CN103723766A - Method for preparing titanium dioxide - Google Patents
Method for preparing titanium dioxide Download PDFInfo
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- CN103723766A CN103723766A CN201310661877.0A CN201310661877A CN103723766A CN 103723766 A CN103723766 A CN 103723766A CN 201310661877 A CN201310661877 A CN 201310661877A CN 103723766 A CN103723766 A CN 103723766A
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- preheating
- titanium tetrachloride
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Abstract
The invention relates to a method for preparing titanium dioxide, which comprises the following steps: (1) heat is supplied through combustion of dimethyl ether, and titanium tetrachloride is primarily preheated; (2) aluminum powder is enabled to react with chlorine to produce aluminum trichloride, so that a mixture containing aluminum trichloride and titanium tetrachloride is obtained, wherein heat produced during the reaction of aluminum powder and chlorine is used for secondarily preheating titanium tetrachloride; (3) heat is supplied through combustion of dimethyl ether, and oxygen is primarily preheated; (4) heat is supplied through combustion of methylbenzene, and the primarily preheated oxygen is secondarily preheated; (5) the mixture containing aluminum trichloride and titanium tetrachloride is mixed with the secondarily preheated oxygen, and the titanium tetrachloride and oxygen are enabled to be subjected to oxidizing reaction, so that an oxidizing reaction mixture containing titanium dioxide and chlorine is obtained; (6) gas-solid separation is performed on the oxidizing reaction mixture to obtain titanium dioxide and chlorine respectively. Titanium dioxide can be effectively prepared through the method.
Description
Technical field
The present invention relates to chemical field.More specifically, relate to a kind of method of preparing titanium dioxide.
Background technology
The method of producing at present titanium dioxide mainly contains sulfuric acid process and chlorination process.Due to the long flow path of sulfuric acid process, seriously polluted, poor product quality and be progressively chlorinated method replace.
CN 1066043 discloses a kind of processing method of preparing Rutile type Titanium Dioxide, it comprises 1), after evenly being mixed with refinery coke, titanium slag puts into chlorination furnace, pass into chlorine and carry out fluidizing chlorination at 800～900 ℃ of temperature, 2), the rough titanium tetrachloride obtaining after chlorination is carried out to separating-purifying to be removed, magnesium, iron, the impurity such as silicon and vanadium, obtain refining titanic chloride, 3), the refining titanic chloride liquid making is in vaporizer, be converted into gas phase, and be preheated to 450～800 ℃, 4), gas phase titanium tetrachloride and a small amount of compound modifying agent gas phase aluminum chloride are mixed into oxidized still, oxygen enters oxidized still through plasma generator heating, at 1300～1500 ℃ of temperature, be less than and in 0.1 second, carry out oxidizing reaction and generate solid phase titanium dioxide, 5), rapidly titanium dioxide pressed powder is shifted out to reaction zone and reaction heat is being removed rapidly, collect titanium dioxide generation chlorine and return to chlorination furnace, 6), the titanium dioxide granule powder of collection is beaten into liquid, through two-stage sorting, the fine particle titanium dioxide that is less than 1 micron carries out aftertreatment again, coarse particles grinds and then classification, 7), make used additives carry out coating aftertreatment in pH=7～8 at 50～70 ℃ of temperature, 8), by titanium dioxide slurries after aftertreatment, through twice filtration, charging is moisture is less than 45%, discharging is moisture is less than 1%, 9) dry at 120～160 ℃ of temperature, micronizing, product mean particle size accounts for 70% below 0.3 μ m.
But the means of preparing at present titanium dioxide still have much room for improvement.
Summary of the invention
The present invention is intended at least solve one of technical problem existing in prior art.For this reason, one object of the present invention is to propose a kind of method and system that can effectively prepare titanium dioxide.
In a first aspect of the present invention, a kind of method of preparing titanium dioxide slurry has been proposed, it comprises: (1) provides heat by burning dme, and titanium tetrachloride is carried out to the first preheating; (2) aluminium powder, chlorine and the described titanium tetrachloride through the first preheating are mixed, and make described aluminium powder and chlorine reaction generate aluminum chloride, to obtain the mixture that contains aluminum chloride and titanium tetrachloride, wherein, the heat that described aluminium powder and chlorine reaction produce is carried out the second preheating to described titanium tetrachloride; (3) by burning dme, provide heat, oxygen is carried out to the first preheating; (4) by burning toluene, provide heat, the described oxygen through the first preheating is carried out to the second preheating; (5) in oxidation reaction apparatus, the mixture that obtains containing aluminum chloride and titanium tetrachloride in step (2) is mixed with the oxygen through the second preheating obtaining in step (4), and make titanium tetrachloride and oxygen generation oxidizing reaction, wherein, in described oxidation reaction apparatus, add silicon-dioxide as removing scar sand, to obtain the oxidation mixtures that contains titanium dioxide and chlorine; And (6) carry out gas solid separation to described oxidation mixtures, to obtain respectively titanium dioxide and chlorine, wherein, described oxidation mixtures is carried out to gas solid separation and further comprise: utilize chuck cooling tube, described oxidation mixtures is carried out cooling; Utilize deep bed filter to carry out gas solid separation to described oxidation mixtures, to obtain respectively the gas tail gas that contains chlorine and comprise titanium dioxide and except the solid mixture of scar sand; Described solid mixture is joined in base-material pulping tank, by adding de-mineralized water to carry out slurrying in described base-material pulping tank; And obtained slurry is joined except in scar sand separating apparatus, to separate, obtain except scar sand and titanium dioxide slurry.Utilize the method for the present invention, can effectively prepare titanium dioxide slurry, and can avoid the titania producing on reactor wall, bond, forms scar layer, the method be a kind of efficiently, clean, the production technology of environmental protection.
According to embodiments of the invention, the temperature of oxidation mixtures is 1800 degrees Celsius, utilizes chuck cooling tube, and the temperature of described oxidation mixtures is cooled to 300 degrees Celsius.Thus, can fast a large amount of reaction heat be passed, thereby avoid titanium dioxide crystal to bond on reactor wall, and then develop into scar layer under high-temperature condition.
According to embodiments of the invention, by the described gas tail gas that contains chlorine for titaniferous ore is carried out to chloridized.Thus, realized the recycle of chlorine, not only can Jie Neng Jian Mao, reduce costs, can also reduce discharge, protection of the environment.
According to embodiments of the invention, the described gas tail gas that contains chlorine is discharged after alkali lye chilling and two-stage alkali liquid washing.Thus, can, when the emergency state, quickly and efficiently by the gas tail gas qualified discharge containing chlorine, reduce environmental pollution.
According to embodiments of the invention, what separation was obtained joins in described oxidation reaction apparatus except scar sand after washing, dry and classification.Thus, can will recycle except scar sand, thereby reduce the cost that generates titanium dioxide slurry.
According to embodiments of the invention, aforesaid method can also have following additional technical feature:
In one embodiment of the invention, through the temperature of the titanium tetrachloride of the first preheating for being not less than 270 degrees Celsius; Through the temperature of the titanium tetrachloride of the second preheating for being not less than 350 degrees Celsius; Through the temperature of the oxygen of the first preheating for being not less than 750 degrees Celsius; Through the temperature of the oxygen of the second preheating for being not less than 1500 degrees Celsius.Thus, can further improve pre-thermo-efficiency, thereby improve the efficiency of preparing titanium dioxide.
In one embodiment of the invention, in step (1) and step (3), described titanium tetrachloride is carried out the first preheating and oxygen is carried out to the first preheating, be indirect heating; In step (4), by toluene and the described oxygen mix through the first preheating, and burning is to by direct heating, carry out the second preheating to the described oxygen through the first preheating.Thus, can further improve pre-thermo-efficiency, thereby improve the efficiency of preparing titanium dioxide.
In one embodiment of the invention, in step (2), described aluminium powder and chlorine are that the ratio that is 1:1～1:5 according to mass ratio is mixed, so as described in contain aluminum chloride and titanium tetrachloride mixture in, the content of described aluminum chloride is 0.01%～0.1%.Thus, can make aluminium powder and chlorine react under optimal conditions of mixture ratios, the amount of the aluminum chloride generating is suitable, thereby be conducive to the generation of the titanium dioxide crystal with desired particle size, and then the production efficiency of raising titanium dioxide, and contriver finds, if the amount of aluminum chloride is too much or very few, will affect titanium dioxide quality.
In one embodiment of the invention, in step (4), the volume ratio of described toluene and the described oxygen through the first preheating be temperature according to actual needs and definite, along with the rising of required temperature, the addition of toluene increases gradually.Thus, can further improve pre-thermo-efficiency, thereby improve the efficiency of preparing titanium dioxide.
Accompanying drawing explanation
Above-mentioned and/or additional aspect of the present invention and advantage accompanying drawing below combination is understood becoming the description of embodiment obviously and easily, wherein:
Fig. 1 is the schematic flow sheet of preparing according to an embodiment of the invention the method for titanium dioxide;
Fig. 2 is the structural representation of preparing according to an embodiment of the invention the system of titanium dioxide;
Fig. 3 is the schematic flow sheet of the method for preparing titanium dioxide of another embodiment according to the present invention;
Fig. 4 is the schematic flow sheet of the method for preparing titanium dioxide of another embodiment according to the present invention;
Fig. 5 is the structural representation of the system of preparing titanium dioxide of another embodiment according to the present invention; And
Fig. 6 is the structural representation of the system of preparing titanium dioxide of another embodiment according to the present invention.
Embodiment
Describe embodiments of the invention below in detail, the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or has the element of identical or similar functions from start to finish.Below by the embodiment being described with reference to the drawings, be exemplary, only for explaining the present invention, and can not be interpreted as limitation of the present invention.
In the present invention, the terms such as unless otherwise clearly defined and limited, term " is connected ", " connection ", " fixing " should be interpreted broadly, and for example, can be to be fixedly connected with, and can be also to removably connect, or connect integratedly; Can be mechanical connection, can be also electrical connection; Can be to be directly connected, also can indirectly be connected by intermediary, can be the connection of two element internals.For the ordinary skill in the art, can understand as the case may be above-mentioned term concrete meaning in the present invention.
It should be noted that, term " first ", " second " be only for describing object, and can not be interpreted as indication or hint relative importance or the implicit quantity that indicates indicated technical characterictic.Thus, one or more these features can be expressed or impliedly be comprised to the feature that is limited with " first ", " second ".
In one aspect of the invention, a kind of method of preparing titanium dioxide has been proposed.With reference to figure 3 and 4, the method comprises:
(1) titanium tetrachloride the first preheating
In this step, by burning dme, provide heat, titanium tetrachloride is carried out to the first preheating, to make, through the temperature of the titanium tetrachloride of the first preheating, reach and be not less than 270 degrees Celsius, wherein, utilize the mode that DME combustion heats titanium tetrachloride to be not particularly limited.According to some embodiments of the present invention, adopt the mode of indirect heating, the heat that utilizes DME combustion to produce carries out the first preheating to titanium tetrachloride.Thus; can effectively utilize have good burning performance, dme that thermo-efficiency is high carries out preheating to titanium tetrachloride; and dme is clean energy; in combustion processes without residue, without black smoke, on heating plate, carbon distribution is little; almost the transmission of heat is not affected; reduced fund and the human input of soot blower system and service work simultaneously, guaranteed, on the basis of quality product, also to have protected environment.
(2) titanium tetrachloride the second preheating
In this step, aluminium powder, chlorine and the described titanium tetrachloride through the first preheating are mixed, and make described aluminium powder and chlorine reaction generate aluminum chloride, to obtain the mixture that contains aluminum chloride and titanium tetrachloride, wherein, the heat that described aluminium powder and chlorine reaction produce is carried out the second preheating to described titanium tetrachloride, to make, through the temperature of the titanium tetrachloride of the second preheating, reaches and is not less than 350 degrees Celsius.Thus, the heat that can effectively utilize aluminium powder and chlorine reaction to produce carries out the second preheating to titanium tetrachloride, thereby improves pre-thermo-efficiency, and reaches joint and can subtract Mao object.
According to embodiments of the invention, the ratio that aluminium powder, chlorine and the titanium tetrachloride through the first preheating mix is not particularly limited, and those skilled in the art can select flexibly according to practical situation.According to concrete examples more of the present invention, by described aluminium powder and chlorine, according to mass ratio, be that 1:1～1:5 mixes.Thus, can make aluminium powder and chlorine react under optimal conditions of mixture ratios, described in maintaining, contain in the mixture of aluminum chloride and titanium tetrachloride simultaneously, the content of described aluminum chloride is 0.01%～0.1%, thereby be conducive to the generation of the titanium dioxide crystal with desired particle size, and then improve the production efficiency of titanium dioxide, and contriver finds, if the amount of aluminum chloride is too much or very few, all will affect titanium dioxide quality.
(3) oxygen the first preheating
In this step, by burning dme, provide heat, oxygen is carried out to the first preheating, to make to reach and be not less than 750 degrees Celsius through the temperature of the oxygen of the first preheating, wherein, the mode of heating is not particularly limited.According to some embodiments of the present invention, adopt the mode of indirect heating, the heat that utilizes DME combustion to produce carries out the first preheating to oxygen.Thus, the heat that can effectively utilize DME combustion generation heats titanium tetrachloride, and then improves pre-thermo-efficiency and titanium dioxide production efficiency, and dme is clean energy, by DME combustion, provide heat, not only heat utilization efficiency is high, energy consumption is low, and environmental pollution is little.
(4) oxygen the second preheating
In this step, by burning toluene, provide heat, the described oxygen through the first preheating is carried out to the second preheating, to make, through the temperature of the oxygen of the second preheating, reach and be not less than 1500 degrees Celsius.Thus, can further improve pre-thermo-efficiency, thereby improve the efficiency of preparing titanium dioxide.
According to embodiments of the invention, the mode that the heat that utilizes toluene burning to produce heats oxygen is not particularly limited.According to concrete examples more of the present invention, can be by toluene and the described oxygen mix through the first preheating, and burning is so that by direct-fired mode, and the described oxygen through the first preheating is carried out to the second preheating.Thus, can utilize efficiently the heat of toluene burning to carry out the second preheating to oxygen, thereby further improve pre-thermo-efficiency, and then improve the efficiency of preparing titanium dioxide.
According to embodiments of the invention, toluene is not particularly limited with the ratio of the oxygen mix through the first preheating.According to concrete examples more of the present invention, temperature according to actual needs of toluene and volume ratio through the oxygen of the first preheating is determined, along with the rising of required temperature, the addition of toluene increases gradually.Thus, can further improve pre-thermo-efficiency, and then improve the production efficiency of titanium dioxide.
(5) oxidizing reaction
In this step, in oxidation reaction apparatus, the mixture that contains aluminum chloride and titanium tetrachloride obtaining in step (2) is mixed with the oxygen through the second preheating obtaining in step (4), and make titanium tetrachloride and oxygen generation oxidizing reaction, wherein, in described oxidation reaction apparatus, add silicon-dioxide as removing scar sand, to obtain the oxidation mixtures that contains titanium dioxide and chlorine.Thus, can, efficiently by titanium tetrachloride oxidation, generate titanium dioxide, thereby improve the efficiency of preparing titanium dioxide, and, silicon-dioxide added for removing scar sand, can avoid the titania producing to bond on reactor wall, and then at high-temperature condition, issue spread and become scar layer.
(6) gas solid separation
In this step, the oxidation mixtures obtaining is carried out to gas solid separation, to obtain respectively titanium dioxide and chlorine in step (5).Thus, can be effectively that titanium dioxide is separation with chlorine, and separate the chlorine obtaining and can be further used for titaniferous ore to carry out chloridized, thereby realize the recycle of chlorine, and then reach the object of Jie Neng Jian Mao, protection of the environment.
In one embodiment of the invention, oxidation mixtures carries out gas solid separation and further comprises: utilize chuck cooling tube, described oxidation mixtures is carried out cooling; Utilize deep bed filter to carry out gas solid separation to described oxidation mixtures, to obtain respectively the gas tail gas that contains chlorine and comprise titanium dioxide and except the solid mixture of scar sand; Described solid mixture is joined in base-material pulping tank, by adding de-mineralized water to carry out slurrying in described base-material pulping tank; And obtained slurry is joined except in scar sand separating apparatus, to separate, obtain except scar sand and titanium dioxide slurry.Wherein, the temperature of oxidation mixtures is 1800 degrees Celsius, by chuck cooling tube, can fast described oxidation mixtures be cooled to 300 degrees Celsius, thereby can avoid titanium dioxide crystal at high temperature to increase rapidly with mutually boning, scabs; The chlorine obtaining through gas solid separation can recycle, for titaniferous ore is carried out to chloridized, thereby reach the object of Jie Neng Jian Mao, and when the emergency state, the described gas tail gas that contains chlorine can be discharged after alkali lye chilling and two-stage alkali liquid washing, thus, can realize the quick qualified discharge of the gas tail gas that contains chlorine, reduce environmental pollution; And described slurry is joined except in scar sand separating apparatus, separate obtain except scar sand is after washing, dry and stage treatment, can be back in described oxidation reaction apparatus and recycle, thereby reduce the cost of preparing titanium dioxide.
With reference to figure 5 and 6, in still another aspect of the invention, the present invention proposes a kind of system of preparing titanium dioxide.According to embodiments of the invention, this system comprises: titanium tetrachloride preheater 610, Alchlor generator 620, oxygen preheat device 630, combustion chamber 640, oxidation reaction apparatus 600(in this article, also referred to as " oxidation reactor ") and gas-solid separating device 650.Contriver finds, utilize the system of preparing titanium dioxide of the present invention, can effectively implement the method for preparing titanium dioxide of the present invention, thereby can to the raw material of titanium tetrachloride oxidizing reaction, carry out preheating effectively rapidly, and obtain aluminum chloride, thereby can effectively generate titanium dioxide, and then can improve the efficiency of preparing titanium dioxide, reduce the cost of preparing titanium dioxide.
According to embodiments of the invention, described titanium tetrachloride preheater 610 adopts dme as fuel, by burning dme, provides heat, and titanium tetrachloride is carried out to the first preheating thus, can improve pre-thermo-efficiency, thereby improves the efficiency of preparing titanium dioxide.
According to some embodiments of the present invention, described titanium tetrachloride preheater 610 further comprises: DME combustion chamber (not shown), and described DME combustion chamber adopts dme as fuel, by burning dme, produces heat; Heat exchange chamber (not shown), described heat exchange chamber is connected with described DME combustion chamber; And titanium tetrachloride pipeline (not shown), described titanium tetrachloride pipeline is through described heat exchange chamber, so that the heat that utilizes burning dme to produce heats described titanium tetrachloride.Thus, can effectively utilize the heat that DME combustion produces, adopt the mode of indirect heating, titanium tetrachloride is heated, not only heat utilization efficiency is higher, and dme is clean energy, can reduce environmental pollution.
According to embodiments of the invention, described Alchlor generator 620 is connected with described titanium tetrachloride preheater 610, and limit reaction compartment in described Alchlor generator 620, in described reaction compartment, be suitable for aluminium powder, chlorine and the described titanium tetrachloride through the first preheating mix, make described aluminium powder and chlorine reaction generate aluminum chloride, to obtain the mixture that contains aluminum chloride and titanium tetrachloride, wherein, the heat that described aluminium powder and chlorine reaction produce is carried out the second preheating to described titanium tetrachloride. thus, the heat that can effectively utilize aluminium powder and chlorine reaction to produce carries out the second preheating to titanium tetrachloride, thereby improve pre-thermo-efficiency, and reach Jie Neng Jian Mao object.
According to embodiments of the invention, the ratio that aluminium powder, chlorine and the titanium tetrachloride through the first preheating mix is not particularly limited, and those skilled in the art can select flexibly according to practical situation.According to concrete examples more of the present invention, by described aluminium powder and chlorine, according to mass ratio, be that 1:1～1:5 mixes.Thus, can make aluminium powder and chlorine react under optimal conditions of mixture ratios, described in maintaining, contain in the mixture of aluminum chloride and titanium tetrachloride simultaneously, the content of described aluminum chloride is 0.01%～0.1%, thereby be conducive to the generation of the titanium dioxide crystal with desired particle size, and then improve the production efficiency of titanium dioxide, and contriver finds, if the amount of aluminum chloride is too much or very few, all will affect titanium dioxide quality.
According to embodiments of the invention, described oxygen preheat device 630 adopts dme as fuel, by burning dme, provides heat, and oxygen is carried out to the first preheating, to make, through the temperature of the oxygen of the first preheating, reaches and is not less than 750 degrees Celsius.Thus, the heat that can effectively utilize DME combustion generation heats titanium tetrachloride, and then improves pre-thermo-efficiency and titanium dioxide production efficiency, and dme is clean energy, by DME combustion, provide heat, not only heat utilization efficiency is high, energy consumption is low, and environmental pollution is little.
According to embodiments of the invention, described oxygen preheat device further comprises: DME combustion chamber, and described DME combustion chamber adopts dme as fuel, by burning dme, produces heat; Heat exchange chamber (not shown), described heat exchange chamber is connected with described DME combustion chamber; And oxygen pipeline, described oxygen pipeline is through described heat exchange chamber, so that the heat that utilizes burning dme to produce heats described oxygen.Thus, the heat that can effectively utilize DME combustion generation heats oxygen, and then improves pre-thermo-efficiency and titanium dioxide production efficiency, and dme is clean energy, by DME combustion, provide heat, not only heat utilization efficiency is high, energy consumption is low, and environmental pollution is little.
According to embodiments of the invention, described combustion chamber 640 be suitable for by toluene with through the oxygen of the first preheating, mix, and provide heat by burning toluene, the described oxygen through the first preheating is carried out to the second preheating, to make, through the temperature of the oxygen of the second preheating, reach and be not less than 1500 degrees Celsius.Thus, can further improve pre-thermo-efficiency, thereby improve the efficiency of preparing titanium dioxide.According to some embodiments of the present invention, toluene is not particularly limited with the ratio of the oxygen mix through the first preheating.According to concrete examples more of the present invention, temperature according to actual needs of toluene and volume ratio through the oxygen of the first preheating is determined, along with the rising of required temperature, the addition of toluene increases gradually.Thus, can further improve pre-thermo-efficiency, and then improve the production efficiency of titanium dioxide.
According to embodiments of the invention, described oxidation reaction apparatus 600 is connected with described Alchlor generator 620 and described combustion chamber 640 respectively, so that by the described mixture that contains aluminum chloride and titanium tetrachloride with through the oxygen of the second preheating, mix, and make titanium tetrachloride and oxygen generation oxidizing reaction, to obtain the oxidation mixtures that contains titanium dioxide and chlorine.Thus, can, efficiently by titanium tetrachloride oxidation, generate titanium dioxide, thereby improve the efficiency of preparing titanium dioxide.
According to embodiments of the invention, described gas-solid separating device 650 is connected with described oxidation reaction apparatus 600, and is suitable for described oxidation mixtures to carry out gas solid separation, to obtain respectively titanium dioxide and chlorine.Thus, can be effectively that titanium dioxide is separation with chlorine, and separate the chlorine obtaining and can further react with aluminium powder, thereby realize the recycle of chlorine, and then reach the object of Jie Neng Jian Mao, protection of the environment.
In one embodiment of the invention, described gas-solid separating device 650 further comprises: chuck cooling tube 6510, and described chuck cooling tube 6510 is suitable for utilizing recirculated water, described oxidation mixtures is carried out cooling fast; And deep bed filter 6520, described deep bed filter 6520 is connected with described chuck cooling tube 6510, and is suitable for described oxidation mixtures to carry out gas solid separation, to obtain respectively titanium dioxide and chlorine.Can be efficiently rapidly that oxidation mixtures is cooling, thus avoid titanium dioxide crystal at high temperature to increase rapidly and mutually bond and scab, and further gas solid separation can be by chlorine recycle, thereby reaches the object of Jie Neng Jian Mao.
In addition, according to embodiments of the invention, titanium tetrachloride can be obtained by titaniferous ore chlorination, for this reason, for convenient, understand, below to preparing titanium dioxide by ore, and with the present invention mutually the compatible method and system of preparing titanium dioxide be described, wherein, below feature described above goes for, described content, repeats no more.
With reference to figure 1, according to embodiments of the invention, the method comprises:
S100: chlorination reaction
In this step, titaniferous ore, reductive agent are supplied in chlorination reactor, and to oxygen gas-supplying, air and chlorine in described chlorination reactor, to there is chlorination reaction in described chlorination reactor, and obtain the chlorination reaction mixture that contains titanium tetrachloride gases, wherein, described reductive agent is refinery coke, and described titaniferous ore is titanium slag or rutile titanium ore.Particularly, the production of titanium tetrachloride gases is mainly in chlorination reactor, continuously to add titanium ore (titanium slag or rutile), reducing substances (refinery coke), and continuously in reactor, passes into oxygen, pressurized air, Cl
2; And temperature is in the time of 850 ℃, and titaniferous ore (titanium slag or rutile) and chlorine recur reaction and continues to generate TiCl
4gas, reaction equation is: 2TiO
2+ 3C+4Cl
2=2TiCl
4+ 2CO+CO
2.In one embodiment of the invention, described chlorination reaction is to carry out at the temperature of 700～900 degrees Celsius.Preferably, chlorination reaction is to carry out at the temperature of 850 degrees Celsius.Contriver surprisingly finds through great many of experiments, carries out chlorination reaction under 850 degrees Celsius, can generate titanium tetrachloride with the efficiency that is significantly better than other temperature.
S200: the first gas solid separation
In this step, the chlorination reaction mixture obtaining is carried out to gas solid separation processing, to obtain the gaseous mixture that contains titanium tetrachloride in preceding step.According to embodiments of the invention, the method and apparatus that carries out the first gas solid separation can be any known means in this area.
S300: condensation process
In this step, the described gaseous mixture that contains titanium tetrachloride is carried out to condensation process, to obtain liquid titanium tetrachloride.In one embodiment of the invention, in this step, further comprise: by a part for described liquid titanium tetrachloride with described in contain titanium tetrachloride gaseous mixture contact, to carry out the first cooling process; And utilize refrigerant to carry out the second cooling process to the gaseous mixture through the first cooling process, to obtain described liquid titanium tetrachloride, wherein, described refrigerant is the R507 cooling medium of temperature-23 degree Celsius.Contriver find, by this method of cooling, can effectively the gaseous mixture that contains titanium tetrachloride be carried out cooling, thereby realize being further purified titanium tetrachloride.Wherein, for the first cooling process, can effectively utilize and obtain cooling liquid titanium tetrachloride and carry out cooling, thereby reduced the production cost of producing titanium dioxide, in addition, adopting the R507 cooling medium of temperature-23 degree Celsius as refrigerant, is that contriver passes through a large amount of screening operations and unexpected acquisition, and find, it can play a role with the cooling medium that is significantly better than other temperature and type.
S400: storage
In this step, the described liquid crude titanium tetrachloride that preceding step is obtained is stored in titanium tetrachloride storing device.
S500: except vanadium processing
In this step, adopt mineral oil to remove vanadium processing to described liquid crude titanium tetrachloride, to described liquid crude titanium tetrachloride is refined, to obtain through refining smart titanium tetrachloride, wherein, in the refining titanium tetrachloride of described process, the content of vanadium is below 3ppm.
S600: oxidizing reaction
In this step, the smart titanium tetrachloride and the oxygen that obtain are supplied in oxidation reactor, to there is oxidizing reaction TiCl in described oxidation reactor in preceding step
4+ O
2=TiO
2+ 2Cl
2, to obtain the oxidation mixtures that contains titanium dioxide and chlorine.In one embodiment of the invention, in obtained smart titanium tetrachloride and oxygen are supplied to oxidation reactor before, in advance described smart titanium tetrachloride and oxygen are carried out respectively to thermal pretreatment.In one embodiment of the invention, described smart titanium tetrachloride and oxygen are preheated to are respectively not less than 350 degrees Celsius and be not less than 1500 degrees Celsius in advance.Thus, can further improve the efficiency of preparing titanium dioxide, reduce the cost of preparing titanium dioxide.Contriver finds, by smart titanium tetrachloride and oxygen are preheated to respectively, is not less than 350 degrees Celsius and be not less than 1500 degrees Celsius, can significantly effectively reduce the cost of preparing titanium dioxide.When excess Temperature, the needed cost of preheating can significantly increase, and when temperature is too low, in oxidation reactor, can consume too much energy.
S700: the second gas solid separation
The described oxidation mixtures obtaining in preceding step is carried out to gas solid separation, to obtain respectively solid titanium dioxide and chlorine.Contriver finds, utilizes the method can effectively prepare titanium dioxide, and then by titanium dioxide is carried out to coating processing, can effectively obtain the titanium dioxide of size-grade distribution excellence.In one embodiment of the invention, further comprise: the chlorine obtaining in preceding step is back to and in chlorination reaction step, carries out chlorination reaction.Contriver finds, by the chlorine obtaining after the second gas solid separation, can be directly used in chlorination reaction, thereby has reduced the cost of producing titanium dioxide, has reduced pollution.
In one side more of the present invention, the present invention proposes a kind of system of preparing titanium dioxide.With reference to figure 2, according to embodiments of the invention, this system comprises: chlorination reactor 100, the first gas-solid separating device 200, condensing works 300, titanium tetrachloride storing device 400, refining plant 500, oxidation reactor 600 and the second gas-solid separating device 700.Root is according to embodiments of the invention, chlorination reactor 100 is provided with titanium ore entrance (not shown), reductive agent entrance (not shown), oxygen intake (not shown), gas inlet (not shown) and chlorine entrance (not shown), so that by titaniferous ore, reductive agent is supplied in described chlorination reactor, and to oxygen gas-supplying in described chlorination reactor, air and chlorine, to there is chlorination reaction in described chlorination reactor, and obtain the chlorination reaction mixture that contains titanium tetrachloride gases, wherein, described reductive agent is refinery coke, described titaniferous ore is titanium slag or rutile titanium ore.The first gas-solid separating device 200 is connected with chlorination reactor 100, for described chlorination reaction mixture is carried out to gas solid separation processing, to obtain the gaseous mixture that contains titanium tetrachloride.Condensing works 300 is connected with the first gas solid separation 200 devices, for the described gaseous mixture that contains titanium tetrachloride is carried out to condensation process, to obtain liquid titanium tetrachloride.Titanium tetrachloride storing device 400 is connected with condensing works 300, for storing described liquid crude titanium tetrachloride.Refining plant 500 is connected with titanium tetrachloride storing device 400, and be suitable for adopting mineral oil to remove vanadium processing to described liquid crude titanium tetrachloride, to described liquid crude titanium tetrachloride is refined, to obtain through refining smart titanium tetrachloride, wherein, in the refining titanium tetrachloride of described process, the content of vanadium is below 3ppm.Oxidation reactor 600 is connected with refining plant 500, and be provided with oxygen intake (not shown), for described smart titanium tetrachloride and oxygen are supplied to oxidation reactor 600, to there is oxidizing reaction in oxidation reactor 600, to obtain the oxidation mixtures that contains titanium dioxide and chlorine.The second gas-solid separating device 700 is connected with oxidation reactor 600, for oxidation mixtures is carried out to gas solid separation, to obtain respectively solid titanium dioxide and chlorine.Utilize this system, can effectively implement the aforementioned method of preparing titanium dioxide.
In one embodiment of the invention, described condensing works 300 further comprises: adverse current cooling unit (not shown), described adverse current cooling unit is provided with chlorination reaction mixture entrance (not shown) and liquid titanium tetrachloride entrance (not shown), so that in described adverse current cooling unit by a part for described liquid titanium tetrachloride with described in contain titanium tetrachloride gaseous mixture counter current contact, to carry out the first cooling process; And tubular heat exchanger (not shown), described tubular heat exchanger is connected with described adverse current cooling unit, and utilize refrigerant to carry out the second cooling process to the gaseous mixture through the first cooling process, to obtain described liquid titanium tetrachloride, wherein, described refrigerant is the R507 cooling medium of temperature-23 degree Celsius.Contriver find, by this method of cooling, can effectively the gaseous mixture that contains titanium tetrachloride be carried out cooling, thereby realize being further purified titanium tetrachloride.Wherein, for the first cooling process, can effectively utilize and obtain cooling liquid titanium tetrachloride and carry out cooling, thereby reduced the production cost of producing titanium dioxide, in addition, adopting the R507 cooling medium of temperature-23 degree Celsius as refrigerant, is that contriver passes through a large amount of screening operations and unexpected acquisition, and find, it can play a role with the cooling medium that is significantly better than other temperature and type.
In one embodiment of the invention, further comprise: smart titanium tetrachloride primary heater unit (not shown), described smart titanium tetrachloride primary heater unit is connected with described oxidation unit 600 with described refining plant 500, in advance described smart titanium tetrachloride is carried out to thermal pretreatment; Oxygen preheat device (not shown), described oxygen preheat device is connected with described oxidation unit 600, in advance described oxygen is carried out to thermal pretreatment.Thus, can further improve the efficiency of preparing titanium dioxide, reduce the cost of preparing titanium dioxide.Contriver finds, by smart titanium tetrachloride and oxygen are preheated to respectively, is not less than 350 degrees Celsius and be not less than 1500 degrees Celsius, can significantly effectively reduce the cost of preparing titanium dioxide.When temperature height is too high, the needed cost of preheating can significantly increase, and when temperature is too low, can the too much energy of consumption in oxidation reactor.
In one embodiment of the invention, described the second gas-solid separating device 700 is connected with described chlorination reactor 600, for obtained chlorine being back to described chlorination reactor 100, carries out chlorination reaction.Contriver finds, by the chlorine obtaining after the second gas solid separation, can be directly used in chlorination reaction, thereby has reduced the cost of producing titanium dioxide, has reduced pollution.
In the description of this specification sheets, the description of reference term " embodiment ", " some embodiment ", " example ", " concrete example " or " some examples " etc. means to be contained at least one embodiment of the present invention or example in conjunction with specific features, structure, material or the feature of this embodiment or example description.In this manual, the schematic statement of above-mentioned term is not necessarily referred to identical embodiment or example.And specific features, structure, material or the feature of description can be with suitable mode combination in any one or more embodiment or example.
Although illustrated and described embodiments of the invention, those having ordinary skill in the art will appreciate that: in the situation that not departing from principle of the present invention and aim, can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited by claim and equivalent thereof.
Claims (8)
1. a method of preparing titanium dioxide, is characterized in that, comprising:
(1) by burning dme, provide heat, titanium tetrachloride is carried out to the first preheating;
(2) aluminium powder, chlorine and the described titanium tetrachloride through the first preheating are mixed, and make described aluminium powder and chlorine reaction generate aluminum chloride, to obtain the mixture that contains aluminum chloride and titanium tetrachloride, wherein, the heat that described aluminium powder and chlorine reaction produce is carried out the second preheating to described titanium tetrachloride;
(3) by burning dme, provide heat, oxygen is carried out to the first preheating;
(4) by burning toluene, provide heat, the described oxygen through the first preheating is carried out to the second preheating;
(5) in oxidation reaction apparatus, the mixture that obtains containing aluminum chloride and titanium tetrachloride in step (2) is mixed with the oxygen through the second preheating obtaining in step (4), and make titanium tetrachloride and oxygen generation oxidizing reaction, wherein, in described oxidation reaction apparatus, add silicon-dioxide as removing scar sand, to obtain the oxidation mixtures that contains titanium dioxide and chlorine; And
(6) described oxidation mixtures is carried out to gas solid separation, to obtain respectively titanium dioxide and chlorine,
Wherein,
Described oxidation mixtures is carried out to gas solid separation further to be comprised:
Utilize chuck cooling tube, described oxidation mixtures is carried out cooling;
Utilize deep bed filter to carry out gas solid separation to described oxidation mixtures, to obtain respectively the gas tail gas that contains chlorine and comprise titanium dioxide and except the solid mixture of scar sand;
Described solid mixture is joined in base-material pulping tank, by adding de-mineralized water to carry out slurrying in described base-material pulping tank; And
Obtained slurry is joined except in scar sand separating apparatus, to separate, obtain except scar sand and titanium dioxide slurry.
2. method according to claim 1, is characterized in that, the temperature of described oxidation mixtures is 1800 degrees Celsius, utilizes chuck cooling tube, and the temperature of described oxidation mixtures is cooled to 300 degrees Celsius.
3. method according to claim 1, is characterized in that, by the described gas tail gas that contains chlorine for titaniferous ore is carried out to chloridized.
4. method according to claim 1, is characterized in that, the described gas tail gas that contains chlorine is discharged after alkali lye chilling and two-stage alkali liquid washing.
5. method according to claim 1, is characterized in that, what separation was obtained joins in described oxidation reaction apparatus except scar sand after washing, dry and classification.
6. method according to claim 1, is characterized in that, through the temperature of the titanium tetrachloride of the first preheating for being not less than 270 degrees Celsius;
Through the temperature of the titanium tetrachloride of the second preheating for being not less than 350 degrees Celsius;
Through the temperature of the oxygen of the first preheating for being not less than 750 degrees Celsius;
Through the temperature of the oxygen of the second preheating for being not less than 1500 degrees Celsius.
7. method according to claim 1, is characterized in that, in step (1) and step (3), described titanium tetrachloride is carried out the first preheating and oxygen is carried out to the first preheating, is indirect heating,
In step (4), by toluene and the described oxygen mix through the first preheating, and burning is to by direct heating, carry out the second preheating to the described oxygen through the first preheating.
8. method according to claim 3, it is characterized in that, in step (2), described aluminium powder and chlorine are that the ratio that is 1:1～1:5 according to mass ratio is mixed, so that described in contain aluminum chloride and titanium tetrachloride mixture in, the content of described aluminum chloride is 0.01%～0.1%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107697949A (en) * | 2017-11-13 | 2018-02-16 | 龙蟒佰利联集团股份有限公司 | A kind of sulfuric acid process falls kiln product and is used for the production process of titanium pigment that chloridising removes scar sand |
| CN111874943A (en) * | 2020-06-22 | 2020-11-03 | 河南佰利联新材料有限公司 | Control method for CO content in boiling chlorination reaction tail gas |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3414379A (en) * | 1964-06-03 | 1968-12-03 | Laporte Titanium Ltd | Manufacture of titanium dioxide |
| CN1066043A (en) * | 1991-12-27 | 1992-11-11 | 天津化工厂 | Rutile-type titanium dioxide powder prepared by plasma chlorination process |
| CN1071396A (en) * | 1991-10-11 | 1993-04-28 | 天津化工厂 | The adding method of gaseous oxidation system titanium white crystal inversion accelerating agent |
| US5266108A (en) * | 1992-04-22 | 1993-11-30 | E. I. Du Pont De Nemours And Company | Using compacted titanium dioxide pigment particles in the cooling section of the chloride process for making TiO2 |
| CN1915833A (en) * | 2006-09-06 | 2007-02-21 | 清华大学 | Oxidation reactor for preparing titanium white through chlorination process, and method |
| CN102583531A (en) * | 2012-01-20 | 2012-07-18 | 锦州钛业有限公司 | Production method of granularity-controllable titanium dioxide |
-
2013
- 2013-12-09 CN CN201310661877.0A patent/CN103723766B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3414379A (en) * | 1964-06-03 | 1968-12-03 | Laporte Titanium Ltd | Manufacture of titanium dioxide |
| CN1071396A (en) * | 1991-10-11 | 1993-04-28 | 天津化工厂 | The adding method of gaseous oxidation system titanium white crystal inversion accelerating agent |
| CN1066043A (en) * | 1991-12-27 | 1992-11-11 | 天津化工厂 | Rutile-type titanium dioxide powder prepared by plasma chlorination process |
| US5266108A (en) * | 1992-04-22 | 1993-11-30 | E. I. Du Pont De Nemours And Company | Using compacted titanium dioxide pigment particles in the cooling section of the chloride process for making TiO2 |
| CN1915833A (en) * | 2006-09-06 | 2007-02-21 | 清华大学 | Oxidation reactor for preparing titanium white through chlorination process, and method |
| CN102583531A (en) * | 2012-01-20 | 2012-07-18 | 锦州钛业有限公司 | Production method of granularity-controllable titanium dioxide |
Non-Patent Citations (3)
| Title |
|---|
| 熊云等: "《清洁燃料基础及应用》", 31 May 2005, 中国石化出版社 * |
| 罗远辉等: "《钛化合物》", 31 January 2011, 冶金工业出版社 * |
| 莫畏，邓国珠等: "《钛冶金》", 30 June 1998 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107697949A (en) * | 2017-11-13 | 2018-02-16 | 龙蟒佰利联集团股份有限公司 | A kind of sulfuric acid process falls kiln product and is used for the production process of titanium pigment that chloridising removes scar sand |
| CN107697949B (en) * | 2017-11-13 | 2023-09-08 | 龙佰集团股份有限公司 | Titanium dioxide production process for chloridizing scar-removing sand by sulfuric acid method kiln dropping product |
| CN111874943A (en) * | 2020-06-22 | 2020-11-03 | 河南佰利联新材料有限公司 | Control method for CO content in boiling chlorination reaction tail gas |
| CN111874943B (en) * | 2020-06-22 | 2023-04-07 | 河南佰利联新材料有限公司 | Control method for CO content in boiling chlorination reaction tail gas |
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