internal diameter of body matches, and in order to stop the coke solids granule glided in described vibration distribution plate, prevents too much coke solids
Granule is directly entered in described interior fluidized-bed reactor.Placing a vibrator in described vibration distribution plate, described vibrator is
Commercial, vibration pressure is the bulkhead formula vibrator of 0.1～0.35MPa, by adjusting frequency of vibration and power, shakes described in imparting
The higher energy of granule on dynamic distribution grid, promotes coke solids granule to enter described outer circulation by the pore of described vibration distribution plate
In fluid bed and in described interior fluidized-bed reactor.
Described gas buffer tank be thickness be 3～10mm, little two big open top face and close bottom surface truncated cone shape
Housing.Two described truncated cone shape housings are assembled into the container of a concentric, and (i.e. gas delays described little truncated cone shape housing
Rush tank 2) a length of 200～1500mm, the internal diameter of open top face and the internal diameter of described interior fluidized-bed reactor housing match,
The internal diameter closing bottom surface is 150～1200mm, and described gas buffer tank 2 passes through method with described disc gas distribution grid 2
Blue affixed described interior fluidized-bed reactor bottom, at the axle center closing bottom surface of described gas buffer tank 2, arranges an aperture
It is the through hole (i.e. chlorine feed charging aperture) of 50～120mm, welds a caliber in described through hole and enter with described chlorine feed
The square gas feed pipe 2 that material mouth matches, total length is 400～2100mm, in order to successfully by defeated for chlorine gas raw material
Enter in described gas buffer tank 2, it is ensured that chlorine gas raw material inputs in described interior fluidized-bed reactor sustainedly and stably, institute
State the gas buffer tank 2 buffering for chlorine gas.Described big truncated cone shape housing (i.e. gas buffer tank 1) a length of
500～2000mm, the internal diameter of end face opening and the internal diameter of described external circulation fluidized bed housing match, the internal diameter of front cover bottom surface is
300～2000mm, described gas buffer tank 1 is fluidized by the affixed described outer circulation of flange with described annular gas distribution grid 1
Bed bottom, and sustained height uniform welding 4～6 saddle on the outer wall of the truncated cone shape housing of described gas buffer tank 1 prop up
Frame or standing support or shield fix on the ground.At the axle center closing bottom surface of described gas buffer tank 1, if
Put the through hole (i.e. the charging aperture of the mixed gas of chlorine and nitrogen) that an aperture is 50～150mm, feed in described mixed gas
The gas feed pipe 1 that at Kou, welding one a length of 100～500mm, caliber match with described mixed gas charging aperture, in order to
Described mixed gas being inputted sustainedly and stably in described gas buffer tank 1, described gas buffer tank 1 is for oxygen and nitrogen
The buffering of oxygen mixture；And on the sidewall of described gas buffer tank 1 and corresponding to the exit of described gas feed pipe 2,
The through hole that the external diameter of one aperture and described feed pipe 2 matches is set, in order to described gas feed pipe 2 stretches out described gas
Outside surge tank 1, it is ensured that allow chlorine gas raw material be input to smoothly in described gas buffer tank 2.
Described cyclone separator is commercially available conventional products, and flow out from the top, free spatial domain of described external circulation fluidized bed takes
Gas with superfine little dust, by the cyclone separator described in described straight tube entrance, carries out gas solid separation, collects from described
The dust that the solid particle discharging opening of cyclone separator bottom is discharged, separated rear recycling, collect from described cyclonic separation
Gas outlet's expellant gas on device top, obtains titanium tetrachloride product after cooling, and collects the residual gas leached, through place
After reason recycling, in order to avoid atmosphere pollution.
A kind of inner circulation fluidized method preparing titanium tetrachloride of vibration type, the high titanium slag high with low-grade calcium-magnesium content and coke are
Solid material, with oxygen, nitrogen and chlorine for gas raw material, utilizes apparatus of the present invention, through chlorination reaction and cooling and gas-solid
Separate and prepare finished product.Described specifically comprises the following steps that
(1) Feedstock treating
The high titanium slag (abbreviation high titanium slag) high with low-grade calcium-magnesium content and coke are as solid material, with oxygen and nitrogen and chlorine
Gas is gas raw material, first by the bolter of 0.7～21 mesh, described solid material is carried out sub-sieve respectively, and presses high titanium slag granule
Mean diameter: the ratio 1: 0.8～1.2 of the mean diameter of coke granule, and press the quality of high titanium slag granule: the matter of coke granule
Amount is got the raw materials ready than the ratio being 1: 0.3～3, heats high titanium slag granule and coke granule the most respectively, is heated to solid particle
Temperature is 400～600 DEG C, standby.Chlorine in described gas raw material is heated to 300～500 DEG C, standby；To oxygen and
Nitrogen is first in oxygen: the volume ratio of nitrogen be 1: 0.1～0.5 ratio mix, then mixed gas is heated to
100～300 DEG C, standby.
(2) chlorination reaction
After (1st) step completes, the raw material after (1st) step is processed, it is separately input in assembly of the invention, i.e. coke
Grain inputs from the coke granule feed pipe of described device with the speed of 1.8～540kg/h, enters institute by described device vibration distribution plate
In stating the external circulation fluidized bed of device and in interior fluidized-bed reactor；High titanium slag granule with 36～180kg/h speed from described device
Titanium slag particulate charge pipe be input in described interior fluidized-bed reactor；Chlorine with 0.5～3.5m/s speed from described device
The gas feed pipe 2 of gas buffer tank 2 bottom surface is input in described interior fluidized-bed reactor, oxygen and the mixed gas of nitrogen
The speed with the 0.2～1.5m/s gas feed pipe 1 from gas buffer tank 1 bottom surface of described device is input to described outer circulation stream
Change in bed.Described coke granule is made to connect with described oxygen and nitrogen mixed gas adverse current in described external circulation fluidized bed is descending
Touch reaction, utilize reaction liberated heat heating coke granule, make coke granule reach 1000～1300 DEG C, obtained high temperature
In the coke granule interior fluidized-bed reactor described in the entrance of granule feedback outlet from described interior fluidized-bed reaction wall, in order to keep
Described interior fluidized-bed reactor internal temperature is 800～1100 DEG C；From the chlorine of described gas feed pipe 2 input with from described titanium
The titanium slag granule that solid impurity particle feed pipe enters carries out high-temperature chlorination in described interior fluidized-bed reactor；With the carrying out of reaction,
Gas-solid mixture is during up, and solid reactant grain diameter is gradually reduced, and enters described external circulation fluidized bed internal upper part
Free spatial domain, gas superficial velocity reduces, and the fine grained carried is shed on described vibration distribution plate, shaken at described vibrator
Dynamic lower smaller particle enters in described external circulation fluidized bed through described vibration distribution plate top aperture, with the coke granule of raw feed
The dirtiest, in described granule feedback outlet enters described interior fluidized-bed reactor, thus form inner circulation fluidized chlorination
Journey；The gas that is that produce after described chlorination reaction and that the carry a small amount of dust freely sky by described external circulation fluidized bed top
Territory and discharge nozzle and straight tube input in the cyclone separator of described device.The pressure that described device is in operation is
0.1～0.35MPa.
(3) gas solid separation
After (2nd) step completes, in the cyclone separator of described device, to (2nd) one-step chlorination reaction produce with on a small quantity
The gas of dust, carries out gas solid separation, is collected in the gas that the gas outlet on described cyclone separator top leaches, natural cooling
After obtain titanium tetrachloride product, and collect the residual gas leached, the most recycling in order to avoid atmosphere pollution；Collect from institute
State the dust that the solid particle discharging opening of cyclone separator bottom leaches, separated rear recycling.
The present invention uses technique scheme, mainly has the following effects
The vibration type ICFB that 1 apparatus of the present invention use, the coke granule of charging passes through granule feedback outlet recycle stream outside
Carry out in changing bed and interior fluidized-bed reactor Matter Transfer and and the gas haptoreaction of charging so that the optimum contact of several materials and
Being fully utilized, it is to avoid the loss of too much material, cost-effective, production efficiency improves further, and gas-particle two-phase is in
Fluidized state, it is to avoid the bigger agglomerate that between granule, mutually bonding is formed, destroys the stable operation of vibration type ICFB；
Secondly, the granule that apparatus of the present invention utilize vibration can will be attached on vibration distribution plate loosens, and the exit plate tilted is conducive to
Sticky particle flows, and prevents granule to be attached on vibration distribution plate.
2 apparatus of the present invention have on vibration distribution plate different size of pore, can be by vibration by gradation, fine grained
First flow out from vibration distribution plate top aperture, slowly flow down with incipient fluidizing state from external circulation fluidized bed, and bigger granule from
Vibration distribution plate bottom macropore flows out, and flows downward along interior fluidized-bed reaction wall, in sticky particle so can be stoped to be attached on
Fluidized-bed reactor inwall, plays antiplastering effect.
3 apparatus of the present invention use Cyclone outlet deslagging not affect the operation of response system, thus system can continuously, surely
Fixed, long-term work, and product quality is high, it is adaptable to large-scale commercial production.
The structure of reactor of 4 apparatus of the present invention is compact, it is easy to operates, overhaul, reduces production cost.
5 the inventive method use part of coke oxidation generation heat to meet reaction institute calorific requirement, such heat supply system and reaction system
It is coupling in a device, and the solid coke granule using thermal capacity big is thermal medium, improve the service efficiency of material heat.
6 the inventive method are easy to operate and can make full use of the low-grade big titanium slag of calcium-magnesium content high viscosity, by material heating and high temperature
Chlorination reaction is coupled, and uses external circulation fluidized bed heating, the method for interior fluidized-bed reactor reaction, reaction temperature profile
Uniformly, easy to control, titanium conversion ratio is high.
The composite can be widely applied to utilize titanium ore to prepare titanium tetrachloride, be particularly well-suited to the height utilizing low-grade calcium-magnesium content high
Titanium slag prepares titanium tetrachloride.
Accompanying drawing explanation
Fig. 1 is the structural representation of apparatus of the present invention；
Fig. 2 is the structural representation of the vibration distribution plate amplified in Fig. 1.
In figure: 1 external circulation fluidized bed, 1-1 external circulation fluidized bed wall, 1-2 coke granule feed pipe, 1-3 titanium slag particulate charge pipe,
2 internal circulation fluidized bed reactors, fluidized-bed reaction wall in 2-1,2-2 granule feedback outlet, 3 vibration distribution plates, 3-1 vibration point
Fabric swatch top aperture, 3-2 vibration distribution plate bottom macropore, 3-3 baffle plate, 4 discharge nozzles, 5 straight tubes, 6 cyclone separator, 6-1
Gas outlet, 6-2 valve, 6-3 solid particle discharging opening, 7 titanium slag granules, 8-1 gas distribution grid 2,8-2 gas distribution grid 1,
9-1 gas buffer tank 2,9-2 gas feed pipe 2,9-3 gas feed tank 1,9-4 gas feed pipe 1,10 coke granule, 11
Vibrator.
Detailed description of the invention
Below in conjunction with detailed description of the invention, further illustrate the present invention.
Embodiment 1
As shown in Figure 1, 2, the inner circulation fluidized device preparing titanium tetrachloride of a kind of vibration type.Mainly include external circulation fluidized bed,
Interior fluidized-bed reactor, vibration distribution plate and vibrator, cyclone separator, gas buffer tank and gas distribution grid etc..Its feature
It is:
Described external circulation fluidized bed, interior fluidized-bed reactor, vibration distribution plate, gas buffer tank, baffle plate, discharge nozzle, straight tube,
The material of feed pipe is stainless steel.
The cylindrical housings being shaped as top closure of described external circulation fluidized bed 1, the internal diameter that described cylindrical housings is arranged is
1800mm, a length of 3000mm, thickness are 5mm.The space of upper height 1700mm in described circular cylindrical shell body
For free spatial domain, free spatial domain is set in order to the charging of coke solids raw material and from the solid of described interior fluidized-bed reactor 2 outflow
The sedimentation of granule.In the circumferential wall in described free spatial domain, (i.e. coke is solid to be symmetrically arranged the through hole that two apertures are 100mm
Body feed(raw material)inlet), outside described coke solids feed(raw material)inlet, it is respectively welded an a length of 1000mm and described outer circulation fluidisation
The coke granule feed pipe 1-2 that the angle of housing of bed 1 is 50 °, internal diameter matches with described coke solids feed(raw material)inlet, in order to
Coke solids raw material can successfully input in described external circulation fluidized bed 1, and entered described by described vibration distribution plate 3
Internal circulation fluidized bed reactor 2 in.At the circle centre position of the top end face of described cylindrical housings, i.e. it is positioned at described free spatial domain
Top circle centre position, arranges the through hole (i.e. discharging opening) that an aperture is 120mm, a length of in described discharge outlet welding one
The discharge nozzle 4 that 1000mm, internal diameter and described discharging opening match, and a length of in the other end welding one of described discharge nozzle 4
3000mm, external diameter are the straight tube 5 that 120mm is perpendicular with described discharge nozzle 4.The other end of described straight tube 5 and described whirlwind
The affixed connection of entrance of separator 6, in order to the mixed gas after chlorination reaction of described external circulation fluidized bed 1 output is smooth
Cyclone separator 6 described in input carries out gas solid separation.The affixed gas distribution grid of flange is passed through in described external circulation fluidized bed 1 bottom
1 8-2, described gas distribution grid 1 8-2 be thickness be 5.5mm, the internal diameter of external diameter and described external circulation fluidized bed 1 housing
Match, annular ceramic wafer that the internal diameter of internal diameter and described internal circulation fluidized bed reactor 2 housing matches.At described gas
Be uniformly arranged on body distribution grid 1 8-2 percent opening be 0.05, aperture be the through hole of 1.5mm, in order to described nitrogen and oxygen
Mixed gas inputs in the housing of described external circulation fluidized bed 1 equably, and described gas distribution grid 1 8-2 is used for oxygen and nitrogen
Mixed gas is uniformly distributed.The lower end in the free spatial domain in the circular cylindrical shell body of described external circulation fluidized bed 1, welding one is shaken
Dynamic distribution grid 3, in order to it is interior and described that coke solids granule enters described external circulation fluidized bed 1 by described vibration distribution plate 3
Interior fluidized-bed reactor 2 in.
The cylindrical housings being shaped as both ends open of described interior fluidized-bed reactor 2, described interior fluidized-bed reactor 2 housing
Top is welded on the outer surface of described vibration distribution plate 3 bottom, and described cylindrical housings internal diameter is 1350mm, a length of
1400mm, thickness is 5mm.Also being uniformly arranged 5 in the circumferential wall of the bottom of described cylindrical housings, aperture is 30mm
Through hole (i.e. granule feedback outlet 2-2), in order to enter described interior stream smoothly through the coke solids raw material of described vibration distribution plate 3
Chlorination reaction is carried out in fluidized bed reactor 2.One is arranged on the wall of fluidized-bed reactor 2 lower housing portion side in described cylinder
Aperture is the through hole (i.e. titanium slag solid feed inlet) of 100mm, weld in described through hole an a length of 500mm,
With the angle of fluidized-bed reactor 2 housing in described cylinder be 50 °, the titanium that matches with described titanium slag solid feed inlet of internal diameter
Solid impurity particle feed pipe 1-3, in order to titanium slag solid material enters in described internal circulation fluidized bed reactor 2 smoothly.Described cylinder
Flange affixed gas distribution grid 2 8-1 is passed through in interior fluidized-bed reactor 2 housing bottom, and described gas distribution grid 2 8-1 is length
For thickness be 5.5mm, the disc ceramic wafer that matches of the internal diameter of external diameter and described interior fluidized-bed reactor 2 housing, described
Gas distribution grid 2 8-1 on be uniformly arranged percent opening be 0.05, aperture be the through hole of 1.5mm, in order to described chlorine gas
Raw material inputs in described cylinder in fluidized-bed reactor 2 housing equably.
The truncated cone shape housing being shaped as both ends open of described vibration distribution plate 3, the internal diameter of the upper end face of described truncated cone shape housing
Match with the internal diameter of described external circulation fluidized bed 1 housing, the internal diameter of bottom surface is 550mm, height for 750mm, thickness is
250mm, described truncated cone shape housing is divided into upper and lower, (i.e. accounts for whole vibration distribution plate on the top of described truncated cone shape housing
The 2/3 of 3 length), be uniformly arranged aperture be 1.2mm, pitch of holes be the aperture (i.e. vibration distribution plate top aperture 3-1) of 4mm,
So that less coke solids granule carries out Matter Transfer in described aperture enters described external circulation fluidized bed 1.At described section
Conical shell bottom (i.e. accounts for the 1/3 of whole vibration distribution plate 3 length), be uniformly arranged aperture be 2mm, pitch of holes be 6.5mm
Macropore (i.e. vibration distribution plate bottom macropore 3-2), in order to bigger coke solids granule through described macropore enter described interior stream
Chlorination reaction is carried out in fluidized bed reactor 2.On bottom face in described truncated cone shape housing, the cylinder that both ends of the surface are all opened wide is set
The baffle plate 3-3 of shape housing, the height of described baffle plate 3-3 is 35mm, thickness is 6.5mm, internal diameter and described truncated cone shape housing
Bottom surface internal diameter match, in order to stop in described vibration distribution plate 3 glide coke solids granule, prevent too much coke solids
Granule is directly entered in described interior fluidized-bed reactor 2.In described vibration distribution plate 3 place a vibrator 11, described in shake
Dynamic device 11 is bulkhead formula vibrator commercial, that vibration pressure is 0.22MPa, by adjusting frequency of vibration and power, gives institute
State the higher energy of granule on vibration distribution plate, promote coke solids granule to be entered by the pore of described vibration distribution plate 3 described
In external circulation fluidized bed 1 and in described interior fluidized-bed reactor 2.
Described gas buffer tank be thickness be 6.5mm, little two big open top face, close bottom surface truncated cone shape shell
Body, two described truncated cone shape housings are assembled into the container of a concentric, described little truncated cone shape housing (i.e. gas buffer
Tank 2 9-1) a length of 900mm, the internal diameter of open top face and the internal diameter of described interior fluidized-bed reactor 2 housing match, seal
The internal diameter closing bottom surface is 700mm, and described gas buffer tank 2 9-1 and described disc gas distribution grid 2 8-1 passes through flange
It is fixed in described interior fluidized-bed reactor 2 bottom, at the axle center closing bottom surface of described gas buffer tank 2 9-1, arranges one
Aperture is the through hole (i.e. chlorine feed charging aperture) of 80mm, welds a caliber in described through hole and enters with described chlorine feed
Square gas feed pipe 2 9-2 that material mouth matches, total length is 1250mm, in order to successfully chlorine gas raw material is inputted
In described gas buffer tank 2 9-1, it is ensured that chlorine gas raw material inputs in described interior fluidized-bed reactor 2 sustainedly and stably,
Described gas buffer tank 2 9-1 is for the buffering of chlorine gas.Described big truncated cone shape housing (i.e. gas buffer tank 1 9-3)
A length of 1250mm, the internal diameter of end face opening matches with the internal diameter of described external circulation fluidized bed 1 housing, front cover bottom surface
Internal diameter is 1200mm, and described gas buffer tank 1 9-3 and described annular gas distribution grid 1 8-2 is fixed in institute by flange
State external circulation fluidized bed 1 bottom, and the sustained height on the outer wall of the truncated cone shape housing of described gas buffer tank 1 9-3 is uniform
Weld 5 standing supports to fix on the ground.At the axle center closing bottom surface of described gas buffer tank 1 9-3, a hole is set
Footpath is the through hole (i.e. chlorine feed charging aperture) of 100mm, weld at described mixed gas charging aperture a length of 300mm,
Gas feed pipe 1 9-4 that caliber and described mixed gas charging aperture match, in order to by the most defeated for described mixed gas
Entering in described gas buffer tank 1 9-3, described gas buffer tank 1 9-3 is used for oxygen and the buffering of nitrogen mixed gas；And
On the sidewall of described gas buffer tank 1 9-3 and corresponding to the exit of described gas feed pipe 2 9-2, an aperture is set with described
The through hole that the external diameter of feed pipe 2 9-2 matches, in order to described gas feed pipe 2 9-2 stretches out described gas buffer tank 1 9-3
Outward, chlorine gas raw material is allowed to input smoothly.
Described cyclone separator 6 is commercially available conventional products, flows out from the top, free spatial domain of described external circulation fluidized bed 1
The gas carrying superfine little dust enter described cyclone separator 6 by described straight tube 5, carry out gas solid separation, receive
The dust that the collection solid particle discharging opening 6-3 from described cyclone separator 6 bottom discharges, separated rear recycling, collect
From gas outlet's 6-1 expellant gas on described cyclone separator top, obtain titanium tetrachloride product after cooling, and collect filter
The residual gas gone out, the most recycling, in order to avoid atmosphere pollution.
Embodiment 2
The inner circulation fluidized device preparing titanium tetrachloride of a kind of vibration type, with embodiment 1, wherein:
The internal diameter of described external circulation fluidized bed 1 is 500mm, a length of 1000mm, thickness are 3mm, at described circular cylindrical shell
Internal free spatial domain upper height is 400mm, two through holes (the i.e. coke solids raw material in the circumferential wall in described free spatial domain
Entrance) aperture be 50mm.Be respectively welded outside described coke solids feed(raw material)inlet an a length of 500mm and described outside
The coke granule feed pipe that the angle of the housing of recirculating fluidized bed 1 is 30 °, internal diameter matches with described coke solids feed(raw material)inlet
1-2.It is 50mm in the aperture of through hole (i.e. discharging opening) of the circle centre position of the top end face of described cylindrical housings, goes out described
Weld, at material mouth, the discharge nozzle 4 that a length of 1500mm, an internal diameter match with described discharging opening, and at described discharge nozzle 4
The other end welding piece a length of 1000mm, an external diameter be straight tube 5 perpendicular with described discharge nozzle 4 for 50mm.Described
Gas distribution grid 1 8-2 be thickness be 1mm.Described gas distribution grid 1 8-2 is uniformly arranged percent opening be 0.01, aperture
Through hole for 0.5mm.
The internal diameter of described interior fluidized-bed reactor 2 cylindrical housings is 250mm, a length of 800mm, thickness are 3mm, institute
Also be uniformly arranged in the circumferential wall of the bottom stating cylindrical housings 2, aperture be the through hole (i.e. granule feedback outlet 2-2) of 10mm.
(i.e. titanium slag is solid to arrange the through hole that an aperture is 50mm in described cylinder on the wall of fluidized-bed reactor 2 lower housing portion side
Body feed(raw material)inlet), fluidized-bed reactor 2 shell in a described through hole piece a length of 200mm of welding and described cylinder
The titanium slag particulate charge pipe 1-3 that the angle of body is 30 °, internal diameter matches with described titanium slag solid feed inlet.State stream in cylinder
Fluidized bed reactor 2 housing bottom is fixed on gas distribution grid 2 8-1 by flange, and described gas distribution grid 2 8-1 is thickness
The disc ceramic wafer matched for the internal diameter of 1mm, external diameter and described interior fluidized-bed reactor 2 housing.Described gas distribution
Be uniformly arranged on plate 2 8-1 percent opening be 0.01, aperture be the through hole of 0.5mm.
The internal diameter of the bottom surface of described vibration distribution plate 3 is 100mm, height is 100mm for 300mm, thickness.Institute
State the top of vibration distribution plate be uniformly arranged aperture be 0.5mm, pitch of holes be aperture (the i.e. vibration distribution plate top aperture of 2mm
3-1).Be uniformly arranged in the bottom of described vibration distribution plate aperture be 1mm, pitch of holes be macropore (the i.e. vibration distribution of 3mm
Plate bottom macropore 3-2).The height of described baffle plate 3-3 is 20mm, thickness is 5mm.Described vibrator 11 is vibration pressure
Bulkhead formula vibrator for 0.1MPa.
Described gas buffer tank be thickness be little two big truncated cone shape housings of 3mm, the length of gas buffer tank 2 9-1
Degree is 200mm, the internal diameter of closing bottom surface is 150mm.At the axle center closing bottom surface of described gas buffer tank 2 9-1,
The through hole (i.e. chlorine feed charging aperture) that one aperture is 50mm is set, welds a caliber and described chlorine in described through hole
Square gas feed pipe 2 9-2 that material inlet matches, total length is 400mm.The length of gas buffer tank 1 9-3
Internal diameter for 500mm, front cover bottom surface is 300mm.On the outer wall of the truncated cone shape housing of described gas buffer tank 1 9-3
4 saddle supports of sustained height uniform welding fix on the ground, at the axle center closing bottom surface of described gas buffer tank 1 9-3,
The through hole (i.e. the charging aperture of the mixed gas of chlorine and nitrogen) that one aperture is 50mm is set, at described mixed gas charging aperture
Gas feed pipe 1 9-4 of a piece a length of 100mm of place's welding.
Embodiment 3
The inner circulation fluidized device preparing titanium tetrachloride of a kind of vibration type, with embodiment 1, wherein:
Described external circulation fluidized bed, interior fluidized-bed reactor, vibration distribution plate, gas buffer tank, baffle plate, discharge nozzle, straight tube,
The material of feed pipe is titanium alloy material.
The internal diameter of described external circulation fluidized bed 1 is 3000mm, a length of 5000mm, thickness are 8mm, described circular cylindrical shell
The height in free spatial domain, internal top is 3000mm, through hole (the i.e. coke solids raw material in the circumferential wall in described free spatial domain
Entrance) aperture be 150mm, outside described coke solids feed(raw material)inlet, be respectively welded an a length of 1500mm with described
The angle of the housing of external circulation fluidized bed 1 is the coke granule feed pipe 1-2 of 70 °.Circle at the top end face of described cylindrical housings
At the heart, the through hole (i.e. discharging opening) that an aperture is 200mm is set, at a described discharge outlet piece a length of 2000mm of welding
Discharge nozzle 4, and described discharge nozzle 4 the other end weld a length of 5000mm, an external diameter be that 200mm is with described
The straight tube 5 that discharge nozzle 4 is perpendicular.Described gas distribution grid 1 8-2 be thickness be the annular ceramic wafer of 10mm, described
Gas distribution grid 1 8-2 on be uniformly arranged percent opening be 0.1, aperture be the through hole of 2.5mm.
The internal diameter of described interior fluidized-bed reactor 2 is 2500mm, a length of 2000mm, thickness are 8mm, at described cylinder
Be uniformly arranged in the circumferential wall of the bottom of shape housing 8, aperture be the through hole (i.e. granule feedback outlet 2-2) of 50mm, described
The through hole (i.e. titanium slag solid feed inlet) that one aperture is 150mm is set on the wall of interior fluidized-bed reactor 2 lower housing portion side,
In a described through hole piece a length of 800mm of welding and described cylinder, the angle of fluidized-bed reactor 2 housing is 70 °
Titanium slag particulate charge pipe 1-3.Described gas distribution grid 2 8-1 be a length of thickness be the disc ceramic wafer of 10mm,
Being uniformly arranged percent opening on described gas distribution grid 2 8-1 is 0.1, and aperture is the through hole of 2.5mm.
The internal diameter of the bottom surface of described vibration distribution plate 3 is 1000mm, height is 400mm for 1200mm, thickness.Described
The top of vibration distribution plate 3 be uniformly arranged aperture be 2mm, pitch of holes be aperture (the i.e. vibration distribution plate top aperture of 6mm
3-1), described vibration distribution plate 3 bottom (i.e. accounting for the 1/3 of whole vibration distribution plate 3 length), be uniformly arranged aperture be 3mm,
Pitch of holes is the macropore (i.e. vibration distribution plate bottom macropore 3-2) of 10mm, and the height of described baffle plate 3-3 is 50mm, thickness
For 8mm.Described vibrator 11 is bulkhead formula vibrator that vibration pressure is 0.35MPa.
Described gas buffer tank be thickness be little two big truncated cone shape housings of 10mm.The length of gas buffer tank 2 9-1
Degree is 1500mm, and the internal diameter closing bottom surface is 1200mm, at the axle center closing bottom surface of described gas buffer tank 2 9-1,
The through hole (i.e. chlorine feed charging aperture) that one aperture is 120mm is set, welds a caliber and described chlorine in described through hole
Square gas feed pipe 2 9-2 that material inlet matches, total length is 2100mm.The length of gas buffer tank 1 9-3
For 2000mm, the internal diameter of front cover bottom surface is 2000mm.On the outer wall of the truncated cone shape housing of described gas buffer tank 1 9-3
Sustained height uniform welding 6 shield fix on the ground, described gas buffer tank 1 9-3 close bottom surface axle center
Place, arranges the through hole (i.e. the charging aperture of the mixed gas of chlorine and nitrogen) that an aperture is 150mm, enters in described mixed gas
Gas feed pipe 1 9-4 of an a length of 500mm is welded at material mouth.
Embodiment 4
A kind of inner circulation fluidized method preparing titanium tetrachloride of vibration type, the high titanium slag high with low-grade calcium-magnesium content and coke are
Solid material, with oxygen, nitrogen and chlorine for gas raw material, utilizes apparatus of the present invention, through chlorination reaction and cooling and gas-solid
Separate and prepare finished product.Described specifically comprises the following steps that
(1) Feedstock treating
The high titanium slag (abbreviation high titanium slag) high with low-grade calcium-magnesium content and coke are as solid material, with oxygen and nitrogen and chlorine
Gas is gas raw material, first by the bolter of 11 mesh, described solid material is carried out sub-sieve respectively, and presses the flat of high titanium slag granule
All particle diameters: the ratio 1: 1 of the mean diameter of coke granule, and the quality by high titanium slag granule: the mass ratio of coke granule is 1:
The ratio of 1.65 is got the raw materials ready, and heats high titanium slag granule and coke granule the most respectively, is heated to solid particle temperature and is all
500 DEG C, standby, the chlorine in described gas raw material is heated to 400 DEG C, standby, oxygen and nitrogen are first pressed oxygen: nitrogen
The volume ratio of gas be 1: 0.3 ratio mix, then mixed gas is heated to 200 DEG C, standby.
(2) chlorination reaction
After (1st) step completes, the raw material after (1st) step is processed, it is separately input in assembly of the invention, i.e. coke
Grain inputs from the coke granule feed pipe 1-2 of described device, by the vibration distribution plate 3 of described device with the speed of 271kg/h
In entering the external circulation fluidized bed 1 of described device and in the interior fluidized-bed reactor 2 of described device, high titanium slag granule is with 110kg/h
Speed be input to described interior fluidized-bed reactor 2 from the titanium slag particulate charge pipe 1-3 of described device, chlorine is with 2m/s's
Speed is input to described interior fluidized-bed reactor 2 from gas feed pipe 2 9-2 of the gas buffer tank 2 9-1 bottom surface of described device
In, the mixed gas of oxygen and nitrogen is with gas feed from the gas buffer tank 1 9-3 bottom surface of described device of the speed of 0.8m/s
Pipe 1 9-4 is input in described external circulation fluidized bed 1.Make described coke granule in described external circulation fluidized bed 1 is descending with
Described oxygen and the reaction of nitrogen mixed gas counter current contacting, utilize reaction liberated heat heating coke granule, make coke granule
Reaching 1200 DEG C, obtained high-temperature coke granule granule feedback outlet 2-2 from described interior fluidized-bed reaction wall 2-1 enters
In described interior fluidized-bed reactor 2, it it is 950 DEG C in order to keep described interior fluidized-bed reactor 2 internal temperature, from described
The chlorine of gas feed pipe 2 9-2 input and the titanium slag granule from described titanium slag particulate charge pipe 1-3 entrance are at described interior fluid bed
Carry out high-temperature chlorination in reactor 2, with reaction carrying out, gas-solid mixture during up, solid reaction composition granule
Particle diameter is gradually reduced, and enters the free spatial domain of described external circulation fluidized bed 1 internal upper part, and gas superficial velocity reduces, and that carries is thin
Granule is shed on described vibration distribution plate 3, and under described vibrator 11 vibrates, smaller particle passes on described vibration distribution plate
Portion aperture 3-1 enters in described external circulation fluidized bed 1, dirty together with the coke granule of raw feed, through described granule feed back
Mouth 2-2 enters in described interior fluidized-bed reactor 2, thus forms inner circulation fluidized chlorination process, produces after described chlorination reaction
And the gas that carries a small amount of dust by the free spatial domain on described external circulation fluidized bed 1 top and discharge nozzle 4 and straight tube 5
Inputting in the cyclone separator 6 of described device, the pressure that described device is in operation is 0.22MPa.
(3) gas solid separation
After (2nd) step completes, in the cyclone separator 6 of described device, to (2nd) one-step chlorination reaction produce with on a small quantity
The gas of dust, carries out gas solid separation, is collected in the gas that the gas outlet 6-1 on described cyclone separator 6 top leaches, from
So obtain titanium tetrachloride product after cooling, and collect the residual gas leached, the most recycling in order to avoid atmosphere pollution；Receive
The dust that collection leaches from the solid particle discharging opening 6-3 of described cyclone separator 6 bottom, separated rear recycling.
The most after measured, the chlorination rate of titaniferous ore reaches 99%, and after refining step, obtaining purity is 99% (mass fraction)
Titanium tetrachloride.
Embodiment 5
A kind of inner circulation fluidized method preparing titanium tetrachloride of vibration type, with embodiment 4, wherein:
In (1st) step, described solid material is carried out sub-sieve by the bolter of 0.7 mesh respectively, high titanium slag granule average
Particle diameter: the ratio 1: 0.8 of the mean diameter of coke granule, the quality of high titanium slag granule: the mass ratio of coke granule is 1: 0.3
Ratio get the raw materials ready, respectively heating high titanium slag granule and coke granule be all 400 DEG C to temperature, to the chlorine in described gas raw material
Carry out being heated to 300 DEG C, to oxygen and nitrogen first in oxygen: the volume ratio of nitrogen be 1: 0.1 ratio mix, more right
Mixed gas carries out being heated to 100 DEG C.
In (2nd) step, coke granule inputs from the coke granule feed pipe 1-2 of described device with the speed of 1.8kg/h, Gao Tai
Solid impurity particle is input to interior fluidized-bed reactor 2 from the titanium slag particulate charge pipe 1-3 of described device with the speed of 36kg/h, chlorine
It is input to interior fluidized-bed reaction from gas feed pipe 2 9-2 of the gas buffer tank 2 9-1 bottom surface of described device with the speed of 0.5m/s
In device 2, the mixed gas of oxygen and nitrogen is with gas from the gas buffer tank 1 9-3 bottom surface of described device of the speed of 0.2m/s
Feed pipe 1 9-4 is input in external circulation fluidized bed 1.Coke granule is utilized to release with described oxygen and nitrogen mixture precursor reactant
Heat coke granule reach 1000 DEG C, be 800 DEG C in order to keep described interior fluidized-bed reactor 2 internal temperature, this
The pressure that bright device is in operation is 0.1MPa.
In (3rd) step, it is collected in the gas that the gas outlet 6-1 on described cyclone separator 6 top leaches, after natural cooling
To titanium tetrachloride product；Collect the dust leached from the solid particle discharging opening 6-3 of described cyclone separator 6 bottom, separated
Rear recycling.
The most after measured, the chlorination rate of titaniferous ore reaches 96%, and after refining step, obtaining purity is 97% (mass fraction)
Titanium tetrachloride.
Embodiment 6
A kind of inner circulation fluidized method preparing titanium tetrachloride of vibration type, with embodiment 4, wherein:
In (1st) step, first described solid material is carried out sub-sieve by the bolter of 21 mesh respectively, and press high titanium slag granule
Mean diameter: the ratio 1: 1.2 of the mean diameter of coke granule, and the quality by high titanium slag granule: the mass ratio of coke granule is
The ratio of 1: 3 is got the raw materials ready, and heating high titanium slag granule and coke granule are all 600 DEG C to temperature respectively.To in described gas raw material
Chlorine carries out being heated to 500 DEG C, to oxygen and nitrogen first in oxygen: the volume ratio of nitrogen be 1: 0.5 ratio mix, then
Mixed gas is heated to 300 DEG C.
In (2nd) step, coke granule inputs from the coke granule feed pipe 1-2 of described device with the speed of 540kg/h, Gao Tai
Solid impurity particle is input to the interior fluidized-bed reactor of described device with the speed of 180kg/h from the titanium slag particulate charge pipe 1-3 of described device
In 2, chlorine is input to institute with the speed of 3.5m/s from gas feed pipe 2 9-2 of the gas buffer tank 2 9-1 bottom surface of described device
In the interior fluidized-bed reactor 2 stated, the mixed gas of oxygen and nitrogen with the speed of 1.5m/s from the gas buffer tank of described device
Gas feed pipe 1 9-4 of 1 9-3 bottom surface is input in described external circulation fluidized bed 1.Utilize coke granule and described oxygen
Reach 1300 DEG C with nitrogen mixture precursor reactant liberated heat heating coke granule, keep described interior fluidized-bed reactor 2 internal
Temperature is 1100 DEG C, and the pressure that described device is in operation is 0.35MPa.
In (3rd) step, it is collected in the gas that the gas outlet 6-1 on described cyclone separator 6 top leaches, after natural cooling
To titanium tetrachloride product；Collect the dust leached from the solid particle discharging opening 6-3 of described cyclone separator 6 bottom, separated
Rear recycling.
The most after measured, the chlorination rate of titaniferous ore reaches 97%, and after refining step, obtaining purity is 98% (mass fraction)
Titanium tetrachloride.
Claims (3)
1. the inner circulation fluidized device preparing titanium tetrachloride of vibration type, mainly include recirculating fluidized bed, cyclone separator (6),
Gas distribution grid, it is characterised in that also include vibration distribution plate (3) and vibrator (11), gas buffer tank, described circulation
Fluid bed is external circulation fluidized bed (1) and interior fluidized-bed reactor (2), and described gas distribution grid is gas distribution grid 1 (8-2)
With gas distribution grid 2 (8-1), described gas buffer tank is gas buffer tank 1 (9-3) and gas surge tank 2 (9-1)；
The cylindrical housings being shaped as top closure of described external circulation fluidized bed (1), the internal diameter of described cylindrical housings is
500～3000mm, a length of 1000～5000mm, thickness is 3～8mm, and the upper height in described circular cylindrical shell body is
The space of 400～3000mm is free spatial domain, and in the circumferential wall in described free spatial domain, being symmetrically arranged two apertures is
The through hole of 50～150mm, i.e. coke granule entrance, be respectively welded outside described coke granule entrance one a length of
500～1500mm with the angle of the housing of described external circulation fluidized bed (1) be 30 °～70 °, internal diameter former with described coke solids
The coke granule feed pipe (1-2) that material entrance matches, coke solids raw material is by described coke granule feed pipe (1-2)
In external circulation fluidized bed (1) described in input, and by the interior fluidized-bed reaction described in described vibration distribution plate (3) entrance
In device (2), at the circle centre position of the top end face of described cylindrical housings, i.e. it is positioned at the top circle centre position in described free spatial domain, arranges
One aperture is the through hole of 50～200mm, i.e. discharging opening, described discharge outlet weld one a length of 1500～2000mm,
The discharge nozzle (4) that internal diameter matches with described discharging opening, and a length of in the other end welding one of described discharge nozzle (4)
1000～5000mm, external diameter is 50～200mm and the perpendicular straight tube (5) of described discharge nozzle (4), described straight tube (5)
The other end affixed with the entrance of described cyclone separator (6) connect, described external circulation fluidized bed (1) bottom is solid by flange
Connect gas distribution grid 1 (8-2), described gas distribution grid 1 (8-2) be thickness be 1～10mm, external diameter outer follows with described
The circle that the internal diameter of ring fluid bed (1) housing matches, the internal diameter of internal diameter and described interior fluidized-bed reactor (2) housing matches
Ring-shaped pottery plate, described gas distribution grid 1 (8-2) is uniformly arranged percent opening be 1%～10%, aperture be 0.5～2.5mm
Through hole, the lower end in the free spatial domain in the circular cylindrical shell body of described external circulation fluidized bed (1), weld a vibration distribution plate
(3):
The cylindrical housings being shaped as both ends open of described interior fluidized-bed reactor (2), described interior fluidized-bed reactor (2)
The top of housing is welded on the outer surface of described vibration distribution plate (3) bottom, and described cylindrical housings internal diameter is
250～2500mm, a length of 800～2000mm, thickness is 3～8mm, in the circumferential wall of the bottom of described cylindrical housings
Also be uniformly arranged 2～8, aperture be 10～50mm through hole, i.e. granule feedback outlet (2-2), at described interior fluidized-bed reaction
The through hole that one aperture is 50～150mm, i.e. titanium slag solid feed inlet are set on the wall of device (2) lower housing portion side, described
Through hole weld the angle of a length of 200～800mm and described interior fluidized-bed reactor (2) housing be 30 °～70 °,
Titanium slag particulate charge pipe (1-3) that internal diameter and described titanium slag solid feed inlet match, described interior fluidized-bed reactor (2)
The affixed gas distribution grid of flange 2 (8-1) is passed through in housing bottom, and described gas distribution grid 2 (8-1) is that a length of thickness is
1～10mm, the disc ceramic wafer that the internal diameter of external diameter and described interior fluidized-bed reactor (2) housing matches, at described gas
Be uniformly arranged on body distribution grid 2 (8-1) percent opening be 1%～10%, aperture be 0.5～2.5mm through hole；
The truncated cone shape housing being shaped as both ends open of described vibration distribution plate (3), the upper end face of described truncated cone shape housing interior
Footpath and the internal diameter of described external circulation fluidized bed (1) housing match, the internal diameter of bottom surface is 100～1000mm, height is
300～1200mm, thickness be 100～400mm, described truncated cone shape housing be divided into upper and lower, at described truncated cone shape housing
Top i.e. accounts for the 2/3 of whole vibration distribution plate (3) length, be uniformly arranged aperture be 0.5～2mm, pitch of holes be 2～6mm
Aperture i.e. vibration distribution plate top aperture (3-1), in described truncated cone shape lower housing portion, i.e. accounts for whole vibration distribution plate (3) long
Degree 1/3, be uniformly arranged aperture be 1～3mm, pitch of holes be 3～10mm macropore i.e. vibration distribution plate bottom macropore (3-2),
The baffle plate (3-3) of the cylindrical housings that one both ends of the surface are all opened wide, described baffle plate are set on the bottom face in described truncated cone shape housing
(3-3) height is 20～50mm, thickness is 5～8mm, internal diameter matches with the bottom surface internal diameter of described truncated cone shape housing,
A vibrator (11) is placed in described vibration distribution plate (3)；
Described gas buffer tank be thickness be 3～10mm, little two big open top face and close bottom surface truncated cone shape
Housing, two described truncated cone shape housings are assembled into the container of a concentric, and described little truncated cone shape housing, i.e. gas are slow
Rush a length of the 200～1500mm of tank 2 (9-1), the internal diameter of open top face interior with described interior fluidized-bed reactor (2) housing
Footpath match, the close internal diameter of bottom surface is 150～1200mm, described gas buffer tank 2 (9-1) and described disc gas
Body distribution grid 2 (8-1) is fixed in described interior fluidized-bed reactor (2) bottom by flange, at described gas buffer tank 2 (9-1)
Close bottom surface axle center at, the through hole that an aperture is 50～120mm, i.e. chlorine feed charging aperture are set, in described through hole
Weld a caliber and described chlorine feed charging aperture match, total length be 400～2100mm square gas feed pipe 2
(9-2), described big truncated cone shape steel housing, i.e. a length of 500～2000mm, end face of gas buffer tank 1 (9-3)
The internal diameter of opening and the internal diameter of described external circulation fluidized bed (1) housing match, the internal diameter of front cover bottom surface is 300～2000mm,
Described gas buffer tank 1 (9-3) and described annular gas distribution grid 1 (8-2) are fixed in described outer circulation stream by flange
Change bed (1) bottom, and the sustained height uniform welding on the outer wall of the truncated cone shape housing of described gas buffer tank 1 (9-3)
4～6 saddle supports or standing support or shield fix on the ground, in the envelope of described gas buffer tank 1 (9-3)
Close at the axle center of bottom surface, the through hole that an aperture is 50～150mm, the i.e. charging aperture of the mixed gas of chlorine and nitrogen are set,
The gas that at described mixed gas charging aperture, welding one a length of 100～500mm, caliber match with described mixed gas charging aperture
Body feed pipe 1 (9-4), and on the sidewall of described gas buffer tank 1 (9-3) and corresponding to described gas feed pipe 2 (9-2)
Exit, the through hole that the external diameter of an aperture and described feed pipe 2 (9-2) matches is set.
2. according to the inner circulation fluidized device preparing titanium tetrachloride of a kind of vibration type described in claim 1, it is characterised in that described
External circulation fluidized bed (1), interior fluidized-bed reactor (2), vibration distribution plate (3), gas buffer tank 1 (9-3), gas
Surge tank 2 (9-1), baffle plate (3-3), discharge nozzle (4), straight tube (5), the material of feed pipe be stainless steel or
Titanium alloy material；Described vibrator (11) be vibration pressure be the bulkhead formula vibrator of 0.1～0.35MPa.
3. the inner circulation fluidized method preparing titanium tetrachloride of vibration type, it is characterised in that utilize the device described in claim 1
Prepare specifically comprising the following steps that of titanium tetrachloride
(1) Feedstock treating
With the high titanium slag that low-grade calcium-magnesium content is high, it is called for short high titanium slag and coke is solid material, with oxygen and nitrogen and chlorine
For gas raw material, first described solid material is carried out sub-sieve by the bolter of 0.7～21 mesh respectively, and press high titanium slag granule
Mean diameter: the ratio 1: 0.8～1.2 of the mean diameter of coke granule, and press the quality of high titanium slag granule: the quality of coke granule
Get the raw materials ready than the ratio being 1: 0.3～3, the most respectively high titanium slag granule and coke granule are heated, be heated to solid particle temperature
Degree is 400～600 DEG C, and the chlorine in described gas raw material is heated to 300～500 DEG C, to oxygen and nitrogen, first presses oxygen:
The volume ratio of nitrogen be 1: 0.1～0.5 ratio mix, then mixed gas is heated to 100～300 DEG C；
(2) chlorination reaction
After (1st) step completes, the raw material after (1st) step is processed, it is separately input in the device described in claim 1,
I.e. coke granule inputs from the coke granule feed pipe (1-2) of described device, by described device with the speed of 1.8～540kg/h
Vibration distribution plate (3) enter the external circulation fluidized bed (1) of described device in and interior fluidized-bed reactor (2) in, high titanium slag
Granule is input to described interior fluidized-bed reactor (2) with the speed of 36～180kg/h from titanium slag particulate charge pipe (1-3) of described device
In, chlorine with 0.5～3.5m/s speed from the gas feed of the described device of gas buffer tank 2 (9-1) bottom surface of described device
Pipe 2 (9-2) is input in described interior fluidized-bed reactor (2), and the mixed gas of oxygen and nitrogen is with 0.2～1.5m/s
The speed gas feed pipe 1 (9-4) from gas buffer tank 1 (9-3) bottom surface of described device is input to described outer circulation fluidisation
Bed (1) in, described coke granule in described external circulation fluidized bed (1) is descending with described oxygen and nitrogen mixed gas
Counter current contacting react, reaction liberated heat heating coke granule reach 1000～1300 DEG C, obtained high-temperature coke granule from
In the interior fluidized-bed reactor (2) described in granule feedback outlet (2-2) entrance on described interior fluidized-bed reaction wall (2-1),
Keeping described interior fluidized-bed reactor (2) internal temperature is 800～1100 DEG C, from described gas feed pipe 2 (9-2) input
Chlorine and the titanium slag granule that enters from described titanium slag charging aperture to carry out high-temp chlorination in described interior fluidized-bed reactor (2) anti-
Should, gas-solid mixture, during up, enters described external circulation fluidized bed (1) because solid reactant grain diameter is gradually reduced
The free spatial domain of internal upper part, the fine grained carried is shed on described vibration distribution plate (3), at described vibrator (11)
In the lower smaller particle of vibration enters described external circulation fluidized bed (1) through described vibration distribution plate top aperture (3-1), with newly
The coke granule of charging is the dirtiest, in described granule feedback outlet (2-2) enters described interior fluidized-bed reactor (2)
Forming inner circulation fluidized chlorination process, that produce after described chlorination reaction and the gas that carries a small amount of dust outer is followed by described
The free spatial domain on ring fluid bed (1) top and discharge nozzle (4) and straight tube (5) input the cyclone separator (6) of described device
In, the pressure that described device is in operation is 0.1～0.35MPa；
(3) gas solid separation
After (2nd) step completes, in the cyclone separator (6) of described device, to (2nd) one-step chlorination reaction produce with a small amount of powder
The gas of dirt, carries out gas solid separation, is collected in the gas that the gas outlet (6-1) on described cyclone separator (6) top leaches,
After natural cooling, obtain titanium tetrachloride product, and collect the residual gas leached, i.e. nitrogen and oxygen and chlorine, collect from institute
State the dust that the solid particle discharging opening (6-3) of cyclone separator (6) bottom leaches.
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| CN104984718B (en) * | 2015-07-15 | 2017-01-11 | 启仲化工（广西）有限公司 | Vibrating-type high-molecular compound treating device |
| US10246342B2 (en) * | 2016-03-31 | 2019-04-02 | Tronox Llc | Centrifugal aluminum chloride generator |
| CN107983765B (en) * | 2017-12-19 | 2020-08-04 | 中石化炼化工程（集团）股份有限公司 | Organic contaminated soil remediation system and process |
| CN109065999B (en) * | 2018-08-17 | 2020-06-19 | 湖南金凯循环科技有限公司 | Method for recycling waste lithium titanate batteries |
| CN114426305A (en) * | 2020-10-29 | 2022-05-03 | 中国科学院过程工程研究所 | Method for preparing artificial rutile by modifying and leaching titanium concentrate containing calcium and magnesium |
| CN112361827B (en) * | 2020-11-13 | 2023-06-20 | 云南国钛金属股份有限公司 | Particle blocking device |
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| AU2006241051A1 (en) * | 2005-04-26 | 2006-11-02 | Tronox Worldwide Llc | Production of titanium tetrachloride using a fluidized bed reactor |
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| AU2006241051A1 (en) * | 2005-04-26 | 2006-11-02 | Tronox Worldwide Llc | Production of titanium tetrachloride using a fluidized bed reactor |
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