CN114426304B - Method for extracting titanium from titanium carbide slag by fluidization low-temperature chlorination - Google Patents
Method for extracting titanium from titanium carbide slag by fluidization low-temperature chlorination Download PDFInfo
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Abstract
The invention discloses a method for extracting titanium from titanium carbide slag by fluidization low-temperature chlorination. The method mainly comprises the working procedures of briquetting, solidification, crushing and grading, fluidization low-temperature chlorination, cooling and leaching of chlorinated flue gas and cooling of chlorinated slag of titanium carbide slag. The ground titanium carbide slag is subjected to briquetting, solidification, crushing and classification to obtain powder raw materials with moderate grain size and good fluidization performance, so that the problems that coarse powder is coated with titanium carbide/carbon to be oxidized difficultly to be chlorinated and fine powder is poor in fluidization performance are solved, and excessive heat generated by the synergistic balance chlorination reaction of the coarse titanium tetrachloride generated by cooling and leaching of returned chlorinated flue gas and the cooled chlorinated slag is utilized to effectively avoid bonding lost flow caused by material heating, so that stable fluidization low-temperature chlorination and efficient extraction of titanium are realized. The invention has simple process, can effectively overcome the problems of low chlorination rate, poor fluidization performance, temperature rise and the like caused by exothermic reaction in the reactor, and has good applicability and application prospect for the high-efficiency utilization of low-grade titanium resources such as vanadium titano-magnetite and the like.
Description
Technical Field
The invention relates to the fields of chemical industry and metallurgy, in particular to a method for extracting titanium by fluidizing titanium carbide slag and chloridizing at low temperature.
Background
Titanium tetrachloride is an intermediate product in the production process of titanium and its compounds, and is an important raw material for the development of titanium industry. The titanium tetrachloride can be used for producing high-end titanium dioxide and sponge titanium, and further producing titanium, titanium alloy and the like. With the rapid development of the titanium industry in recent years, the demand for titanium raw materials is increasingly expanding, and although China belongs to the large country of titanium resources, the titanium resource reserves account for 40 percent of the total amount of titanium worldwide, the natural rutile and the artificial rutile are deficient, and the titanium concentrate can only meet the demand of titanium white production. However, the vanadium titano-magnetite with rich reserves is smelted and recycled to have higher titanium content of iron (and vanadium), and the titanium-rich slag is obtained by separating titanium-containing blast furnace slag generated by blast furnace smelting, molten titanium slag generated by prereduction-electric furnace melting or prereduction-grinding, and titanium oxide can be converted into titanium carbide or titanium oxycarbide which is favorable for rapid low-temperature chlorination after high-temperature carbonization treatment, so that comprehensive recycling of titanium is realized. Therefore, the titanium carbide slag is used as a raw material, and the titanium tetrachloride is produced through fluidization chlorination, so that the problem of high-quality utilization of the part of low-grade titanium resources can be solved, and the problem of deficient raw materials of natural rutile and artificial rutile can be partially compensated.
For this reason, a process technology for preparing titanium tetrachloride by fluidizing and low-temperature chlorination of titanium carbide slag has been developed. Chinese patent application No. cn2015199846. X uses ultra-fine grain grade water quenched titanium carbide fluidization chlorination to prepare titanium tetrachloride. Because superfine grain grade carbide slag can not be fluidized normally, the patent technology mainly adopts raw materials with grain diameter not smaller than 200 meshes to enter a fluidized bed reactor, and meanwhile, 80-140 meshes of quartz sand is mixed with the raw materials according to the mass ratio of 1:1, and the technical means adopted by the technology can solve the fluidization problem of the raw materials, but also has the following two problems: (1) a portion of titanium carbide or titanium oxycarbide is difficult to be chlorinated. Since the titanium carbide slag or the titanium oxycarbide is obtained by treating a titanium-containing raw material at a high temperature, a part of the titanium carbide or the titanium oxycarbide is wrapped in a silicate phase, and therefore, when a raw material with a coarse particle diameter is adopted, the wrapped titanium carbide/titanium oxycarbide phase is difficult to be chlorinated, and the chlorination rate of the raw material is reduced. In addition, the portion of the fine particle size material smaller than 200 mesh is not utilized. A similar problem exists with chinese patent application CN 201711115507.1. (2) The throughput per unit time is significantly reduced and the amount of residue is significantly increased. As quartz sand with the same quality as the raw materials is added, the treatment capacity of titanium carbide slag in unit time is reduced by one time, thereby reducing the production efficiency. In addition, the difference between the particle sizes of the quartz sand and the reaction residue is not large, and the quartz sand and the reaction residue are difficult to separate and recycle, so that the solid waste amount is increased, and the environment protection is not facilitated. The titanium carbide chlorination process is an exothermic process, and if no measures are taken to control the temperature, the temperature in the reactor will rise significantly, and if the melting point of the calcium and magnesium chlorides is reached, the risk of lost flow will result. Chinese patent CN200810304181.1 controls the temperature in the fluidized bed reactor by taking measures of partially cooling the chlorinated residues back to the chlorination reactor, or discharging part of the reaction residues into an external heat collector for cyclic heat extraction. It can be seen from all the examples cited in the patent art that the amount of recycle to cool the chlorinated residues is equal to the amount of feed to the reactor, which means that the flexibility of temperature regulation in the reactor is poor. With regard to the way of discharging part of the residue, it is also possible to discharge part of the unreacted material out of the reaction system at the same time. Therefore, the resource waste and the low chlorination rate can be caused, and the unreacted chlorine gas can also enter the tail gas treatment system. Chinese patent CN201410165805.1 uses titanium tetrachloride liquid as a heat transfer medium to be sprayed into a fluidized bed reactor. The titanium tetrachloride is independently used as a heat transfer medium, so that the circulation amount is large, local supercooling is easy to cause, the reaction is unfavorable, and great pressure is brought to the cooling of the back-end chlorination flue gas and the tail gas treatment.
In summary, although the prior art can solve the problems of lost flow and exothermic temperature rise of reaction, the problems of lower raw material utilization rate and chlorination rate, higher solid waste discharge, large heat transfer medium circulation and the like are brought. Therefore, a technical route which is more suitable for the material characteristics of the titanium carbide slag is developed through technological innovation, so that the problems of fluidization performance and temperature rise in a reactor are solved, raw materials can be fully utilized, the chlorination rate is high, the high-quality utilization of the titanium carbide slag is achieved, and the purposes of energy conservation and emission reduction are achieved.
Disclosure of Invention
Aiming at the problems of low raw material utilization rate and chlorination rate, high solid waste discharge, large heat transfer medium circulation amount and the like in the conventional titanium carbide slag fluidization low-temperature chlorination titanium tetrachloride preparation technology, the invention provides a method for extracting titanium by fluidization low-temperature chlorination of titanium carbide slag. The invention adopts the low-temperature chlorination technology of raw material particle size reconstruction and cooperative heat removal, solves the problems that fine particle size is difficult to fluidize and coarse particle size is difficult to be chlorinated through the raw material particle size reconstruction, can fully utilize titanium carbide slag raw materials for extracting titanium, and can obviously improve the chlorination rate of titanium. The partially cooled chlorous slag and the cooled silicon tetrachloride are recycled back to the fluidized bed reactor for cooperative heat removal and recycling, so that the temperature rise caused by strong heat release can be effectively inhibited, and the solid waste discharge amount and the recycling amount of a heat removal medium are obviously reduced.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for extracting titanium from titanium carbide slag by fluidization low-temperature chlorination, which comprises the following steps:
the method comprises a briquetting-solidifying process 1, a crushing-classifying process 2, a fluidization low-temperature chlorination process 3, a cooling leaching process 4 and a cooling process 5, and specifically comprises the following steps of:
1) Feeding the ground titanium carbide slag raw material into a briquetting-curing process 1, adding a binder and a proper amount of water, mixing with the fine powder returned from the crushing-classifying process 2, briquetting, and drying and curing to obtain a cured briquette raw material;
2) Feeding the solidified briquette raw material obtained in the briquetting-solidifying step 1 into a crushing-classifying step 2, crushing the solidified briquette raw material by adopting mechanical crushing equipment, classifying the obtained powder to obtain three parts of titanium carbide slag raw material powder of coarse powder, moderate powder and fine powder, wherein the coarse powder is circularly returned to the crushing treatment, and the fine powder is returned to the briquetting-solidifying step 1;
3) The moderate powder titanium carbide slag raw material obtained in the crushing-classifying step 2 is sent into a fluidization low-temperature chlorination step 3), is continuously sent into a fluidization low-temperature chlorination reactor through a feed bin and a feeder to react with the continuously-introduced chlorine raw material, so that titanium carbide or titanium oxycarbide in the raw material is chlorinated to generate gaseous titanium tetrachloride, and meanwhile, the crude titanium tetrachloride obtained in the cooling leaching step 4 and the cooling chlorination slag part obtained in the cooling step 5 are returned into the fluidization low-temperature chlorination reactor to be used for realizing stable fluidization low-temperature chlorination by synergically balancing excessive heat generated by the chlorination reaction, and the generated chlorination slag is continuously discharged after dust removal;
4) Delivering the chloridized flue gas discharged from the fluidization low-temperature chloridizing process 3 into a cooling leaching process 4, delivering the residual tail gas after cooling leaching into water washing, alkali washing and other environment-friendly treatments to reach standards, and then evacuating to obtain crude titanium tetrachloride liquid, wherein one part of the crude titanium tetrachloride liquid is circulated and returned to the fluidization low-temperature chloridizing reactor of the fluidization low-temperature chloridizing process 3, and the other part of the crude titanium tetrachloride liquid is delivered to a subsequent refining process for purifying and producing titanium products;
5) And (3) conveying the chloride slag discharged from the fluidization low-temperature chlorination process 3 into a cooling process 5, and recycling part of cooled chloride slag obtained by heat exchange and cooling back to the fluidization low-temperature chlorination reactor of the fluidization low-temperature chlorination process 3, wherein the other part is comprehensively utilized to realize harmless and recycling of the chloride slag.
Preferably, the titanium carbide slag raw materials are as follows:
separating one or more of titanium-containing blast furnace slag generated by the blast furnace smelting of vanadium titano-magnetite, molten titanium slag generated by the pre-reduction-electric furnace molten separation and pre-reduction-grinding to obtain titanium-rich slag, and performing high-temperature carbonization-cooling grinding to obtain titanium carbide slag; the mass content of titanium carbide or titanium oxycarbide in the titanium carbide slag raw material is 10-40%.
Preferably, the binder in the briquetting-curing process 1 is one or a combination of clay, cement, water glass and slaked lime, the addition amount of the binder and water is respectively 0.5-8% and 5-25% of the mass of the titanium carbide slag raw material, the briquetting process pressure is 5-30 MPa, the equivalent diameter of the briquette is 5-50 cm, the drying and curing temperature is 0-300 ℃ and the time is 2-500 h;
preferably, the classification in the crushing-classifying process 2 adopts screening or air separation, the upper limit of the granularity of the moderate powder is 200-1000 μm, the lower limit of the granularity is 50-110 μm, the coarse powder refers to powder with the granularity larger than the upper limit of the granularity of the moderate powder, and the fine powder refers to powder with the granularity smaller than the lower limit of the granularity of the moderate powder.
Preferably, the low-temperature chlorination temperature in the fluidization low-temperature chlorination process 3 is 350-600 ℃, the average residence time of powder materials is 10-90 min, the volume fraction of chlorine in the chlorine raw material is 50-100%, and the number of adding ports of the crude titanium tetrachloride and the cooled chlorination slag returned to the fluidized bed reactor is 2-8, and the raw titanium tetrachloride and the cooled chlorination slag are symmetrically and uniformly distributed.
Preferably, the temperature of the crude titanium tetrachloride recycled to the chlorination reactor in the step 3 in the cooling leaching step 4 is 0-100 ℃, and the mass of the crude titanium tetrachloride is 10-200% of the titanium carbide slag raw material added into the chlorination reactor.
Preferably, in the cooling step 5, the temperature of the cooled chloride slag circularly returned to the chlorination reactor in the step 3 is 25-120 ℃, and the mass of the cooled chloride slag is 10-200% of that of the titanium carbide slag raw material added into the chlorination reactor.
Compared with the prior art, the low-temperature chlorination technology adopting the raw material particle size reconstruction-synergistic heat removal has the following outstanding advantages:
(1) Effectively solves the problem of current losing caused by existence of fine particle size. The original coarse grain diameter particles with the porous structure are formed by aggregation and combination of the raw materials with the fine grain diameter through particle diameter reconstruction, and become B-class particles which are easy to fluidize, so that the fluidization problem can be effectively solved.
(2) The utilization rate and the chlorination rate of the raw materials are obviously improved. Because of adopting the raw material particle size reconstruction technology, the raw material is completely refined into the raw material with superfine particle size, and the raw material with superfine particle size is changed into the raw material with coarse particle size which comprises a plurality of superfine particles and has a porous structure through means of briquetting, solidification, crushing, screening and the like. The raw material particle size reconstruction technology ensures that titanium carbide or titanium oxycarbide which is wrapped in a silicate phase in large particles is leaked outside, so that the contact area between reaction media is effectively increased, and the chlorination performance of the raw material is obviously improved; the fine particle size material contained in the material itself can also be utilized.
(3) The reaction process is strengthened, and the low-temperature rapid chlorination is realized. The particles with porous structures formed by the fine particles are formed after the particles are reconstituted, which is favorable for heat mass transfer-reaction between reaction media, so that the reaction process can be enhanced, and the rapid chlorination reaction under the low-temperature condition can be realized.
(4) Effectively solves the problem of large recycling amount of heat transfer medium in the prior art. The circulating use amount of a single medium can be obviously reduced by partially cooling the chloridized slag and cooling the titanium tetrachloride to serve as heat transfer mediums and cooperatively returning to the fluidized bed reactor in the fluidization low-temperature chloridizing process. If the reaction system needs to be maintained at 600 ℃, if the cooled chloride slag is used alone as a heat transfer medium, at least 1.5 times of the mass of the cooled chloride slag needs to be added, obviously, the processing capacity of the fluidized bed reactor to the raw materials can be obviously reduced, and the production efficiency and the productivity are reduced; the cooled titanium tetrachloride is used as a heat transfer medium alone, at least 1.5 times of the mass of the raw material is required to be added, and obviously, a large amount of titanium tetrachloride enters the reactor, so that the local temperature in the reactor is likely to be obviously reduced, and in addition, a large amount of titanium tetrachloride enters the reactor for heat transfer and then is discharged out of the reactor together with the chloridized flue gas, so that huge pressure is brought to the back-end cooling and environmental protection treatment.
Drawings
The accompanying drawings are included to provide a further illustration of the invention and are a part of the specification, and together with the description serve to explain the invention, and do not limit the invention.
FIG. 1 is a schematic flow chart of a method for extracting titanium by fluidization low-temperature chlorination of titanium carbide slag;
reference numerals: 1. the method comprises the following steps of briquetting-solidifying, 2, crushing-grading, 3, fluidization low-temperature chlorination, 4, cooling and leaching, 5 and cooling.
Detailed Description
Any feature disclosed in this specification may be replaced by alternative features serving the same or equivalent purpose, unless expressly stated otherwise. Each feature is one example only of a generic series of equivalent or similar features, unless expressly stated otherwise. The description is only intended to aid in the understanding of the invention and should not be taken as limiting the invention in any way.
The invention is described in further detail below with reference to the drawings and the detailed description.
Example 1
FIG. 1 is a schematic flow chart of a method for extracting titanium from titanium carbide slag by fluidization low-temperature chlorination. Referring to fig. 1, a method for extracting titanium from titanium carbide slag by fluidization low-temperature chlorination comprises the following steps:
the method comprises a briquetting-solidifying process 1, a crushing-classifying process 2, a fluidization low-temperature chlorination process 3, a cooling leaching process 4 and a cooling process 5, and specifically comprises the following steps of:
1) Feeding the titanium carbide slag raw material which is ground into the average granularity of 5-50 mu m into a briquetting-curing process 1, adding a binder and a proper amount of water, mixing with the fine powder returned from the crushing-grading process, briquetting, and drying and curing to obtain a cured briquette raw material;
2) Feeding the solidified briquette raw material obtained in the briquetting-solidifying step 1 into a crushing-classifying step 2, crushing the solidified briquette raw material by adopting mechanical crushing equipment, classifying the obtained powder to obtain three parts of powder of coarse powder, moderate powder and fine powder, wherein the coarse powder is circularly returned to the crushing treatment, and the fine powder is returned to the briquetting-solidifying step 1;
3) The moderate powder titanium carbide slag raw material obtained in the crushing-classifying step 2 is sent into a fluidization low-temperature chlorination step 3, is continuously sent into a fluidization low-temperature chlorination reactor through a feed bin and a feeder to react with continuously introduced chlorine gas, so that titanium carbide or titanium oxycarbide in the raw material is chlorinated to generate gaseous titanium tetrachloride, and meanwhile, the crude titanium tetrachloride obtained in the cooling leaching step 4 and the cooled chlorinated slag part obtained in the cooling step 5 are returned into the chlorination reactor to be used for realizing stable fluidization low-temperature chlorination in cooperation with excessive heat generated by balanced chlorination reaction, and the generated chlorinated flue gas is continuously discharged after dust removal and the generated chlorinated slag is also continuously discharged;
4) Delivering the chloridized flue gas discharged from the fluidization low-temperature chloridizing process 3 into a cooling leaching process 4, delivering the residual tail gas after cooling leaching into water washing, alkali washing and other environment-friendly treatments to reach standards, and then evacuating to obtain crude titanium tetrachloride liquid, wherein part of the crude titanium tetrachloride liquid is circulated and returned to the chloridizing reactor of the fluidization low-temperature chloridizing process 3, and the rest of the crude titanium tetrachloride liquid is delivered to a subsequent refining process for purifying and producing titanium products;
5) Delivering the chloride slag discharged from the fluidization low-temperature chlorination process 3 into a cooling process 5, and partially recycling the cooled chloride slag obtained by heat exchange and cooling back to the chlorination reactor of the fluidization low-temperature chlorination process 3, wherein the rest is comprehensively utilized to realize harmless and recycling of the chloride slag;
example 2
This example uses a method for extracting titanium from titanium carbide slag by fluidization low-temperature chlorination as described in example 1. The method comprises the steps of taking titanium-containing blast furnace slag generated by smelting vanadium titano-magnetite in a blast furnace as a raw material, wherein the mass content of titanium carbide is 10%, grinding the titanium carbide to an average particle size of 50 mu m, then sending the crushed titanium to a briquetting-curing process 1, adding clay with the mass of 0.5% of the raw material as a binder, adding water with the mass of 5% of the raw material, stirring and mixing uniformly, pressing the mixture into pellets with the mass of 10cm under the pressure of 5MPa, and drying the pellets at 300 ℃ for 2 hours; the dried pellets are sent to a crushing-classifying process 2, moderate powder raw material powder of 50-200 mu m is obtained, coarse fraction raw materials of more than 200 mu m and fine fraction raw materials of less than 50 mu m are respectively returned to the crushing-classifying process 2 and the briquetting-curing process 1; the obtained moderate powder raw material powder is sent into a fluidization low-temperature chlorination process 3, raw material gas with the chlorine gas volume content of 50% is introduced as fluidization gas, the reaction is carried out for 90min at 350 ℃, meanwhile, crude titanium tetrachloride at 50 ℃ obtained in a cooling leaching process 4 and cooled chlorination slag at 25 ℃ obtained in a cooling process 5 are respectively returned into a chlorination reactor according to 100% and 10% of the mass of the raw material entering the fluidized bed reactor, so that stable fluidization low-temperature chlorination is realized by the excessive heat generated by the synergistic balance chlorination reaction, and the quantity of the adding ports is 4 and the adding ports are symmetrically and uniformly distributed; and (3) conveying chloridized flue gas generated by chloridizing into a cooling leaching process 4 after dust removal, carrying out environmental protection treatment such as water washing, alkali washing and the like on the residual tail gas after cooling leaching, emptying, recycling the obtained 50 ℃ crude titanium tetrachloride liquid part into a chloridizing reactor of the process 3, conveying the rest to a subsequent refining process for purifying and producing titanium products, conveying the discharged chloridized slag into a cooling process 5, recycling the obtained 25 ℃ cooled chloridized slag part into the chloridizing reactor of the process 3 through heat exchange cooling, and comprehensively utilizing the rest to realize innocuity and recycling of chloridized slag. Operating under the condition, the chlorination rate of titanium in the titanium carbide slag can reach 94.74%.
Example 3
This example uses a method for extracting titanium from titanium carbide slag by fluidization low-temperature chlorination as described in example 1. The method comprises the steps of taking carbide slag obtained by high-temperature carbonization of titanium-rich materials obtained by pre-reduction-grinding separation as a raw material, grinding the carbide slag to have the mass content of 40%, enabling the titanium carbide slag to have the average particle size of 25 mu m, then sending into a briquetting-curing process 1, adding water glass with the mass of 8% of the raw material as a binder, adding water with the mass of 10% of the raw material, stirring and mixing uniformly, pressing the mixture into pellets with the mass of 25cm under the pressure of 30MPa, and drying the pellets at the temperature of 100 ℃ for 2 hours; the dried pellets are sent to a crushing-classifying process 2, so as to obtain moderate powder raw material powder of 110-500 mu m, coarse fraction raw material of more than 500 mu m and fine fraction raw material of less than 110 mu m, and the coarse fraction raw material and the fine fraction raw material are respectively returned to the crushing-classifying process 2 and the briquetting-curing process 1; feeding the obtained moderate powder raw material powder into a fluidization low-temperature chlorination process 3, introducing raw material gas with the chlorine gas volume content of 100% as fluidization gas, reacting for 45min at 550 ℃, and simultaneously returning 200% and 100% of the mass of the raw titanium tetrachloride at 0 ℃ obtained in a cooling leaching process 4 and 120 ℃ cooling chlorination slag obtained in a cooling process 5 into a chlorination reactor respectively according to the mass of the raw material entering the fluidized bed reactor, wherein the raw material gas is used for realizing stable fluidization low-temperature chlorination by the excessive heat generated by the synergistic balance chlorination reaction, and the number of the adding ports is 6 and the raw material gas is symmetrically and uniformly distributed; and (3) conveying chloridized flue gas generated by chloridizing into a cooling leaching process 4 after dust removal, carrying out environmental protection treatment such as water washing, alkali washing and the like on the residual tail gas after cooling leaching, emptying, recycling the obtained 0 ℃ crude titanium tetrachloride liquid part into a chloridizing reactor of the process 3, conveying the rest to a subsequent refining process for purifying and producing titanium products, conveying the discharged chloridized slag into a cooling process 5, recycling the 120 ℃ cooled chloridized slag part obtained by heat exchange cooling into the chloridizing reactor of the process 3, and comprehensively utilizing the rest to realize innocuity and recycling of chloridized slag. Operating under the condition, the chlorination rate of titanium in the titanium carbide slag can reach 94.80 percent.
Example 4
This example uses a method for extracting titanium from titanium carbide slag by fluidization low-temperature chlorination as described in example 1. The method comprises the steps of taking electric furnace molten titanium slag as a raw material, grinding the titanium slag with the mass content of 14% to an average particle size of 5 mu m, then sending into a briquetting-curing process 1, adding cement with the mass of 5% of the raw material as a binder, adding water with the mass of 15% of the raw material, stirring and mixing uniformly, pressing into pellets with the mass of 50cm under the pressure of 25MPa, and drying the pellets at the temperature of 0 ℃ for 500 hours; the dried pellets are sent to a crushing-classifying process 2, moderate powder raw material powder of 500-1100 mu m is obtained, coarse fraction raw materials larger than 1100 mu m and fine fraction raw materials smaller than 500 mu m are respectively returned to the crushing-classifying process 2 and the briquetting-curing process 1; feeding the obtained raw material powder into a fluidization low-temperature chlorination process 3, introducing raw material gas with the chlorine gas volume content of 75% as fluidization gas, reacting for 60min at 450 ℃, and simultaneously returning the 100 ℃ crude titanium tetrachloride obtained in the cooling leaching process 4 and the 25 ℃ cooling chlorination slag obtained in the cooling process 5 into a chlorination reactor according to 150% and 50% of the mass of the raw material entering the fluidized bed reactor respectively, wherein the raw material powder is used for realizing stable fluidization low-temperature chlorination by synergically balancing excessive heat generated by the chlorination reaction, and the number of the adding ports is 8 and the raw material powder is symmetrically and uniformly distributed; and (3) conveying chloridized flue gas generated by chloridizing into a cooling leaching process 4 after dust removal, carrying out environmental protection treatment such as water washing, alkali washing and the like on the residual tail gas after cooling leaching, emptying, recycling the obtained 100 ℃ crude titanium tetrachloride liquid part into a chloridizing reactor of the process 3, conveying the rest to a subsequent refining process for purifying and producing titanium products, conveying the discharged chloridized slag into a cooling process 5, recycling the obtained 25 ℃ cooled chloridized slag part into the chloridizing reactor of the process 3 through heat exchange cooling, and comprehensively utilizing the rest to realize innocuity and recycling of chloridized slag. Operating under the condition, the chlorination rate of titanium in the titanium carbide slag can reach 91.39 percent.
Example 5
This example uses a method for extracting titanium from titanium carbide slag by fluidization low-temperature chlorination as described in example 1. The method comprises the steps of taking titanium-containing blast furnace slag generated by smelting vanadium titano-magnetite in a blast furnace as a raw material, grinding the titanium carbide to have the mass content of 25%, enabling the average particle diameter to be 40 mu m, then sending the crushed titanium carbide into a briquetting-solidifying process 1, adding slaked lime accounting for 8% of the mass of the raw material as a binder, adding water accounting for 25% of the mass of the raw material, stirring and mixing uniformly, pressing the mixture into pellets of 10cm under the pressure of 15MPa, and drying the pellets at 105 ℃ for 10 hours; the dried pellets are sent to a crushing-classifying process 2, moderate powder raw material powder of 100-300 mu m is obtained, coarse fraction raw materials of more than 300 mu m and fine fraction raw materials of less than 100 mu m are respectively returned to the crushing-classifying process 2 and the briquetting-curing process 1; feeding the obtained raw material powder into a fluidization low-temperature chlorination process 3, introducing raw material gas with the chlorine gas volume content of 80% as fluidization gas, reacting for 60min at 500 ℃, and simultaneously returning the crude titanium tetrachloride at 10 ℃ obtained in a cooling leaching process 4 and the cooled chlorination slag at 50 ℃ obtained in a cooling process 5 into a chlorination reactor according to 100% and 40% of the mass of the raw material entering the fluidized bed reactor respectively, wherein the raw material powder is used for realizing stable fluidization low-temperature chlorination by synergically balancing excessive heat generated by the chlorination reaction, and the number of the adding ports is 8 and the raw material powder is symmetrically and uniformly distributed; and (3) conveying chloridized flue gas generated by chloridizing into a cooling leaching process 4 after dust removal, carrying out environmental protection treatment such as water washing, alkali washing and the like on the residual tail gas after cooling leaching, emptying, recycling the obtained 10 ℃ crude titanium tetrachloride liquid part into a chloridizing reactor of the process 3, conveying the rest to a subsequent refining process for purifying and producing titanium products, conveying the discharged chloridized slag into a cooling process 5, recycling the obtained 50 ℃ cooled chloridized slag part into the chloridizing reactor of the process 3 through heat exchange cooling, and comprehensively utilizing the rest to realize innocuity and recycling of chloridized slag. Operating under the condition, the chlorination rate of titanium in the titanium carbide slag can reach 94.80 percent.
The method can be realized by the upper and lower limit values of the interval and the interval value of the process parameters (such as temperature, time and the like), and the examples are not necessarily listed here.
The invention may be practiced without these specific details, using any knowledge known in the art.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and are not limiting. Although the present invention has been described in detail with reference to the embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention, which is intended to be covered by the appended claims.
Claims (5)
1. A method for extracting titanium from titanium carbide slag by fluidization low-temperature chlorination, which comprises the following steps: the method comprises a briquetting-solidifying process (1), a crushing-classifying process (2), a fluidization low-temperature chlorination process (3), a cooling leaching process (4) and a cooling process (5), and specifically comprises the following steps of:
1) Feeding the titanium carbide slag raw material which is ground into the average granularity of 5-50 mu m into a briquetting-curing process (1), adding a binder and water, mixing with the fine powder returned from the crushing-grading process (2), briquetting, and drying and curing to obtain a cured briquette raw material;
2) Feeding the solidified briquette raw material obtained in the briquette-solidifying step (1) into a crushing-classifying step (2), crushing, classifying the obtained powder to obtain three parts of titanium carbide slag raw material powder of coarse powder, moderate powder and fine powder, wherein the coarse powder is circularly returned to the crushing treatment, and the fine powder is returned to the briquette-solidifying step (1);
3) The moderate powder titanium carbide slag raw material obtained in the crushing-grading step (2) is sent into a fluidization low-temperature chlorination step (3), is continuously sent into a fluidization low-temperature chlorination reactor through a feed bin and a feeder to react with the continuously-introduced chlorine raw material, so that titanium carbide or titanium oxycarbide in the raw material is chlorinated to generate gaseous titanium tetrachloride, and meanwhile, the crude titanium tetrachloride obtained in the cooling leaching step (4) and the cooling chlorination slag part obtained in the cooling step (5) are returned into the fluidization low-temperature chlorination reactor to be used for realizing stable fluidization low-temperature chlorination by the excessive heat generated by the synergistic balance chlorination reaction, and the generated chlorination slag is continuously discharged after the chloridizing flue gas is dedusted;
4) Delivering the chloridized flue gas discharged from the fluidization low-temperature chloridizing process (3) into a cooling leaching process (4), carrying out environmental protection treatment on the residual tail gas after cooling leaching, and then evacuating, wherein one part of the obtained crude titanium tetrachloride liquid is circulated and returned to the fluidization low-temperature chloridizing reactor of the fluidization low-temperature chloridizing process (3), and the other part is delivered to a subsequent refining process for purifying and producing titanium products;
5) Delivering the chloride slag discharged from the fluidization low-temperature chlorination process (3) into a cooling process (5), and recycling part of cooled chloride slag obtained by heat exchange and cooling back to the fluidization low-temperature chlorination reactor of the fluidization low-temperature chlorination process (3), wherein the other part is comprehensively utilized to realize harmless and recycling of the chloride slag;
the titanium carbide slag raw material is obtained by the following method:
separating one or more of titanium-containing blast furnace slag generated by the blast furnace smelting of vanadium titano-magnetite, molten titanium slag generated by the pre-reduction-electric furnace molten separation and pre-reduction-grinding to obtain titanium-rich slag, and carrying out high-temperature carbonization-cooling grinding; the mass content of titanium carbide or titanium oxycarbide in the titanium carbide slag raw material is 10-40%;
the binder in the briquetting-curing process (1) is one or a combination of clay, cement, water glass and slaked lime, the addition amount of the binder and water is respectively 0.5-8% and 5-25% of the mass of the titanium carbide slag raw material, the briquetting process pressure is 5-30 MPa, the equivalent diameter of the briquette is 5-50 cm, the drying curing temperature is 0-300 ℃ and the time is 2-500 h.
2. The method for extracting titanium from titanium carbide slag by fluidization low-temperature chlorination according to claim 1, wherein the classification adopted in the crushing-classification step (2) is sieving or air separation, the upper limit of the granularity of the moderate powder is 200-1000 μm, the lower limit of the granularity is 50-110 μm, the coarse powder refers to powder with granularity larger than the upper limit of the moderate powder granularity, and the fine powder refers to powder with granularity smaller than the lower limit of the moderate powder granularity.
3. The method for extracting titanium from titanium carbide slag by fluidization low-temperature chlorination according to claim 1, wherein the low-temperature chlorination temperature in the fluidization low-temperature chlorination process (3) is 350-600 ℃, the average residence time of powder materials is 10-90 min, the volume fraction of chlorine in chlorine raw materials is 50% -100%, and the number of adding ports of crude titanium tetrachloride and cooling chlorination slag returned to the fluidized bed reactor is 2-8, and the raw materials are symmetrically and uniformly distributed.
4. The method for extracting titanium from titanium carbide slag by fluidization low-temperature chlorination according to claim 1, wherein the temperature of the crude titanium tetrachloride recycled back to the fluidization low-temperature chlorination process (3) in the cooling leaching process (4) is 0-100 ℃, and the mass of the crude titanium tetrachloride is 10-200% of the mass of the raw material added with the titanium carbide slag with moderate powder.
5. The method for extracting titanium from titanium carbide slag by fluidization low-temperature chlorination according to claim 1, wherein the temperature of the cooled chloride slag circularly returned to the fluidization low-temperature chlorination process (3) in the cooling process (5) is 25-120 ℃, and the mass of the cooled chloride slag is 10-200% of that of the titanium carbide slag raw material added with moderate powder.
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| CN1005629B (en) * | 1987-10-27 | 1989-11-01 | 冶金工业部攀枝花钢铁公司钢铁研究院 | Method for preparing titanium tetrachloride from titanium-containing blast furnace slag |
| CN101016167A (en) * | 2006-02-09 | 2007-08-15 | 朱作远 | Process of preparing high-purity TiCl4 by preheating chlorine gas low-temperature chlorination method |
| CN101164895B (en) * | 2007-10-08 | 2011-06-29 | 清华大学 | Chlorination method for producing titanium tetrachloride at low temperature |
| CN101337689B (en) * | 2008-08-26 | 2010-12-01 | 攀钢集团有限公司 | Method for producing titanium tetrachloride using low grade titan raw material |
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| CN107758730A (en) * | 2017-10-31 | 2018-03-06 | 攀钢集团攀枝花钢铁研究院有限公司 | Carbide slag low temperature chlorination stove material-heat-exchanging system and heat-exchanging process |
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