CN103663552B - Prepare method and the system of titanium dioxide - Google Patents
Prepare method and the system of titanium dioxide Download PDFInfo
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- CN103663552B CN103663552B CN201310664609.4A CN201310664609A CN103663552B CN 103663552 B CN103663552 B CN 103663552B CN 201310664609 A CN201310664609 A CN 201310664609A CN 103663552 B CN103663552 B CN 103663552B
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Abstract
The present invention relates to the method and system of preparing titanium dioxide. The method comprises: (1) provides heat by burning dme, and titanium tetrachloride is carried out the first preheating; (2) making aluminium powder and chlorine reaction generate aluminum chloride, to obtain the mixture containing aluminum chloride and titanium tetrachloride, wherein, titanium tetrachloride is carried out the 2nd preheating by the heat that aluminium powder and chlorine reaction produce; (3) provide heat by burning dme, oxygen is carried out the first preheating; (4) provide heat by burning toluene, the oxygen through the first preheating is carried out the 2nd preheating; (5) mixture containing aluminum chloride and titanium tetrachloride is mixed with the oxygen through the 2nd preheating, and make titanium tetrachloride and oxygen generation oxidizing reaction, to obtain the oxidation mixtures containing titanium dioxide and chlorine; And oxidation mixtures is carried out gas solid separation by (6), to obtain titanium dioxide and chlorine respectively. The method is utilized can effectively to prepare titanium dioxide.
Description
Technical field
The present invention relates to chemical field. More specifically, it relates to prepare method and the system of titanium dioxide.
Background technology
The method producing titanium dioxide at present 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.
CN1066043 discloses a kind of processing method preparing Rutile type Titanium Dioxide, it comprises 1), chlorination furnace is put into by after titanium slag and refinery coke Homogeneous phase mixing, lead to chlorine at 800��900 DEG C of temperature, carry out fluidizing chlorination, 2), the rough titanium tetrachloride obtained after chlorination carries out separation purification remove, magnesium, iron, the impurity such as silicon and vanadium, obtain refining titanic chloride, 3), obtained refining titanic chloride liquid is in vaporizer, it is converted into gas phase, and it is preheated to 450��800 DEG C, 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 DEG C of temperature, it is less than in 0.1 second and carries out oxidizing reaction generation solid phase titanium dioxide, 5), rapidly titanium dioxide pressed powder is moved out of reaction zone and reaction heat is gone in shifting rapidly, collect titanium dioxide generation chlorine and return chlorination furnace, 6), the titanium dioxide granule powder of collection is beaten into liquid, through two-stage sorting, the fine particle titanium dioxide being less than 1 micron carries out aftertreatment again, coarse particles grinding and then classification, 7), used additives pH=7��8 at 50��70 DEG C of temperature are made to carry out coating aftertreatment, 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 DEG C of temperature, micronizing, product mean particle size accounts for 70% below 0.3 ��m.
But, the means preparing titanium dioxide at present still have much room for improvement.
Summary of the invention
The present invention is intended to one of technical problem at least solving existence in prior art. For this reason, it is an object of the present invention to propose a kind of method and system that can effectively prepare titanium dioxide.
In a first aspect of the present invention, it is proposed that a kind of method preparing titanium dioxide. According to embodiments of the invention, the method comprises: (1) provides heat by burning dme, and titanium tetrachloride is carried out the first preheating; (2) by aluminium powder, chlorine and the mixing of the described titanium tetrachloride through the first preheating, and make described aluminium powder and chlorine reaction generate aluminum chloride, to obtain the mixture containing aluminum chloride and titanium tetrachloride, wherein, described titanium tetrachloride is carried out the 2nd preheating by the heat that described aluminium powder and chlorine reaction produce; (3) in oxygen preheater, provide heat by burning dme, oxygen is carried out the first preheating; (4) provide heat by burning toluene, the described oxygen through the first preheating is carried out the 2nd preheating; (5) mix step (2) obtains the mixture containing aluminum chloride and titanium tetrachloride with the oxygen through the 2nd preheating obtained in step (4), and make titanium tetrachloride and oxygen generation oxidizing reaction, to obtain the oxidation mixtures containing titanium dioxide and chlorine; And described oxidation mixtures is carried out gas solid separation by (6), to obtain titanium dioxide and chlorine respectively. Heat wherein, described oxygen preheater comprises: dme combustion chamber, described dme combustion chamber adopt dme as fuel, by burning dme produce heat; Heat exchanging chamber room, described heat exchanging chamber room is connected with described dme combustion chamber, and is provided with smoke inlet and exhanst gas outlet; And oxygen pipeline, for described oxygen pipeline through described heat exchanging chamber room, so that described titanium tetrachloride is heated by the heat utilizing burning dme to produce. Pass through the method, effectively fast the raw material of titanium tetrachloride oxidation reaction can be carried out preheating, and obtain aluminum chloride, such that it is able to effectively generate titanium dioxide, and then the efficiency preparing titanium dioxide can be improved, reduce the cost preparing titanium dioxide, adopt dme that titanium tetrachloride and oxygen are carried out preheating simultaneously, not only heat utilization efficiency height, and dme is clean energy, decreases environmental pollution.
According to embodiments of the invention, described oxygen preheater comprises multiple oxygen pipeline. According to embodiments of the invention, the inwall of described heat transfer space is lined with refractory brick. According to embodiments of the invention, described oxygen pipeline comprises oxygen inlet and oxygen outlet, wherein, described on the axial direction due of described heat exchanging chamber room, described dme combustion chamber is located at the lower section of described oxygen inlet, and described exhanst gas outlet is positioned at the top of described oxygen outlet. Thus, the oxygen in oxygen pipeline is carried out preheating by convection action by the high-temperature flue gas that dme burning produces, and heat utilization efficiency is higher, it is possible to improves titanium tetrachloride preheat efficiency, and then can improve the efficiency preparing titanium dioxide.
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 titanium tetrachloride of the first preheating for being not less than 270 degrees Celsius; Through the temperature of titanium tetrachloride of the 2nd preheating for being not less than 350 degrees Celsius; Through the temperature of oxygen of the first preheating for being not less than 750 degrees Celsius; Through the temperature of oxygen of the 2nd preheating for being not less than 1500 degrees Celsius. Thus, it is possible to improve pre-thermo-efficiency further, thus improve the efficiency preparing titanium dioxide.
In one embodiment of the invention, in step (1) and step (3), described titanium tetrachloride carried out the first preheating and oxygen is carried out the first preheating, it is indirect heating, in step (4), by toluene and the described oxygen mix through the first preheating, and burn by direct heating, the described oxygen through the first preheating is carried out the 2nd preheating. Thus, it is possible to improve heat utilization efficiency, improve pre-thermo-efficiency further, thus improve the efficiency preparing titanium dioxide.
In one embodiment of the invention, in step (2), described aluminium powder and chlorine are that the ratio being 1:1��1:5 according to mass ratio carries out mixing, so that in the described mixture containing aluminum chloride and titanium tetrachloride, the content of described aluminum chloride is 0.01%��0.1%. Thus, can so that aluminium powder and chlorine react under the most applicable conditions of mixture ratios, the amount of the aluminum chloride generated is suitable for, thus be conducive to having the generation of the titanium dioxide crystal of 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.
In one embodiment of the invention, in step (4), the volume ratio of described toluene and the described oxygen through the first preheating temperature according to actual needs and determine, along with the rising of required temperature, the addition of toluene increases gradually. Thus, it is possible to improve pre-thermo-efficiency further, thus improve the efficiency preparing titanium dioxide.
In one embodiment of the invention, in step (6), described oxidation mixtures is carried out gas solid separation comprise further: (6-1) utilizes recirculated water, described oxidation mixtures is cooled fast, the temperature of described oxidation mixtures was cooled to less than 500 degrees Celsius in one minute; And (6-2) utilizes deep bed filter that described oxidation mixtures is carried out gas solid separation, to obtain titanium dioxide and chlorine respectively. Being cooled by oxidation mixtures fast consequently, it is possible to efficient, thus avoid titanium dioxide crystal at high temperature increase rapidly and mutually bond and scab, further gas solid separation by chlorine recycle, thus can reach the energy-conservation object subtracted.
In still another aspect of the invention, the present invention proposes a kind of system preparing titanium dioxide. According to embodiments of the invention, this system comprises: Titanium tetrachloride preheater, and described Titanium tetrachloride preheater adopts dme as fuel, provides heat by burning dme, titanium tetrachloride is carried out the first preheating; Alchlor generator, described Alchlor generator is connected with described Titanium tetrachloride preheater, and described Alchlor generator limits reaction compartment, be suitable for aluminium powder, chlorine and the mixing of the described titanium tetrachloride through the first preheating in described reaction compartment, described aluminium powder and chlorine reaction is made to generate aluminum chloride, to obtain the mixture containing aluminum chloride and titanium tetrachloride, wherein, described titanium tetrachloride is carried out the 2nd preheating by the heat that described aluminium powder and chlorine reaction produce; Oxygen preheater, described oxygen preheater adopts dme as fuel, provides heat by burning dme, oxygen is carried out the first preheating; Combustion chamber, described combustion chamber is suitable for mixing toluene with the oxygen through the first preheating, and provides heat by burning toluene, and the described oxygen through the first preheating carries out the 2nd preheating; Oxidation reaction apparatus, described oxidation reaction apparatus is connected with described Alchlor generator and described combustion chamber respectively, the described mixture containing aluminum chloride and titanium tetrachloride is mixed with the oxygen through the 2nd preheating, and make titanium tetrachloride and oxygen generation oxidizing reaction, to obtain the oxidation mixtures containing titanium dioxide and chlorine; And gas-solid separating device, described gas-solid separating device is connected with described oxidation reaction apparatus, and is suitable for described oxidation mixtures is carried out gas solid separation, to obtain titanium dioxide and chlorine respectively. Consequently, it is possible to effectively implement aforementioned method, prepare titanium dioxide efficiently, adopt dme titanium tetrachloride and oxygen to be carried out preheating, not only heat utilization efficiency height, and dme is clean energy, decreases environmental pollution simultaneously.
According to embodiments of the invention, oxygen preheater comprises: dme combustion chamber, and described dme combustion chamber adopts dme as fuel, produces heat by burning dme; Heat exchanging chamber room, described heat exchanging chamber room is connected with described dme combustion chamber, and is provided with smoke inlet and exhanst gas outlet; And oxygen pipeline, for described oxygen pipeline through described heat exchanging chamber room, so that described titanium tetrachloride is heated by the heat utilizing burning dme to produce. Thus; can effectively utilize have good burning performance, dme that thermo-efficiency is high oxygen is carried out preheating; and without residue in dme combustion processes, without black cigarette, on heating plate, long-pending carbon is little; almost the transmission of heat is not affected; decrease fund and the human input of soot blower system and service work simultaneously; on the basis that ensure that quality product, also protect environment.
According to embodiments of the invention, described oxygen preheater comprises multiple oxygen pipeline. According to embodiments of the invention, the inwall of described heat transfer space is lined with refractory brick. According to embodiments of the invention, described oxygen pipeline comprises oxygen inlet and oxygen outlet, wherein, described on the axial direction due of described heat exchanging chamber room, described dme combustion chamber is located at the lower section of described oxygen inlet, and described exhanst gas outlet is positioned at the top of described oxygen outlet. Thus, the oxygen in oxygen pipeline is carried out preheating by convection action by the high-temperature flue gas that dme burning produces, and heat utilization efficiency is higher, it is possible to improve titanium tetrachloride preheat efficiency, and then improves the efficiency preparing titanium dioxide.
Accompanying drawing explanation
Above-mentioned and/or the additional aspect of the present invention and advantage from accompanying drawing below combining to the description of embodiment becoming obviously and it should be readily understood that wherein:
Fig. 1 is the schematic flow sheet of the method preparing titanium dioxide according to an embodiment of the invention;
Fig. 2 is the structural representation of the system preparing titanium dioxide according to an embodiment of the invention;
Fig. 3 is the schematic flow sheet of the method preparing titanium dioxide according to another embodiment of the present invention;
Fig. 4 is the schematic flow sheet of the method preparing titanium dioxide according to another embodiment of the present invention;
Fig. 5 is the structural representation of the system preparing titanium dioxide according to another embodiment of the present invention; And
Fig. 6 is the structural representation of the system preparing titanium dioxide according to another embodiment of the present invention.
Embodiment
Being described below in detail embodiments of the invention, the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or has element that is identical or similar functions from start to finish. It is exemplary below by the embodiment being described with reference to the drawings, only for explaining the present invention, and limitation of the present invention can not be interpreted as.
In the present invention, unless otherwise clearly defined and limited, term " is connected ", " connection ", the term such as " fixing " should be interpreted broadly, and such as, it is possible to be fixedly connected with, it is also possible to be removably connect, or connects integratedly; Can be mechanically connected, it is also possible to be electrical connection; Can be directly be connected, it is also possible to be indirectly connected by intermediary, it is possible to be the connection of two element internals. For the ordinary skill in the art, it is possible to understand above-mentioned term concrete implication in the present invention according to particular case.
It should be noted that, term " first ", " the 2nd " are only for describing object, and can not be interpreted as instruction or hint relative importance or imply the quantity indicating indicated technology feature. Thus, be limited with " first ", the feature of " the 2nd " can express or implicit comprise one or more these features.
In one aspect of the invention, it is proposed that a kind of method preparing titanium dioxide. With reference to figure 3 and 4, according to embodiments of the invention, the method comprises the following steps:
(1) titanium tetrachloride first preheating
In this step, there is provided heat by burning dme, titanium tetrachloride is carried out the first preheating, to make the temperature through the titanium tetrachloride of the first preheating reach be not less than 270 degrees Celsius, wherein, the mode utilizing dme burning to be heated by titanium tetrachloride is not particularly limited. According to some embodiments of the present invention, adopting the mode of indirect heating, titanium tetrachloride is carried out the first preheating by the heat utilizing dme burning to produce. Thus; can effectively utilize have good burning performance, dme that thermo-efficiency is high titanium tetrachloride is carried out preheating; and dme is clean energy; without residue in combustion processes, without black cigarette, on heating plate, long-pending carbon is little; almost the transmission of heat is not affected; decrease fund and the human input of soot blower system and service work simultaneously, on the basis that ensure that quality product, also protect environment.
(2) titanium tetrachloride the 2nd preheating
In this step, by aluminium powder, chlorine and the mixing of the described titanium tetrachloride through the first preheating, and make described aluminium powder and chlorine reaction generate aluminum chloride, to obtain the mixture containing aluminum chloride and titanium tetrachloride, wherein, described titanium tetrachloride is carried out the 2nd preheating by the heat that described aluminium powder and chlorine reaction produce, to make the temperature through the titanium tetrachloride of the 2nd preheating reach be not less than 350 degrees Celsius. Thus, it is possible to titanium tetrachloride is carried out the 2nd preheating by the heat effectively utilizing aluminium powder and chlorine reaction to produce, thus improves pre-thermo-efficiency, and reaches energy-conservation and subtract object, and generate aluminum chloride can effectively as the nucleus of titanium dioxide crystallization.
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. Described aluminium powder and chlorine are that 1:1��1:5 mixes according to mass ratio by some the concrete examples according to the present invention. Thus, can so that aluminium powder and chlorine react under the most applicable conditions of mixture ratios, maintain in the described mixture containing aluminum chloride and titanium tetrachloride simultaneously, the content of described aluminum chloride is 0.01%��0.1%, thus be conducive to having the generation of the titanium dioxide crystal of 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, titanium dioxide quality all will be affected.
(3) oxygen first preheating
In this step, in oxygen preheater, providing heat by burning dme, oxygen is carried out the first preheating, to make the temperature through the oxygen of the first preheating reach be not less than 750 degrees Celsius, wherein, the mode of heating is not particularly limited. According to some embodiments of the present invention, adopting the mode of indirect heating, oxygen is carried out the first preheating by the heat utilizing dme burning to produce. Thus, it is possible to titanium tetrachloride is heated by the heat effectively utilizing dme burning generation, and then improves pre-thermo-efficiency and titanium dioxide production efficiency, and dme is clean energy, thering is provided heat by dme burning, not only heat utilization efficiency height, energy consumption are low, and environmental pollution is little.
According to embodiments of the invention, oxygen preheater comprises: dme combustion chamber, and described dme combustion chamber adopts dme as fuel, produces heat by burning dme; Heat exchanging chamber room, described heat exchanging chamber room is connected with described dme combustion chamber, and is provided with smoke inlet and exhanst gas outlet; And oxygen pipeline, for described oxygen pipeline through described heat exchanging chamber room, so that described titanium tetrachloride is heated by the heat utilizing burning dme to produce. According to embodiments of the invention, described oxygen preheater comprises multiple oxygen pipeline. Thus; can effectively utilize have good burning performance, dme that thermo-efficiency is high oxygen is carried out preheating; and without residue in dme combustion processes, without black cigarette, on heating plate, long-pending carbon is little; almost the transmission of heat is not affected; decrease fund and the human input of soot blower system and service work simultaneously; on the basis that ensure that quality product, also protect environment.
According to embodiments of the invention, the inwall of described heat transfer space is lined with refractory brick. According to embodiments of the invention, described oxygen pipeline comprises oxygen inlet and oxygen outlet, wherein, described on the axial direction due of described heat exchanging chamber room, described dme combustion chamber is located at the lower section of described oxygen inlet, and described exhanst gas outlet is positioned at the top of described oxygen outlet. Thus, the oxygen in oxygen pipeline is carried out preheating by convection action by the high-temperature flue gas that dme burning produces, and heat utilization efficiency is higher, it is possible to improve titanium tetrachloride preheat efficiency, and then improves the efficiency preparing titanium dioxide.
(4) oxygen the 2nd preheating
In this step, provide heat by burning toluene, the described oxygen through the first preheating is carried out the 2nd preheating, to make the temperature through the oxygen of the 2nd preheating reach be not less than 1500 degrees Celsius. Thus, it is possible to improve pre-thermo-efficiency further, thus improve the efficiency preparing titanium dioxide.
According to embodiments of the invention, the mode that oxygen is heated by the heat utilizing toluene burning to produce is not particularly limited. Some concrete examples according to the present invention, it is possible to by toluene and the described oxygen mix through the first preheating, and burn so that by direct-fired mode, the described oxygen through the first preheating is carried out the 2nd preheating. Thus, it is possible to utilize the heat that toluene burns that oxygen carries out the 2nd preheating efficiently, thus improve pre-thermo-efficiency further, and then improve and prepare the efficiency of titanium dioxide.
According to embodiments of the invention, toluene is not particularly limited with the ratio of the oxygen mix through the first preheating. Some concrete examples according to the present invention, determine toluene and the volume ratio temperature according to actual needs of the oxygen through the first preheating, along with the rising of required temperature, the addition of toluene increases gradually. Thus, it is possible to improve pre-thermo-efficiency further, and then improve the production efficiency of titanium dioxide.
(5) oxidizing reaction
In this step, the mixture containing aluminum chloride and titanium tetrachloride obtained in step (2) is mixed with the oxygen through the 2nd preheating obtained in step (4), and make titanium tetrachloride and oxygen generation oxidizing reaction, to obtain the oxidation mixtures containing titanium dioxide and chlorine. Thus, it is possible to efficiently by titanium tetrachloride oxidation, generate titanium dioxide, thus improve the efficiency preparing titanium dioxide.
(6) gas solid separation
In this step, the oxidation mixtures obtained in step (5) is carried out gas solid separation, to obtain titanium dioxide and chlorine respectively. Consequently, it is possible to be effectively separated with chlorine by titanium dioxide, and the chlorine being separated acquisition can be further used for titanium ore is carried out chloridized, thus realizes the recycle of chlorine, so reach energy-conservation and subtract, the object of protection of the environment.
In one embodiment of the invention, in step (6), described oxidation mixtures is carried out gas solid separation comprise further: (6-1) utilizes recirculated water, described oxidation mixtures is cooled fast, the temperature of described oxidation mixtures was cooled to less than 500 degrees Celsius in one minute; And (6-2) utilizes deep bed filter that described oxidation mixtures is carried out gas solid separation, to obtain titanium dioxide and chlorine respectively. Fast oxidation mixtures is cooled consequently, it is possible to efficient, thus avoid titanium dioxide crystal at high temperature increase rapidly and mutually bond and scab, the chlorine recycle that separation can be obtained by further gas solid separation, thus reach the energy-conservation object subtracted.
With reference to figure 5 and 6, in still another aspect of the invention, the present invention proposes a kind of system preparing titanium dioxide. According to embodiments of the invention, this system comprises: Titanium tetrachloride preheater 610, Alchlor generator 620, oxygen preheater 630, combustion chamber 640, oxidation reaction apparatus 600(herein, also referred to as " oxidation reactor ") and gas-solid separating device 650. Contriver finds, utilize the system preparing titanium dioxide of the present invention, can effectively implement the method preparing titanium dioxide of the present invention, it is thus possible to effectively fast the raw material of titanium tetrachloride oxidation reaction is carried out preheating, and obtain aluminum chloride, such that it is able to effectively generate titanium dioxide, and then the efficiency preparing titanium dioxide can be improved, reduce the cost preparing titanium dioxide.
According to embodiments of the invention, described Titanium tetrachloride preheater 610 adopts dme as fuel, provides heat by burning dme, titanium tetrachloride is carried out the first preheating. Consequently, it is possible to improve pre-thermo-efficiency, thus improving and prepare the efficiency of titanium dioxide, and dme is clean energy, provide heat by dme burning, not only heat utilization efficiency height, energy consumption are low, and environmental pollution is little.
According to embodiments of the invention, described Alchlor generator 620 is connected with described Titanium tetrachloride preheater 610, and described Alchlor generator 620 limits reaction compartment (not shown), be suitable for aluminium powder, chlorine and the mixing of the described titanium tetrachloride through the first preheating in described reaction compartment, described aluminium powder and chlorine reaction is made to generate aluminum chloride, to obtain the mixture containing aluminum chloride and titanium tetrachloride, wherein, described titanium tetrachloride is carried out the 2nd preheating by the heat that described aluminium powder and chlorine reaction produce. Thus, while obtaining aluminum chloride, it is possible to titanium tetrachloride is carried out the 2nd preheating by the heat effectively utilizing aluminium powder and chlorine reaction to produce, thus improve pre-thermo-efficiency, and reach energy-conservation and subtract object, wherein, aluminum chloride can effectively as the nucleus of titanium dioxide crystallization.
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. Some concrete examples according to the present invention, described aluminium powder and chlorine are that the ratio being 1:1��1:5 according to mass ratio carries out mixing. Thus, can so that aluminium powder and chlorine react under the most applicable conditions of mixture ratios, maintain in the described mixture containing aluminum chloride and titanium tetrachloride simultaneously, the content of described aluminum chloride is 0.01%��0.1%, thus be conducive to having the generation of the titanium dioxide crystal of 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, titanium dioxide quality all will be affected.
According to embodiments of the invention, described oxygen preheater 630 adopts dme as fuel, provides heat by burning dme, oxygen is carried out the first preheating, to make the temperature through the oxygen of the first preheating reach be not less than 750 degrees Celsius. Thus, it is possible to titanium tetrachloride is heated by the heat effectively utilizing dme burning generation, and then improves pre-thermo-efficiency and titanium dioxide production efficiency, and dme is clean energy, thering is provided heat by dme burning, not only heat utilization efficiency height, energy consumption are low, and environmental pollution is little.
According to embodiments of the invention, described oxygen preheater comprises: dme combustion chamber, and described dme combustion chamber adopts dme as fuel, produces heat by burning dme; Heat exchanging chamber room, described heat exchanging chamber room is connected with described dme combustion chamber, and is provided with smoke inlet and exhanst gas outlet; And oxygen pipeline, for described oxygen pipeline through described heat exchanging chamber room, so that described oxygen is heated by the heat utilizing burning dme to produce. Thus; can effectively utilize have good burning performance, dme that thermo-efficiency is high oxygen is carried out preheating; and without residue in dme combustion processes, without black cigarette, on heating plate, long-pending carbon is little; almost the transmission of heat is not affected; decrease fund and the human input of soot blower system and service work simultaneously; on the basis that ensure that quality product, also protect environment.
According to embodiments of the invention, described oxygen preheater comprises multiple oxygen pipeline. According to embodiments of the invention, the inwall of described heat transfer space is lined with refractory brick. According to embodiments of the invention, described oxygen pipeline comprises oxygen inlet and oxygen outlet, wherein, described on the axial direction due of described heat exchanging chamber room, described dme combustion chamber is located at the lower section of described oxygen inlet, and described exhanst gas outlet is positioned at the top of described oxygen outlet. Thus, the oxygen in oxygen pipeline is carried out preheating by convection action by the high-temperature flue gas that dme burning produces, and heat utilization efficiency is higher, it is possible to improves titanium tetrachloride preheat efficiency, and then can improve the efficiency preparing titanium dioxide.
According to embodiments of the invention, described combustion chamber 640 is suitable for mixing toluene with the oxygen through the first preheating, and provide heat by burning toluene, the described oxygen through the first preheating is carried out the 2nd preheating, to make the temperature through the oxygen of the 2nd preheating reach be not less than 1500 degrees Celsius. Thus, it is possible to improve pre-thermo-efficiency further, thus improve the efficiency 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. Some concrete examples according to the present invention, toluene is determined according to volume ratio temperature according to actual needs with the oxygen through the first preheating, and along with the rising of required temperature, the addition of toluene increases gradually. Thus, it is possible to improve pre-thermo-efficiency further, 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, the described mixture containing aluminum chloride and titanium tetrachloride is mixed with the oxygen through the 2nd preheating, and make titanium tetrachloride and oxygen generation oxidizing reaction, to obtain the oxidation mixtures containing titanium dioxide and chlorine. Thus, it is possible to efficiently by titanium tetrachloride oxidation, generate titanium dioxide, thus improve the efficiency 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 is carried out gas solid separation, to obtain titanium dioxide and chlorine respectively. Consequently, it is possible to effectively titanium dioxide is separated with chlorine, and be separated acquisition chlorine can further with aluminium powder reaction, thus realize the recycle of chlorine, so reach energy-conservation and subtract, the object of protection of the environment.
In one embodiment of the invention, described gas-solid separating device 650 comprises further: water cooling unit 6510, and described water cooling unit 6510 is suitable for utilizing recirculated water, is cooled fast by described oxidation mixtures; And deep bed filter 6520, described deep bed filter 6520 is connected with described water cooling unit 6510, and is suitable for described oxidation mixtures is carried out gas solid separation, to obtain titanium dioxide and chlorine respectively. Efficiently can being cooled by oxidation mixtures fast, thus avoid titanium dioxide crystal at high temperature increase rapidly and mutually bond and scab, further gas solid separation by chlorine recycle, thus can reach the energy-conservation object subtracted.
In addition, according to embodiments of the invention, titanium tetrachloride can be obtained by titaniferous ore chlorination, for this reason, understand in order to convenient, prepare titanium dioxide to by ore below, and the method preparing titanium dioxide compatible mutually and system are described with the present invention, wherein, content described below feature described above goes for, 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 in described chlorination reactor, air and chlorine, there is chlorination reaction in described chlorination reactor, and obtain the chlorination reaction mixture containing titanium tetrachloride gases, wherein, described reductive agent is refinery coke, and described titaniferous ore is titanium slag or rutile titanium ore. Specifically, mainly successive in the chlorination reactor interpolation titanium ore (titanium slag or rutile) of the production of titanium tetrachloride gases, reducing substances (refinery coke), and successive leading to into oxygen, pressurized air, Cl in reactor2; And temperature is when 850 DEG C, titaniferous ore (titanium slag or rutile) and chlorine recur reaction to be continued to generate TiCl4Gas, reaction equation is: 2TiO2+3C+4Cl2=2TiCl4+2CO+CO2. In one embodiment of the invention, described chlorination reaction carries out at the temperature of 700��900 degrees Celsius. Preferably, chlorination reaction carries out at the temperature of 850 degrees Celsius. Contriver, through the unexpected discovery of a large amount of experiment, carries out chlorination reaction under 850 degrees Celsius, it is possible to generate titanium tetrachloride to be significantly better than the efficiency of other temperature.
S200: the first gas solid separation
In this step, the chlorination reaction mixture obtained in preceding step is carried out gas solid separation process, to obtain the gaseous mixture containing titanium tetrachloride. According to embodiments of the invention, the method and the device that carry out the first gas solid separation can be any known means in this area.
S300: condensation process
In this step, the described gaseous mixture containing titanium tetrachloride is carried out condensation process, to obtain liquid titanium tetrachloride. In one embodiment of the invention, in this step, comprise further: by a part for described liquid titanium tetrachloride and the described gas mixture contacts containing titanium tetrachloride, to carry out the first cooling process; And utilize refrigerant that the gaseous mixture through the first cooling process is carried out the 2nd cooling process, to obtain described liquid titanium tetrachloride, wherein, described refrigerant is the R507 cooling medium of temperature-23 degrees Celsius. Contriver finds, by this method of cooling, it is possible to effectively cooled by the gaseous mixture containing titanium tetrachloride, thus realizes being further purified titanium tetrachloride. Wherein, for the first cooling process, the liquid titanium tetrachloride obtaining cooling can be effectively utilized cool, thus reduce the production cost producing titanium dioxide, in addition, adopting the R507 cooling medium of temperature-23 degrees Celsius as refrigerant, being that contriver is unexpected by a large amount of screening operation obtains, and finding, it can play a role to be significantly better than the cooling medium of other temperature and type.
S400: store
In this step, described liquid crude titanium tetrachloride preceding step obtained is stored in titanium tetrachloride storing device.
S500: except vanadium process
In this step, mineral oil is adopted to be carried out by described liquid crude titanium tetrachloride except vanadium process, to be refined by described liquid crude titanium tetrachloride, to obtain through refining refined titanic chloride, wherein, in the titanium tetrachloride that described process is refining, the content of vanadium is below 3ppm.
S600: oxidizing reaction
In this step, the refined titanic chloride obtained in preceding step and oxygen are supplied in oxidation reactor, there is oxidizing reaction TiCl in described oxidation reactor4+O2=TiO2+2Cl2, to obtain the oxidation mixtures containing titanium dioxide and chlorine. In one embodiment of the invention, before being supplied in oxidation reactor by the refined titanic chloride obtained and oxygen, in advance described refined titanic chloride and oxygen are carried out thermal pretreatment respectively. In one embodiment of the invention, described refined titanic chloride and oxygen are preheated to respectively are not less than 350 degrees Celsius and be not less than 1500 degrees Celsius in advance. Thus, it is possible to improve the efficiency preparing titanium dioxide further, the cost preparing titanium dioxide is reduced. Contriver finds, is not less than 350 degrees Celsius with being not less than 1500 degrees Celsius by refined titanic chloride and oxygen being preheated to respectively, it is possible to significantly effectively reduce the cost preparing titanium dioxide. When temperature is too high, the cost required for preheating can significantly increase, and when the temperature is too low, then can consume too much energy in oxidation reactor.
S700: the two gas solid separation
The described oxidation mixtures obtained in preceding step is carried out gas solid separation, to obtain solid titanium dioxide and chlorine respectively. Contriver finds, utilizes the method can effectively prepare titanium dioxide, and then by titanium dioxide is carried out coating process, it is possible to effectively obtain the titanium dioxide of size-grade distribution excellence. In one embodiment of the invention, comprise further: the chlorine obtained in preceding step is back in chlorination reaction step and carries out chlorination reaction. Contriver finds, by the chlorine obtained after the 2nd gas solid separation, it is possible to be directly used in chlorination reaction, thus reduces the cost producing titanium dioxide, decreases pollution.
In another aspect of the invention, the invention allows for a kind of system preparing titanium dioxide. with reference to figure 2, according to embodiments of the invention, this system comprises: chlorination reactor 100, first gas-solid separating device 200, condensing works 300, titanium tetrachloride storing device 400, refining plant 500, oxidation reactor 600 and the 2nd gas-solid separating device 700. 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, there is chlorination reaction in described chlorination reactor, and obtain the chlorination reaction mixture containing titanium tetrachloride gases, wherein, described reductive agent is refinery coke, described titaniferous ore is titanium slag or rutile titanium ore. first gas-solid separating device 200 is connected with chlorination reactor 100, for described chlorination reaction mixture is carried out gas solid separation process, to obtain the gaseous mixture containing titanium tetrachloride. condensing works 300 is connected with the first gas solid separation 200 device, for the described gaseous mixture containing titanium tetrachloride is carried out 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 be carried out by described liquid crude titanium tetrachloride except vanadium process, described liquid crude titanium tetrachloride is refined, to obtain through refining refined titanic chloride, wherein, in the titanium tetrachloride that described process is refining, the content of vanadium is below 3ppm. oxidation reactor 600 is connected with refining plant 500, and it is provided with oxygen intake (not shown), for described refined titanic chloride and oxygen are supplied in oxidation reactor 600, there is oxidizing reaction in oxidation reactor 600, to obtain the oxidation mixtures containing titanium dioxide and chlorine. 2nd gas-solid separating device 700 is connected with oxidation reactor 600, for oxidation mixtures is carried out gas solid separation, to obtain solid titanium dioxide and chlorine respectively. utilize this system, it is possible to effectively implement the aforementioned method preparing titanium dioxide.
In one embodiment of the invention, described condensing works 300 comprises further: 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 by a part for described liquid titanium tetrachloride and the described gaseous mixture counter current contact containing titanium tetrachloride in described adverse current cooling unit, 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 that the gaseous mixture through the first cooling process is carried out the 2nd cooling process, to obtain described liquid titanium tetrachloride, wherein, described refrigerant is the R507 cooling medium of temperature-23 degrees Celsius. Contriver finds, by this method of cooling, it is possible to effectively cooled by the gaseous mixture containing titanium tetrachloride, thus realizes being further purified titanium tetrachloride. Wherein, for the first cooling process, the liquid titanium tetrachloride obtaining cooling can be effectively utilized cool, thus reduce the production cost producing titanium dioxide, in addition, adopting the R507 cooling medium of temperature-23 degrees Celsius as refrigerant, being that contriver is unexpected by a large amount of screening operation obtains, and finding, it can play a role to be significantly better than the cooling medium of other temperature and type.
In one embodiment of the invention, comprise further: refined titanic chloride primary heater unit (not shown), described refined titanic chloride primary heater unit is connected with described oxidation unit 600 with described refining plant 500, in advance described refined titanic chloride is carried out thermal pretreatment; Oxygen preheat equipment (not shown), described oxygen preheat equipment is connected with described oxidation unit 600, in advance described oxygen is carried out thermal pretreatment. Thus, it is possible to improve the efficiency preparing titanium dioxide further, the cost preparing titanium dioxide is reduced. Contriver finds, is not less than 350 degrees Celsius with being not less than 1500 degrees Celsius by refined titanic chloride and oxygen being preheated to respectively, it is possible to significantly effectively reduce the cost preparing titanium dioxide. When temperature height is too high, the cost required for preheating can significantly increase, and when the temperature is too low, then can consume too much energy in oxidation reactor.
In one embodiment of the invention, described 2nd gas-solid separating device 700 is connected with described chlorination reactor 600, carries out chlorination reaction for being back in described chlorination reactor 100 by the chlorine obtained. Contriver finds, by the chlorine obtained after the 2nd gas solid separation, it is possible to be directly used in chlorination reaction, thus reduces the cost producing titanium dioxide, decreases pollution.
In the description of this specification sheets, at least one embodiment that the description of reference term " embodiment ", " some embodiments ", " example ", " concrete example " or " some examples " etc. means to be contained in the present invention in conjunction with concrete feature, structure, material or feature that this embodiment or example describe or example. In this manual, the schematic representation of above-mentioned term is not necessarily referred to identical embodiment or example. And, the concrete feature of description, structure, material or feature can combine in an appropriate manner in any one or more embodiment or example.
Although it has been shown and described that embodiments of the invention, it will be understood by those skilled in the art that: these embodiments can be carried out multiple change, amendment, replacement and modification when not departing from principle and the objective of the present invention, the scope of the present invention by claim and etc. jljl limit.
Claims (9)
1. prepare the method for titanium dioxide for one kind, it is characterised in that, comprising:
(1) provide heat by burning dme, titanium tetrachloride is carried out the first preheating;
(2) aluminium powder, chlorine and the described titanium tetrachloride through the first preheating are mixed in Alchlor generator, and make described aluminium powder and chlorine reaction generate aluminum chloride, to obtain the mixture containing aluminum chloride and titanium tetrachloride, wherein, described titanium tetrachloride is carried out the 2nd preheating by the heat that described aluminium powder and chlorine reaction produce;
(3) in oxygen preheater, provide heat by burning dme, oxygen is carried out the first preheating;
(4) provide heat by burning toluene, the described oxygen through the first preheating is carried out the 2nd preheating;
(5) mix step (2) obtains the mixture containing aluminum chloride and titanium tetrachloride with the oxygen through the 2nd preheating obtained in step (4), and make titanium tetrachloride and oxygen generation oxidizing reaction, to obtain the oxidation mixtures containing titanium dioxide and chlorine; And
(6) described oxidation mixtures is carried out gas solid separation, to obtain titanium dioxide and chlorine respectively,
Wherein, described oxygen preheater comprises:
Dme combustion chamber, described dme combustion chamber adopts dme as fuel, produces heat by burning dme;
Heat exchanging chamber room, described heat exchanging chamber room is connected with described dme combustion chamber, and is provided with smoke inlet and exhanst gas outlet; And
Oxygen pipeline, described oxygen pipeline is through described heat exchanging chamber room, so that described oxygen is heated by the heat utilizing burning dme to produce,
Wherein, through the temperature of titanium tetrachloride of the first preheating for being not less than 270 degrees Celsius;
Through the temperature of titanium tetrachloride of the 2nd preheating for being not less than 350 degrees Celsius;
Through the temperature of oxygen of the first preheating for being not less than 750 degrees Celsius;
Through the temperature of oxygen of the 2nd preheating for being not less than 1500 degrees Celsius,
In step (2), described aluminium powder and chlorine are that the ratio being 1:1��1:5 according to mass ratio carries out mixing, so that in the described mixture containing aluminum chloride and titanium tetrachloride, the content of described aluminum chloride is 0.01%��0.1%.
2. method according to claim 1, it is characterised in that, described oxygen preheater comprises multiple oxygen pipeline.
3. method according to claim 1, it is characterised in that, the inwall of described heat transfer space is lined with refractory brick.
4. method according to claim 2, it is characterised in that, described oxygen pipeline comprises oxygen inlet and oxygen outlet,
Wherein,
Described on the axial direction due of described heat exchanging chamber room, described dme combustion chamber is located at the lower section of described oxygen inlet, and described exhanst gas outlet is positioned at the top of described oxygen outlet.
5. method according to claim 1, it is characterised in that, in step (6), described oxidation mixtures is carried out gas solid separation and comprises further:
(6-1) utilize recirculated water, described oxidation mixtures is cooled fast, the temperature of described oxidation mixtures was cooled to less than 500 degrees Celsius in one minute; And
(6-2) utilize deep bed filter that described oxidation mixtures is carried out gas solid separation, to obtain titanium dioxide and chlorine respectively.
6. prepare the system of titanium dioxide for one kind, it is characterised in that, comprising:
Titanium tetrachloride preheater, described Titanium tetrachloride preheater adopts dme as fuel, provides heat by burning dme, titanium tetrachloride is carried out the first preheating;
Alchlor generator, described Alchlor generator is connected with described Titanium tetrachloride preheater, and described Alchlor generator limits reaction compartment, be suitable for aluminium powder, chlorine and the mixing of the described titanium tetrachloride through the first preheating in described reaction compartment, described aluminium powder and chlorine reaction is made to generate aluminum chloride, to obtain the mixture containing aluminum chloride and titanium tetrachloride, wherein, described titanium tetrachloride is carried out the 2nd preheating by the heat that described aluminium powder and chlorine reaction produce;
Oxygen preheater, described oxygen preheater adopts dme as fuel, provides heat by burning dme, oxygen is carried out the first preheating;
Combustion chamber, described combustion chamber is suitable for mixing toluene with the oxygen through the first preheating, and provides heat by burning toluene, and the described oxygen through the first preheating carries out the 2nd preheating;
Oxidation reaction apparatus, described oxidation reaction apparatus is connected with described Alchlor generator and described combustion chamber respectively, the described mixture containing aluminum chloride and titanium tetrachloride is mixed with the oxygen through the 2nd preheating, and make titanium tetrachloride and oxygen generation oxidizing reaction, to obtain the oxidation mixtures containing titanium dioxide and chlorine; And
Gas-solid separating device, described gas-solid separating device is connected with described oxidation reaction apparatus, and is suitable for described oxidation mixtures is carried out gas solid separation, to obtain titanium dioxide and chlorine respectively,
Wherein, described oxygen preheater comprises:
Dme combustion chamber, described dme combustion chamber adopts dme as fuel, produces heat by burning dme;
Heat exchanging chamber room, described heat exchanging chamber room is connected with described dme combustion chamber, and is provided with smoke inlet and exhanst gas outlet; And
Oxygen pipeline, for described oxygen pipeline through described heat exchanging chamber room, so that described oxygen is heated by the heat utilizing burning dme to produce.
7. system according to claim 6, it is characterised in that, described oxygen preheater comprises multiple oxygen pipeline.
8. system according to claim 6, it is characterised in that, the inwall of described heat transfer space is lined with refractory brick.
9. system according to claim 6, it is characterised in that, described oxygen pipeline comprises oxygen inlet and oxygen outlet,
Wherein,
Described on the axial direction due of described heat exchanging chamber room, described dme combustion chamber is located at the lower section of described oxygen inlet, and described exhanst gas outlet is positioned at the top of described oxygen outlet.
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