CN1314595C - Reactor, its device for making titanium tetrachloride using rich state material chlorination and its method - Google Patents
Reactor, its device for making titanium tetrachloride using rich state material chlorination and its method Download PDFInfo
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- CN1314595C CN1314595C CNB2004100392057A CN200410039205A CN1314595C CN 1314595 C CN1314595 C CN 1314595C CN B2004100392057 A CNB2004100392057 A CN B2004100392057A CN 200410039205 A CN200410039205 A CN 200410039205A CN 1314595 C CN1314595 C CN 1314595C
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Abstract
The present invention relates to a reactor, a device for making titanium tetrachloride by rich state material chlorination and a method thereof. The reactor comprises a fast fluidization bed and an oblique pipe connected with a solid particle charging system on the wall, wherein the top of the oblique pipe is connected with a reactor main body by a transition cone; a distribution plate is arranged between the transition cone and the reactor main body. The present invention is characterized in that the aperture ratio of the distribution plate is from 0.2% to 0.4%; both of a half-cone angle of the transition cone and an included angle of the oblique pipe and the fast fluidization bed are smaller than a complementary angle of a granule stacking angle. The method of the present invention makes the gas speed of raw material gas in the fast fluidization bed higher than the terminal speed of rich state material and petroleum coke granules by a control gas flowmeter. The method ensures that a circulation bed formed by a prior rich state material granule is superimposed on a dense phase turbulent bed formed in the petroleum coke granules in the reactor main body. The present invention can effectively prevent the reactor from sticking. Consequently, the present invention can use the rich state material with a low taste for direct chlorination production and has the advantage of high productive efficiency.
Description
Technical field
The present invention relates to producing of titanium tetrachloride in the industrial production, relate in particular to a kind of reactor and with the apparatus and method of titanium-riched material chlorination producing titanium tetrachloride t 5 bx.
Background technology
Titanium tetrachloride (TiCl
4) be to produce titanium white (TiO
2) and the intermediate of titanium sponge etc., in the smelting of titanium resource, trans-utilization process in occupation of important status.At present, in industrial production, chlorination process is produced TiCl
4Method mainly contain molten-salt growth method and fluidizing chlorination method, the required equipment of molten-salt growth method is huge, complicated operation, production capacity are not high, especially there are a large amount of abraum salts to discharge in the production process, still can not recycle so far, caused very big secondary pollution, in addition, also exist to be difficult for amplify, be difficult to the problem that is connected with the subsequent oxidation operation, fused salt chlorimation has been not suitable for the requirement of large-scale chloride process titanium dioxide production, has not adopted molten-salt growth method to prepare titanium tetrachloride in the chloride process titanium dioxide production technique of developed country.
At present, the fluidizing chlorination method is the main flow technology that titanium tetrachloride is produced, it carries out titanium tetrachloride production with ebullated bed (bubbling) as reactor, boiling chloridizing furnace is by air chamber, gas distributor or sieve plate, conversion zone, transition section, expanding reach, top cover and reinforced, deslagging, collect compositions such as gas system, chlorine enters conversion zone through furnace bottom, make material form boiling state with certain flow rate, conversion zone is generally cylindrical, the employing taper is also arranged, can have the characteristic that reduces gradually along height of bed flow line speed, it is conversion zone bottom high cycle speed, top gas speed is low, raw meal particle size adapts along the tapered characteristic of the height of bed in this and the conversion zone, expanding reach and conversion zone sectional area maintenance certain proportion, can alleviate molecule in process of production carry phenomenon secretly, the material slide angle of transition section is difficult for too small, not so, easily pile up material, produce the bridging phenomenon.The fluidizing chlorination method is compared with molten-salt growth method, and is simple to operate though production capacity is higher, do not have serious three wastes problem, the boiling point that generates in reaction process CaCl higher, that be the liquid phase existence
2, MgCl
2Can in bed, accumulate in a large number, cause channel to occur, destroy fluidized state, therefore, the ebullated bed chloridization process is too harsh to the requirement of raw material, require the weight ratio of CaO in the raw material and MgO must be less than 1%, and cause the transformation efficiency of rich titanium material lower because mass transfer, rate of heat transfer are low between gas-solid, production capacity be not high.
From the distribution of world's titanium resource, with TiO
2Meter is according to statistic data in 1980, TiO
2Content higher, can be directly used in ebullated bed chlorating rutile reserves and only accounted for for 7% (not comprising China), the rutile mineral reserve of this GOOD TASTE are petered out; China's titanium resource reserves account for 45% of the world, occupy first of the world, but be mainly the vanadium titano-magnetite that is difficult for utilization, wherein more than 90.5% at Flos Bombacis Malabarici, and the rich titanium material Ca that the Flos Bombacis Malabarici ore deposit produces, Mg content height, wherein, the weight ratio of CaO and MgO is up to 6～9%, can not be directly used in the ebullated bed chloridization process, this has just produced conflict between raw material sources and technique for producing raw material, titanium resource utilization and exploitation to China have caused great obstruction, therefore, can directly utilize high Ca, the technology that the raw material of Mg content carries out titanium tetrachloride production is developing tendency in future.
Summary of the invention
The objective of the invention is to: overcome main TiCl at present
4Bonding difficult problem during the rich titanium material of low taste (calcium-magnesium content height) chlorination that industrial process-fluidizing chlorination method exists is for the titanium resource that directly utilizes high Ca, Mg content is produced TiCl
4Thereby, provide a kind of reactor and with the apparatus and method of titanium-riched material chlorination producing titanium tetrachloride t 5 bx.
The reactor of the present invention's design, comprise the first order reaction bed, this reaction bed comprises a fast fluidized bed, an inclined tube that is connected with the solid particulate charging system on its wall, its top is connected with reactor body by a transition circular cone, be provided with grid distributor between transition circular cone and reactor body, the percentage of open area of described grid distributor is 0.2～0.4%, and the angle of the semi-cone angle of described transition circular cone, inclined tube and fast fluidized bed is all less than the complementary angle at particle packing angle.Described reactor is made of the reaction of high order bed, is equipped with refinery coke charging inclined tube on the reactor body of each order reaction bed.
The angle of circular cone semi-cone angle, inclined tube and fast fluidized bed all should be piled up at transition section to prevent particle less than the complementary angle at particle packing angle.In order to realize well distributed in reactor body of solid particulate and gas, the flow pattern grid distributor was set, its opening diameter usually should be at more than 2 times of granule materials maximum diameter.Each reactor body is provided with refinery coke charging inclined tube to control the refinery coke content in every stage reactor main body, in first step reactor body, can set up refinery coke charging inclined tube and can be directly by the refinery coke content in the refinery coke proportioning controlling reactor main body of granule materials.
Device with the titanium-riched material chlorination producing titanium tetrachloride t 5 bx provided by the invention, comprise one or more levels reaction bed, described reaction bed comprises a fast fluidized bed that is communicated with the raw material gas tank, an inclined tube that is connected with the solid particulate charging system on its wall, its top is connected with reactor body by a transition circular cone, is provided with grid distributor between transition circular cone and reactor body; On the described raw material gas tank connection fast fluidized bed passage gas meter is set, the reactor body of last step reaction bed is communicated with a gas solid separation system, this gas solid separation system also links to each other with a condensing works, storage tank respectively, described condensing works connects a tail gas absorption cell, the percentage of open area of described grid distributor is 0.2～0.4%, and the angle of the semi-cone angle of described transition circular cone, inclined tube and fast fluidized bed is all less than the complementary angle at particle packing angle.
Described solid particulate charging system adopts feeding screw.
Method with the titanium-riched material chlorination producing titanium tetrachloride t 5 bx provided by the invention, by the pilot-gas under meter, make that gas speed terminal velocity than rich titanium material and petroleum coke particles in fast fluidized bed of unstripped gas is all high, simultaneously, diameter ratio from structure control fast fluidized bed and reactor body, make that gas speed is between the rapids bed velocity of transformation and its terminal velocity of petroleum coke particles in the reactor body, and on the terminal velocity of fine grain rich titanium material, guarantee on the close bed of rapids mutually that petroleum coke particles forms, to be superimposed with a granuloplastic circulation bed of rich state material in the reactor body; Refinery coke content in the described reaction bed is by refinery coke charging inclined tube control refinery coke inlet amount.
Refinery coke content in the described first step reaction bed is by the refinery coke proportioning control of granule materials, and the refinery coke content in other reaction bed is controlled by the refinery coke inlet amount that is entered by refinery coke charging inclined tube.
The inventive method, in fast fluidized bed, the structure that adopts gas-solid and flow to, the terminal velocity of rich titanium material of the gas speed ratio of the mixed gas of chlorine and oxygen and petroleum coke particles is all high, guarantees that rich titanium material, petroleum coke particles all are in air conveying state in fast bed; At the fast fluidized bed top, granule materials passed the flow pattern grid distributor and entered in the reactor body; In reactor body, the mixed gas gas speed of chlorine and oxygen is along with the expansion of reactor radius, superficial gas velocity decreases, make gas speed between the rapids bed velocity of transformation and its terminal velocity of the bigger petroleum coke particles of particle diameter, and this gas speed is on the terminal velocity of fine grain rich titanium material, guarantee to be rapids bed state at the burnt particle of reactor body PetroChina Company Limited., rich titanium material particle is air conveying state and is superimposed upon on the rapids bed.Wherein, the oxygen volume content should be according to full bed heat balance, need to determine heat that the refinery coke burning provides after, determine according to the refinery coke combustion reactions.As not needing to utilize the rich titanium material of first step fast-fluidized-bed conversion part and in order to reduce the wearing and tearing of particle to first step grid distributor, rich titanium material is entered from the fast fluidized bed inclined tube, and the refinery coke content in the reactor body must be by being built up in the refinery coke charging inclined tube control in the reactor body.
At the reactor body top, second stage fast fluidized bed reacts and cross the flow pattern grid distributor by the second stage enters second stage reactor body because of the petroleum coke particles that attenuates of reaction particle diameter enters for rich titanium material particle that unreacted finishes and part, the refinery coke inlet amount control of refinery coke content in the reactor body of the second stage by entering by refinery coke charging inclined tube, later similarly at different levels.Abundant for what guarantee to react, can increase the air conveying reactor reaction device of the many particles main body of arranging multistage fast bed and top thereof.In a word, the rich titanium material of fine particle is always finished reaction with air conveying state, and oarse-grained refinery coke in fast fluidized bed with air conveying state, be to finish reaction in reactor body with a rapids bed state, at last, reacting remaining particle and reactant gases discharges reactor by the fast fluidized bed at top and enters follow-up unit.
In theory, the key that solves the anti stick problem is: under the situation that causes the agglutinating liquid phase substance to exist, prevent that the key that bonding takes place between particle is gas-solid, there is stronger shearing force between the particle and guarantees the characteristic time that strengthen less than particle bond intergranular duration of contact, promptly can directly use high Ca, the method that the Mg raw material carries out chlorination production should have following characteristics: can react under 800～1000 ℃ of suitable reaction temperature that (this moment, speed of reaction was higher, equipment material can bear), shearing force etc. is stronger between fluid, the contact time is shorter between particle, titaniferous particulate material is finished reaction substantially an one way in the reaction times simultaneously, thereby does not need to circulate.In the inventive method, because the particle in the fast bed is in air conveying state, granule density very low (＜0.05), the contact time is short between particle, turbulence intensity is big, thus intergranular bonding phenomenon is effectively controlled; The rich state material that calcium-magnesium content is high is the particle transport state in refinery coke rapids bed, compare with traditional ebullated bed, the fluidic shearing force is more remarkable, and rich titanium material back-mixing is very little, the residence time in reactor body shortens dramatically, and can effectively avoid the chance of the intergranular collision contact of rich titanium material, has played the effect that cuts off and break away from fast reaction zone, thereby can effectively destroy and suppress particle bond, mass transfer, heat-transfer effect also will be higher than ebullated bed simultaneously.But, compare with ebullated bed, concerning rich titanium material, the raising of gas speed has also caused the shortening of the residence time simultaneously, does not transform thereby might reach comparatively completely, in order to finish reaction in the reaction times substantially and don't to make the reactor body bed too high an one way, can be according to real reaction efficient, increase the second stage, perhaps increase is more, till reaction conversion ratio reaches requirement.
The invention has the beneficial effects as follows: reactor of the present invention and with the apparatus and method of titanium-riched material chlorination producing titanium tetrachloride t 5 bx, can prevent effectively that agglutinating from taking place, thereby can utilize the low rich titanium material of taste (calcium-magnesium content height) directly to carry out chlorination production, enlarge raw material sources, the production efficiency height provides a feasible approach for solving Chinese titanium resource utilization.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is a structural representation of the present invention
Fig. 2 is the process flow diagram that the present invention is used for chlorination production
The accompanying drawing sign
1, one-level fast bed 2, grid distributor 3, the air conveying reactor of one-level
4, secondary fast bed 5, grid distributor 6, the air conveying reactor of secondary
7, three grades of fast beds 8, refinery coke charging inclined tube 9, gas mixing tank
10, gas meter 11, feeding screw 12, reactor body
13, gas-solid separating device 14a, the first storage tank 14b, second storage tank
15, condensing works 16, tail gas absorption cell
E, exit gas F, fast bed
G, unstripped gas G1, oxygen G2, chlorine
H, water coolant M, air conveying bed P1, refinery coke+rich titanium material
P2, refinery coke S1, reactor first step S2, the reactor second stage
Embodiment
As depicted in figs. 1 and 2, (proportioning requires according to temperature maintenance and the reactor scale is determined, perhaps adopts TiCl with suitable proportioning for chlorine G2 and oxygen G1
4The oxidized tail gas Cl that titanium white produces is produced in oxidation
2Amount 〉=75mol%, O
2After amount 〉=1mol%) mixed in mixing tank 9, unstripped gas G entered in advance the baking temperature to 800～1000 ℃ one-level fast bed 1; Suitable ore deposit proportioning, mixing/carbon granule raw material P1 (wherein, TiO
2C=100 in the/refinery coke: 30～35) enter one-level fast bed 1 by feeding screw 11 control metering backs by inclined tube, when the granularity of rich titanium material was-90～+ 200 orders, the granularity of refinery coke was-20～+ 35 orders.Gas line speed in the one-level fast bed 1 is 4～6m/s, and refinery coke and rich titanium material particle all are air conveying state, and therefore, the contact time is short between particle, turbulence intensity is big, thereby intergranular bonding phenomenon is effectively controlled.
Shown in Fig. 1-a, the chlorination rate of rich titanium material in fast bed 1 is no more than 20%, the grid distributor 2 (percentage of open area 0.2～0.4%) that the intact gas-solid mixture of unreacted is upward through enters the air conveying reactor 3 of many particles, the bed footpath enlarges, the gas prompt drop is low, and form the air conveying bed of particle more than M thereon, wherein: the gas speed after the reduction is between the rapids bed velocity of transformation and terminal velocity of the bigger petroleum coke particles of particle diameter, makes petroleum coke particles be rapids bed state; Gas speed after reducing simultaneously is still big than rich titanium material particulate terminal velocity, makes rich titanium material particle be feed status.Because petroleum coke particles stirs the existence of violent turbulence layer, rich state material particle back-mixing in bed in calcium magnesium source is very little simultaneously, the residence time is shorter, gas-solid, the shearing force between solid solid are strong, between particle the contact time shorter, thereby make bonding be difficult for taking place and strengthening.The incomplete rich titanium material particle of reaction that leaves from the air conveying reactor S1 of one-level, in the air conveying reactor S2 of secondary, enter the air conveying reactor 6 of the many particles of secondary and further transform through secondary fast bed 4, grid distributor 5, simultaneously, add refinery coke P2 by refinery coke charging inclined tube 8, until TiO
2Reaction conversion ratio＞93%.The CaCl that generates in the reaction process
2, MgCl
2, and upwards flow through beds at different levels successively and go out furnace gases by air-flow and turbulence material aerosol dispersion Deng liquid impurity with logistics, and and part enter gas solid separation system 13 together than fine particle and exit gas E, and CaCl
2, MgCl
2Then be cooled in separation system and be collected among the storage tank 14a with solid-state form Deng liquid impurity, the gaseous products of being discharged by separation system 13 enters condensing works 15 usefulness water coolant H and cools off, with product TiCl
4Collect among the storage tank 14b, tail gas is then handled back emptying, wherein Cl through tail gas absorption cell 16
2Content＜1mol%.
Apparatus and method of the present invention adopt fast bed dilute phases (air conveying) operation, gas-solid, solid between reactive force big, shearing action is strong, the contact time is short between particle; Reactor body is formed by stacking by the refinery coke bed of turbulence and the rich titanium material circulation bed of feed status, the work high cycle speed reaches 0.9～1.8m/s, the kinergety of petroleum coke particles is approximately than order of magnitude of the general boiling height of bed, can make the liquid phase of separating out in the reaction by aerosol dispersion, shearing force is strong, a small amount of adhesive there is the very strong ability of pulverizing, makes it to be difficult to grow up; Simultaneously rich titanium material solid back-mixing is less, to each other duration of contact short, can not interrupted when strengthening fully in bonding, thereby be difficult to form bonding.Apparatus and method of the present invention except that having stronger anti-seizure performance, generally seethe with excitement about 4 times of the height of bed of its unit surface productivity ratio, if press unit volume calculating, then production capacity can improve more than 10 times.
Claims (2)
1, a kind of method with the titanium-riched material chlorination producing titanium tetrachloride t 5 bx, it is characterized in that: in chlorination reactor, this chlorination reactor comprises one or more levels reaction bed, described reaction bed comprises a fast fluidized bed that is communicated with the raw material gas tank, an inclined tube that is connected with the solid particulate charging system on its wall, its top is connected with reactor body by a transition circular cone, is provided with grid distributor between transition circular cone and reactor body; On the described raw material gas tank connection fast fluidized bed passage gas meter is set, the reactor body of last step reaction bed is communicated with a gas solid separation system, this gas solid separation system also links to each other with a condensing works, storage tank respectively, described condensing works connects a tail gas absorption cell, it is characterized in that, the percentage of open area of described grid distributor is 0.2～0.4%, and the angle of the semi-cone angle of described transition circular cone, inclined tube and fast fluidized bed is all less than the complementary angle at particle packing angle; By control chloridating gas Cl
2And O
2Flow, make that gas speed terminal velocity than rich titanium material and petroleum coke particles in fast fluidized bed of unstripped gas is all high, simultaneously, diameter ratio from structure control fast fluidized bed and reactor body, make gas speed in the reactor body between the turbulent fluidized bed velocity of transformation and its terminal velocity of petroleum coke particles, and on the terminal velocity of fine grain rich titanium material, guarantee on the close phase turbulent fluidized bed that petroleum coke particles forms, to be superimposed with a granuloplastic circulation bed of rich titanium material in the reactor body; Described rich titanium material is the rich titanium material of high contents of calcium and magnesium.
2, by the described method of claim 1 with the titanium-riched material chlorination producing titanium tetrachloride t 5 bx, it is characterized in that, the refinery coke proportioning of the ore deposit/carbon granule raw material of the refinery coke content in the first step reaction bed of described multistage chlorination reactor by entering first step reaction bed is controlled, and described ore deposit/carbon granule raw material is TiO
2C in the/refinery coke; Described TiO
2Weight part proportioning=100: 30～35 with C in the refinery coke; Refinery coke content in other order reaction bed is controlled by the refinery coke inlet amount that enters in this order reaction bed.
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| CNB2004100392057A CN1314595C (en) | 2004-02-05 | 2004-02-05 | Reactor, its device for making titanium tetrachloride using rich state material chlorination and its method |
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| CN1314595C true CN1314595C (en) | 2007-05-09 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TR201010131T1 (en) * | 2008-06-05 | 2011-10-21 | Synthesis Energy Systems, Inc. | Fluid bed gasifier with solids discharge and sorting device. |
| CN101475210B (en) * | 2009-01-13 | 2010-08-18 | 重庆大学 | Method for preparing titanic chloride by half cycle fluidization |
| WO2011028869A1 (en) * | 2009-09-03 | 2011-03-10 | E.I. Du Pont De Nemours And Company | Titanium bearing material flow control in the manufacture of titanium tetrachloride using a combination of feedback and feed forward responses |
| CN105197989B (en) * | 2015-08-20 | 2017-01-25 | 四川宏达(集团)有限公司 | Flash suspension chlorination method for raw materials containing titanium |
| CN106379935B (en) * | 2016-11-11 | 2018-01-26 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of apparatus and method for producing titanium tetrachloride |
| CN115725859B (en) * | 2022-11-21 | 2024-03-26 | 河南龙佰智能装备制造有限公司 | Titanium sponge fluidization reaction system and method |
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| JPH061613A (en) * | 1992-06-24 | 1994-01-11 | Ishihara Sangyo Kaisha Ltd | Production of titanium tetrachloride |
| JP2000109322A (en) * | 1998-10-01 | 2000-04-18 | Sumitomo Sitix Amagasaki:Kk | Production of titanium tetrachloride |
| JP2003226522A (en) * | 2002-02-04 | 2003-08-12 | Ishihara Sangyo Kaisha Ltd | Method for producing titanium tetrachloride |
| CN1454849A (en) * | 2002-04-30 | 2003-11-12 | 中国科学院过程工程研究所 | Apparatus and method of preparing titanium tetrachloride for chlorination of titanium-containing mineral |
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Patent Citations (4)
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| JPH061613A (en) * | 1992-06-24 | 1994-01-11 | Ishihara Sangyo Kaisha Ltd | Production of titanium tetrachloride |
| JP2000109322A (en) * | 1998-10-01 | 2000-04-18 | Sumitomo Sitix Amagasaki:Kk | Production of titanium tetrachloride |
| JP2003226522A (en) * | 2002-02-04 | 2003-08-12 | Ishihara Sangyo Kaisha Ltd | Method for producing titanium tetrachloride |
| CN1454849A (en) * | 2002-04-30 | 2003-11-12 | 中国科学院过程工程研究所 | Apparatus and method of preparing titanium tetrachloride for chlorination of titanium-containing mineral |
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