CN113753945B - Composite chlorination preparation method of titanium tetrachloride - Google Patents
Composite chlorination preparation method of titanium tetrachloride Download PDFInfo
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Abstract
The invention discloses a composite chlorination preparation method of titanium tetrachloride, belonging to the technical field of chlorination titanium dioxide production. The process combines boiling chlorination and meltingThe salt chlorination method is combined, two kinds of chlorination reactions are carried out in a composite chlorination furnace, and TiCl is produced 4 The mixed gas passes through the atomizer, the dust collector, the pulping device, the solid-liquid separation device and the drying device to mix TiCl 4 Separating out the gas and recovering the furnace charge into the composite chlorination furnace. TiO entrained in the chlorine gas is returned by the recovery of bottom discharge furnace charge, the recovery of dust collection slag material and the oxidation 2 The recovery rate of titanium is improved; through the secondary reaction of the molten salt reaction tail gas, the operation of a subsequent system is simpler, and the labor intensity is greatly reduced.
Description
Technical Field
The invention relates to the technical field of titanium dioxide production by a chlorination method, in particular to a composite chlorination preparation method of titanium tetrachloride.
Background
Titanium dioxide is a white inorganic pigment, is the best white pigment in performance in the world at present, is the second inorganic chemical product to synthesize ammonia and phosphoric acid and is sold in the third place in the world, and is widely applied to the industries of coatings, plastics, papermaking, printing ink and the like. Titanium dioxide is the most important one of titanium products, more than 90% of titanium ores are used for producing the titanium dioxide in the world, the industrial production of the titanium dioxide comprises a chlorination process and a sulfuric acid process, the chlorination process titanium dioxide product has good quality and stable performance, does not basically cause pollution to the environment, is the mainstream technology of the international titanium dioxide production at present, and nearly 75% of the titanium dioxide in the world (excluding China) is produced by the chlorination process.
One of the key processes for titanium dioxide by chlorination is TiCl 4 Production of TiCl, the present industrial production 4 The method mainly comprises two processes of boiling chlorination and molten salt chlorination, but has certain technical difficulties which are difficult to break through, and mainly comprises the following steps: on one hand, in the boiling chlorination process, along with the collision and friction between materials and the reaction, the particle size of the materials is gradually reduced, and along with the tail gas, the recovery rate of titanium is reduced; on the other hand, due to the limitation of reaction parameters and materials, boiling chlorination is not suitable for most domestic titanium resources (mainly high-calcium magnesium titanium resources), so that the resource advantages cannot be embodied. Due to the limitation of the structural form of the molten salt chlorination, the capacity cannot be greatly improved; meanwhile, the high-temperature volatile salt is difficult to recover and has adverse effect on the subsequent process; third, molten salt chlorination is more difficult to handle than boiling chlorination.
Disclosure of Invention
In order to solve the technical problems, the invention provides a composite chlorination preparation method of titanium tetrachloride, which realizes large chlorination of domestic high-calcium magnesium titanium resources, and simultaneously recovers bottom-discharge furnace burden, dust-collecting slag material and TiO carried in chlorine gas through oxidation 2 The recovery rate of titanium is improved; through the secondary reaction of the molten salt reaction tail gas, the operation of a subsequent system is simpler, and the labor intensity is greatly reduced.
In order to realize the technical purpose, the invention adopts the following scheme: the preparation method of titanium tetrachloride by complex chlorination comprises the following steps:
s1, mixing a titanium-rich material with high calcium and magnesium with a reducing agent, and adding the mixture into an upper boiling chlorination section and a lower molten salt chlorination section of a composite chlorination furnace respectively; adding molten NaCl into the molten salt chlorination section in advance, and introducing chlorine into the molten salt chlorination section of the composite chlorination furnace to perform chlorination reaction;
s2, allowing the mixed gas after the reaction in the molten salt chlorination section to enter a boiling chlorination section through a gas distributor of the composite chlorination furnace to participate in chlorination reaction;
in the molten salt chlorination stage, excessive chlorine and titanium-rich material are subjected to chlorination reaction to generate TiCl 4 And metal chloride, and simultaneously volatilizing in the molten salt chlorination section and reacting the entrained molten salt with the metal chloride to generate double salt;
s3, along with the reaction of the boiling chlorination section, the calcium and magnesium impurities in the titanium-rich material generate CaCl in the chlorination reaction 2 、MgCl 2 Enriching in the furnace charge of the boiling chlorination section, and periodically adding CaCl 2 、MgCl 2 Feeding the mixture which does not react into a molten salt chlorination section to participate in the reaction of the molten salt chlorination section;
TiCl generated in boiling section in S4 and S2 4 The mixed gas is discharged from the furnace top of the composite chlorination furnace and is mixed with atomized TiCl in an atomizer 4 Slurry and coarse TiCl 4 The mixture is directly contacted with TiCl 4 Cooling the mixed gas to solidify the metal chloride;
s5, cooling by the aid of the S4, feeding the mixed gas into a dust collector, and separating solid dust collecting slag from the gasThe mixed gas after gas-solid separation is sent to a condensation process to collect TiCl 4 ；
S6, adding water and dilute hydrochloric acid into the dust-collecting slag separated in the S5 in a pulping device, and stirring to prepare a slag-slurry mixture;
s7, carrying out solid-liquid separation on the slag-slurry mixture in a solid-liquid separation device, further treating the filtrate in a downstream process, and drying the separated solid in a drying device;
s8, taking the dried dust-collecting slag as a recovered furnace charge to return to a molten salt chlorination section of the composite chlorination furnace, and further recovering the furnace charge.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention relates to a composite chlorination process combining side-deslagging boiling chlorination and molten salt chlorination, which is characterized in that a high-calcium magnesium titanium raw material is reacted in a boiling chlorination section, and calcium and magnesium are reacted to generate CaCl 2 、MgCl 2 The calcium, magnesium and titanium are enriched in a fluidized bed, and are discharged into a molten salt section through side deslagging, and the molten salt section is periodically discharged and treated, so that a beneficial solution is provided for the comprehensive utilization of high-calcium, magnesium and titanium resources in China and the improvement of the additional value of the resources;
(2) Although the fused salt chlorination has a wider application range on the titanium raw material with high calcium and magnesium, the limitation of the structure, the operation mode and the like of the fused salt chlorination is large, and the single fused salt chlorination has large limitation on the improvement of the capacity, so that the method is difficult to match with the large-scale chlorination titanium dioxide production;
(3) The gas entrainment and high-temperature volatile NaCl in the molten salt chlorination section enter the boiling chlorination section to be used as a raw material of the boiling section to participate in the reaction, so that the problem of uneven reaction caused by uneven blending of boiling chlorinated solid NaCl is solved, and the problems of blockage and the like caused by the gas entrainment and high-temperature volatile NaCl in the molten salt chlorination section to subsequent dust collection, condensation and other processes are solved;
(4) The dust-collecting slag is subjected to liquid-solid separation after pulping under an acidic condition, so that most harmful impurities (aiming at a chlorination process) enter the filtrate, and the separated solid components can be recovered in a molten salt section;
(5) The TiO entrained chlorine is returned by the bottom discharge furnace burden of the boiling section, the recovery furnace burden of the molten salt section and the oxidation 2 The recovery rate of titanium is greatly improved.
Further, the titanium-rich material is TiO 2 Acid-soluble titanium slag or TiO with the content of 74-75wt% 2 High titanium slag with content more than 85 wt%; the titanium-rich material with high calcium and magnesium content means that the sum of the contents of CaO and MgO is more than 2.5wt%.
Further, the reducing agent is any one or more of charcoal, petroleum coke and metallurgical coke.
Further, the mixture is composed of 70-80wt% of high-calcium magnesium rich titanium material and 20-30wt% of reducing agent.
Further, the chlorine is the chlorine returned by oxidation and/or the newly added chlorine, wherein the chlorine returned by oxidation is introduced into the molten salt chlorination section of the composite chlorination furnace from below the liquid level of the molten salt; the newly added chlorine gas is introduced into the molten salt chlorination section from the position above the molten salt liquid level and enters the boiling chlorination section through a gas distributor.
Further, the molten salt volatilized and entrained in S2 refers to NaCl and AlCl 3 、MnCl 2 、FeCl 2 The generated double salt, wherein NaCl and AlCl 3 To generate double salt NaAlCl 4 ，NaAlCl 4 The separation in a dust collector can reduce the blockage of the subsequent condensation process.
Further, tiCl in S4 4 The composition of the mixed gas comprises gas TiCl 4 、CO、CO 2 、N 2 HCl, controlling TiCl entering the atomizer 4 The amount of the mixed gas ensures that the tail gas heat will TiCl 4 Slurry and coarse TiCl 4 In a liquid TiCl state 4 All are vaporized.
Further, the liquid TiCl mentioned above 4 All vaporization is carried out by the outlet temperature of the atomizer, the inlet temperature of the dust collector, the outlet temperature of the dust collector and liquid TiCl 4 And realizing flow linkage.
Further, the temperature control range of the outlet of the dust collector is 140-260 ℃, and TiCl is used for controlling the temperature of the outlet of the dust collector to be 140-260 DEG C 4 The flow rate of the slurry is compared with the total liquid TiCl entering the atomizer 4 The flow rate is 10% or less.
Further, the solid content of the slurry mixture in the S6 is less than or equal to 45wt%, and the water content of the dried material in the S8 is less than 1wt%.
Drawings
FIG. 1 is a schematic structural diagram of a composite chlorination furnace provided in an embodiment of the invention;
FIG. 2 is a schematic structural diagram of a gas distributor according to an embodiment of the present invention;
FIG. 3 is a flow chart of a complex chlorination process provided in an embodiment of the present invention;
labeled as: 1. an exhaust port; 2. a first mixture inlet; 3. a first chlorine pipe; 4. a second chlorine pipe; 5. a molten salt discharge port; 6. an electrode; 7. a discharge outlet; 8. a molten salt discharge port; 9. a gas distributor; 91. a cylindrical member; 92. a breather pipe; 93. a pipe cap; 94. air holes; 10. a second mixture inlet; 11. a pneumatic conveying device; 12. a composite chlorination furnace; 13. a bottom grate furnace charge discharge device; 14. an atomizer; 15. a dust collector; 16. a stirring tank; 17. a solid-liquid separation device; 18. and (7) a drying device.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to fully understand the objects, features and effects of the invention, but the present invention is not limited thereto.
Referring to fig. 1 and 2, a composite chlorination furnace for producing titanium tetrachloride comprises a boiling chlorination section and a molten salt chlorination section, wherein the boiling chlorination section is the upper part of the composite chlorination furnace, the molten salt chlorination section is positioned at the lower part of the composite chlorination furnace, and a gas distributor 9 is arranged between the lower end of the boiling chlorination section and the upper end of the molten salt chlorination section. The gas distributor 9 is a cylindrical member 91 cast from a refractory casting material, in which uniformly distributed ventilation pipes 92 are embedded. The material of the vent pipe 92 is nickel-based alloy pipe, siC pipe and Al 2 O 3 One kind of ceramic tube. The bottom end of the breather pipe 92 is flush with the lower surface of the cylindrical member 91; the upper end of the breather pipe 92 is communicated with the upper surface of the cylindrical castable member, and the side wall of the breather pipe 92 higher than the upper surface of the cylindrical member 91 is uniformly drilledThe number of the air holes 94 is not less than 8, and the aperture is 2-4mm. An umbrella-shaped pipe cap 93 is fixed at the top end of the breather pipe 92 to prevent solid materials from blocking the breather pipe 92, and the material of the pipe cap 93 is the same as that of the breather pipe 92. The diameter of the vent tube 92 is typically 15-30mm, most preferably 25mm.
The top of the boiling chlorination section is a furnace top, an exhaust port 1 is arranged on the furnace top, the exhaust port 1 directly enters an atomizer, and TiCl generated by the reaction is mixed with the gas 4 The mixed gas is directly fed into the atomizer. The furnace top is also provided with a plurality of thermocouples and pressure sensors. Boiling chlorination section lateral wall is provided with a plurality of first mixture import 2 and bin outlet 7, and first mixture pipe is connected to bin outlet 7, first mixture pipe and fused salt chlorination section intercommunication.
The side wall of the upper part of the molten salt chlorination section is provided with a first chlorine inlet, the first chlorine inlet is connected with a first chlorine pipe 3, a pressure sensor and a control valve (P represents the pressure sensor, M represents the control valve, and T represents a thermocouple in the figure 1) are sequentially arranged on the first chlorine pipe 3 according to the gas flowing direction, and the first chlorine pipe 3 conveys fresh chlorine to the molten salt chlorination section. The lower part lateral wall of fused salt chlorination section is provided with the second chlorine import, and second chlorine import connection second chlorine pipe 4 has set gradually control valve and pressure sensor on the second chlorine pipe 4 according to the gas flow direction, and second chlorine pipe 4 carries the chlorine that the oxidation returns to the fused salt chlorination section. The first chlorine pipe 3 and the second chlorine pipe 4 are connected through a pipeline, and a control valve is arranged on the pipeline.
The side wall of the middle upper part of the fused salt chlorination section is also provided with a second mixed material inlet 10, the second mixed material inlet 10 is connected with a second mixed material pipe, the first mixed material pipe is connected with the middle part of the second mixed material pipe, and the first mixed material pipe and the second mixed material pipe are respectively provided with a control valve. A molten salt discharge port 8 is formed in the side wall of the molten salt chlorination section below the second mixture inlet 10, an electrode 6 and a thermocouple are fixed to the side wall of the lower portion of the molten salt chlorination section, and a molten salt discharge port 5 is formed in the bottom of the molten salt chlorination section.
The furnace body and the furnace top of the composite chlorination furnace are both composed of a shell and a lining, the shell is a steel shell, and the lining is made of refractory materials.
The invention provides a composite chlorination process for producing titanium tetrachloride, which comprises the following steps:
s1-1, mixing a high-calcium high-magnesium titanium-rich material and a reducing agent according to the weight ratio of 60 to 80%: mixing the components by mass ratio of 40 to 20 percent, and adding the mixture into a composite chlorination furnace in a pneumatic conveying mode. Pneumatic conveying devices such as pneumatic blowing equipment.
The titanium-rich material is TiO 2 Acid-soluble titanium slag with the content of 74 to 75wt%, or TiO 2 High titanium slag with a content of more than 85wt%, preferably TiO 2 High titanium slag with the content of more than 90wt percent. The titanium-rich material with high calcium and magnesium content means that the sum of the content of CaO and MgO is more than 2.5wt%, and more preferably the sum of the content of CaO and MgO is 2.5 to 4.5wt%.
The reducing agent is selected from charcoal, petroleum coke, metallurgical coke, etc., preferably petroleum coke, more preferably calcined petroleum coke.
The mixture is a mixture containing 70-80wt% of a titanium-rich material and 20-30wt% of a reducing agent (the sum of the contents of the titanium-rich material and the reducing agent is 100%), and preferably a mixture containing 75wt% of the titanium-rich material and 25wt% of the reducing agent.
S1-2, adding the mixture in the S1-1 into an upper boiling chlorination section of the composite chlorination furnace.
S1-3, adding molten NaCl in a molten salt chlorination section in advance, adding molten mixed salt into a molten salt chlorination section at the lower part of the composite chlorination furnace, and then adding one or more of the mixed material, the bottom row furnace charge and the recovered furnace charge into the molten salt chlorination section according to any proportion.
S1-4, cl returning from oxidation 2 And/or newly adding Cl 2 And introducing the mixture into a molten salt chlorination section of a chlorination furnace for chlorination reaction. In normal production, the heat of reaction of the chlorination reaction is sufficient to maintain its heat requirement, and in the case of insufficient heat, it is maintained by electrode heating.
Oxidation of returned Cl 2 Introducing the Cl newly added into the molten salt chlorination section from the position above the molten salt liquid level 2 And introducing the molten salt chlorination section from the position above the molten salt liquid level, and introducing the mixed gas after reaction in the molten salt chlorination section into the boiling chlorination section through a gas distributor. Preferably, the catalyst can be prepared by a subsequent process stageRealizing newly adding Cl for liquid level of titanium chloride storage tank 2 And (4) automatically adjusting the flow.
Oxidized back to Cl 2 And newly added Cl 2 And realizing mutual manual switching according to the process requirement. Preferably, the switching is performed manually in the control system by means of a control valve.
Oxidation of returned Cl 2 The compound chlorination furnace can be simultaneously introduced from the position below the molten salt liquid level and the position above the molten salt liquid level for a long time, and the respective proportions are manually set.
S2, allowing the mixed gas after the reaction in the S1-4 to enter a boiling chlorination section through a gas distributor of the composite chlorination furnace;
excess Cl in the molten salt chlorination stage 2 Carrying out chlorination reaction with a titanium-rich material to generate TiCl 4 Gas and metal chloride, and the volatilized molten salt and entrained molten salt (mainly NaCl) react with the metal chloride to produce double salt (at least comprising NaMnCl) 3 、NaAlCl 4 、NaFeCl 3 、NaFeCl 4 One of them) is separated in a subsequent process.
Compared with the traditional process that solid NaCl is added into the initial mixture, the method has the advantages that the molten NaCl is added in advance in the molten salt chlorination section, then the NaCl is brought into the boiling section through the mixed gas generated in the molten salt section, the distribution is more uniform, and the reaction for generating the complex salt is more thorough.
The volatilized and entrained molten salt is mainly NaCl and AlCl 3 、MnCl 2 、FeCl 2 The metal chlorides are generated into double salts, wherein the most important is NaCl and AlCl 3 The reaction generates double salt NaAlCl 4 ，NaAlCl 4 The dust collector is separated, so that the blockage of the subsequent process is reduced, wherein the blockage of the subsequent process refers to the blockage of a condensation process, particularly the blockage of heat exchange equipment.
S3, along with the proceeding of the boiling chlorination reaction in the S2, the calcium and magnesium impurities in the titanium-rich material generate CaCl in the chlorination reaction 2 、MgCl 2 The enrichment in the furnace burden of the boiling chlorination section can cause the furnace burden to be slagging, and the further proceeding of the reaction is influenced. Therefore, the bottom grate furnace charge discharging device 13 is periodically started to discharge CaCl 2 、MgCl 2 And the unreacted mixture is sent into S1-3, so that the direct recovery of bottom discharge furnace charge is realized, the recovery rate of titanium is improved, and CaCl 2 、MgCl 2 And (5) remaining in the mixed molten salt, and periodically discharging for treatment.
S4 TiCl formed in S2 4 The mixed gas is discharged from the top of the composite chlorination furnace and is mixed with the atomized TiCl in an atomizer 4 Slurry and coarse TiCl 4 The mixture is directly contacted with TiCl 4 And cooling the mixed gas to solidify the metal chloride.
TiCl 4 The component of the mixed gas is mainly TiCl 4 （g）、CO、CO 2 、N 2 HCl, etc. The TiCl entering the atomizer needs to be strictly controlled in production 4 To ensure that the tail gas heat will TiCl 4 Slurry and coarse TiCl 4 In (1) TiCl 4 (l) All vaporizing without TiCl 4 (l) And enters a subsequent dust collector.
TiCl as described above 4 (l) All vaporization can be achieved by atomizer outlet temperature, dust collector inlet temperature (on the gas line to the condenser, same below), dust collector outlet temperature and TiCl 4 (l) The flow linkage is realized, and more preferably, the outlet temperature of the dust collector and coarse TiCl are adopted 4 (l) Flow rate interlock, tiCl 4 The mud flow rate is set to a fixed value.
The control range of the outlet temperature of the dust collector is 140 to 260 o C, the preferable range is 145 to 220 o C, the more preferable range is 150 to 180 o C。
TiCl as described above 4 The slurry flow rate is compared with the total TiCl entering the atomizer 4 (l) In terms of flow, the ratio is very low, tiCl 4 The flow rate of the slurry is based on the total TiCl 4 (l) The flow rate ratio (mass ratio or volume ratio) is less than 10%, preferably 4 to 7%.
S5, after cooling in the step S4, the mixed gas containing the double salts in the step S2 enters a dust collector, so that most of solids (dust collecting slag) are separated from the gas, and the mixed gas after gas-solid separation is subjected to a condensation process to collect TiCl 4 。
S6, adding water and 10-15wt% of dilute hydrochloric acid into the dust-collecting slag separated in the S5 in a pulping device, wherein the volume ratio of the water to the dilute hydrochloric acid is 1-2. The solid content of the slurry mixture is less than or equal to 45wt%, and more preferably 35 to 40wt%.
And S7, carrying out solid-liquid separation on the slag slurry mixture prepared in the S6 in a solid-liquid separation device, and carrying out further treatment on the filtrate in a downstream process. The solid-liquid separation device adopts a centrifugal machine, a plate-and-frame filter press or a rotary drum filter, preferably a plate-and-frame press.
And S8, drying the solid separated in the S7 in a drying device. The drying device is selected from a small rotary kiln, a vibration fluidized bed or a microwave dryer, preferably a microwave dryer.
S9, returning the dust-collecting slag dried in the step S8 as a recovered furnace charge to a molten salt chlorination section of the compound chlorination furnace, and further recovering the furnace charge. The moisture content of the dried material is less than 1wt%, preferably less than 0.5wt%, most preferably less than 0.3wt%.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Referring to FIG. 3, the specific steps of the titanium tetrachloride complex chlorination process are
(1) Mixing the high titanium slag and the calcined petroleum coke from the storage bin by a mixing screw, and adding the mixture into a pneumatic conveying device 11, wherein the mass ratio of the high titanium slag to the calcined petroleum coke is 3.
(2) Passing N through the mixing feeder 11 2 The mixture is injected into the boiling chlorination section of the composite chlorination furnace 12, and the mixture can be added into the molten salt chlorination section through a screw at the initial stage of the start-up.
(3) During operation, the bottom discharge charge discharging device 13 is opened periodically or according to the analysis and test result, and N is passed 2 And (3) spraying and blowing the bottom grate furnace charge into a molten salt chlorination section of the composite chlorination furnace.
(4) Returned Cl from the Oxidation Process 2 Enters the molten salt chlorination section of the compound chlorination furnace 12 below the molten salt liquid level and reacts with the high titanium slag to produce TiCl under the reduction action of calcined petroleum coke 4 While returning Cl 2 In-band TiO 2 Is intercepted by the molten salt to obtainThe adding amount of high titanium slag in the molten salt chlorination stage is controlled to ensure that Cl 2 More than two times in excess.
(5) After a period of reaction and enrichment, the molten salt components in the molten salt chlorination section are changed, so that the molten salt in the molten salt chlorination section is discharged periodically, solid NaCl is supplemented into the molten salt, and the molten salt components are controlled within a certain range.
(6) Excess Cl in the molten salt chlorination stage 2 TiCl formed by the reaction 4 The molten salt mixed gas and the like enter a boiling chlorination section of the composite chlorination furnace for further reaction to prepare TiCl 4 。
(7) The mixed gas after the boiling chlorination section reaction is mixed with TiCl 4 Mainly contains N 2 、CO 2 CO, HCl, solid dust, metal chloride and the like enter the atomizer 14 and are mixed with the TiCl atomized by the atomizer 14 4 Slurry and coarse TiCl 4 Directly contacting and mixing to obtain liquid TiCl 4 Evaporating to solidify the high-boiling metal chlorides and, in this process stage, fixing the TiCl 4 The flow rate of the slurry is controlled by the outlet temperature of the dust collector 15 to control coarse TiCl 4 The amount of the additive (c) is set at 140 to 260 ℃ based on the temperature at the outlet of the dust collector 15 o In the range of C, tiCl entering the dust collector 15 is ensured 4 All in the gaseous state.
(8) The mixed gas from the atomizer 14 enters a dust collector 15 for gas-solid separation, the dust collector 15 adopts a cyclone dust collector, 99% of solid impurities are separated from the mixed gas, and the gas is condensed for further treatment.
(9) The solid separated from the dust collector 15 is discharged through a discharge valve into a stirring tank 16 filled with dilute hydrochloric acid and water in advance, and is stirred to prepare a slag-slurry mixture, and when the solid content reaches 40wt%, the solid-liquid mixture is discharged to a solid-liquid separation device 17.
(10) The solid-liquid separation device 17 adopts a plate-and-frame filter press, the filter cake is subjected to alkali washing and water washing in the filter pressing process, when the conductivity of the filtrate is less than 10mS, the washing end point is the filtrate obtained by filter pressing, the filtrate obtained by filter pressing is sent to a downstream process, and the filter cake is mainly unreacted TiO 2 And C, sent to drying.
(11) The filter cake discharged from the filter press is sent to a drying device 18 through a belt conveyor, the drying device 18 adopts a rotary kiln for drying, and indexes such as speed, temperature and the like of the rotary kiln are controlled, so that the water content of the dried material is less than 0.5wt%.
(12) The dried materials are called as recovery furnace materials, are conveyed to a recovery furnace bin in front of the composite chlorination furnace through a pipe belt conveyor, and are further fed to a molten salt chlorination section of the chlorination furnace through a spiral feeder to realize recovery.
Finally, it is noted that: the above-mentioned list is only the preferred embodiment of the present invention, and naturally those skilled in the art can make modifications and variations to the present invention, which should be considered as the protection scope of the present invention provided they are within the scope of the claims of the present invention and their equivalents.
Claims (10)
1. The composite chlorination preparation method of titanium tetrachloride is characterized by comprising the following steps:
s1, mixing a titanium-rich material with high calcium and magnesium with a reducing agent, and adding the mixture into an upper boiling chlorination section and a lower molten salt chlorination section of a composite chlorination furnace respectively; adding molten NaCl into the molten salt chlorination section in advance, and introducing chlorine into the molten salt chlorination section of the composite chlorination furnace to perform chlorination reaction;
s2, allowing the mixed gas after the reaction in the molten salt chlorination section to enter a boiling chlorination section through a gas distributor of the composite chlorination furnace to participate in chlorination reaction;
in the molten salt chlorination stage, excessive chlorine and titanium-rich material are subjected to chlorination reaction to generate TiCl 4 And metal chloride, and simultaneously volatilizing in the molten salt chlorination section and reacting the entrained molten salt with the metal chloride to generate double salt;
s3, along with the proceeding of the boiling chlorination stage reaction, the calcium and magnesium impurities in the titanium-rich material generate CaCl in the chlorination reaction 2 、MgCl 2 Enriching in the furnace charge of the boiling chlorination section, and periodically adding CaCl 2 、MgCl 2 Feeding the mixture and the unreacted mixture into a molten salt chlorination section to participate in the reaction of the molten salt chlorination section;
TiCl generated in boiling section in S4 and S2 4 The mixed gas is discharged from the top of the composite chlorination furnace and is mixed with the atomized TiCl in the atomizer 4 Slurry and coarse TiCl 4 The mixture is directly contacted with TiCl 4 Cooling the mixed gas to solidify the metal chloride;
s5, after the mixed gas is cooled in the step S4, the mixed gas enters a dust collector to separate solid dust collecting slag from the gas, and the mixed gas after gas-solid separation is subjected to condensation process to collect TiCl 4 ；
S6, adding water and dilute hydrochloric acid into the dust-collecting slag separated in the S5 in a pulping device, and stirring to prepare a slag-slurry mixture;
s7, carrying out solid-liquid separation on the slag-slurry mixture in a solid-liquid separation device, further treating the filtrate in a downstream process, and drying the separated solid in a drying device;
s8, taking the dried dust-collecting slag as a recovered furnace charge to return to a molten salt chlorination section of the composite chlorination furnace, and further recovering the furnace charge.
2. The complex chlorination preparation method of titanium tetrachloride according to claim 1, wherein the titanium-rich material is TiO 2 Acid-soluble titanium slag or TiO with the content of 74-75wt% 2 High titanium slag with content more than 85 wt%; the titanium-rich material with high calcium and magnesium content means that the sum of the contents of CaO and MgO is more than 2.5 percent by weight.
3. The complex chlorination preparation method of titanium tetrachloride according to claim 1, wherein the reducing agent is any one or more of charcoal, petroleum coke, and metallurgical coke.
4. The complex chlorination preparation method of titanium tetrachloride according to claim 1, wherein the mixture is composed of 70 to 80wt% of high calcium magnesium rich titanium material and 20 to 30wt% of reducing agent.
5. The complex chlorination preparation method of titanium tetrachloride according to claim 1, wherein the chlorine gas is oxidation returned chlorine gas and/or newly added chlorine gas, wherein the oxidation returned chlorine gas is introduced into the molten salt chlorination section of the complex chlorination furnace from below the molten salt liquid level; newly added chlorine is introduced into the molten salt chlorination section from the position above the liquid level of the molten salt and enters the boiling chlorination section through the gas distributor.
6. The complex chlorination preparation method of titanium tetrachloride according to claim 1, wherein the molten salt volatilized and entrained in S2 is NaCl and AlCl 3 、MnCl 2 、FeCl 2 The generated double salt, wherein NaCl and AlCl 3 To generate double salt NaAlCl 4 ，NaAlCl 4 The separation in a dust collector can reduce the blockage of the subsequent condensation process.
7. The complex chlorination preparation method of titanium tetrachloride according to claim 1, wherein TiCl is used as S4 4 The composition of the mixed gas comprises gas TiCl 4 、CO、CO 2 、N 2 HCl, controlling TiCl entering the atomizer 4 The amount of the mixed gas ensures that the tail gas heat can mix TiCl 4 Slurry and coarse TiCl 4 In a liquid TiCl state 4 All are vaporized.
8. The complex chlorination preparation method of titanium tetrachloride according to claim 7, wherein the liquid TiCl is 4 All vaporization is carried out by the outlet temperature of the atomizer, the inlet temperature of the dust collector, the outlet temperature of the dust collector and liquid TiCl 4 And realizing flow linkage.
9. The complex chlorination preparation method of titanium tetrachloride according to claim 8, wherein the outlet temperature of the dust collector is controlled within a range of 140 to 260 ℃, and TiCl is used as the material 4 The flow rate of the slurry is compared with the total liquid TiCl entering the atomizer 4 The volume ratio or the mass ratio of the flow rate is below 10%.
10. The complex chlorination preparation method of titanium tetrachloride according to claim 1, wherein the solid content of the slurry mixture in S6 is less than or equal to 45wt%, and the water content of the dried material in S8 is less than 1wt%.
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| CN115924964A (en) * | 2022-11-24 | 2023-04-07 | 云南国钛金属股份有限公司 | Titanium tetrachloride refining system for recovering waste heat of preheater |
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| FR1120230A (en) * | 1955-01-20 | 1956-07-03 | Thann Fab Prod Chem | Improvements in the preparation of titanium tetrachloride |
| FR1284324A (en) * | 1961-03-20 | 1962-02-09 | Gas distributor | |
| DE2431597A1 (en) * | 1974-07-02 | 1976-01-22 | Werner Fuchs | Top cover bottom poured ingot moulds - consists of hemispherical ceramic shell which reduces piping in steel ingots |
| RU2136772C1 (en) * | 1998-10-12 | 1999-09-10 | Государственный научный центр РФ Государственный научно-исследовательский и проектный институт редкометаллической промышленности "Гиредмет" | Method of reprocessing of titanium slags |
| JP5897488B2 (en) * | 2013-03-19 | 2016-03-30 | 東邦チタニウム株式会社 | Method for producing titanium tetrachloride |
| CN103818951B (en) * | 2014-02-27 | 2015-04-08 | 重庆大学 | Boiling chlorination furnace adapting to fine-graded titanium-rich material |
| CN204952849U (en) * | 2015-09-24 | 2016-01-13 | 中国科学院上海有机化学研究所 | Air distributor reaches bubbling reactor including it |
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| CN212504027U (en) * | 2020-07-21 | 2021-02-09 | 青海北辰科技有限公司 | Device for preparing titanium tetrachloride |
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