TW201406663A - Method for producing titanium dioxide particles - Google Patents
Method for producing titanium dioxide particles Download PDFInfo
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- TW201406663A TW201406663A TW102111550A TW102111550A TW201406663A TW 201406663 A TW201406663 A TW 201406663A TW 102111550 A TW102111550 A TW 102111550A TW 102111550 A TW102111550 A TW 102111550A TW 201406663 A TW201406663 A TW 201406663A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000002245 particle Substances 0.000 title claims abstract description 35
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 128
- 239000007789 gas Substances 0.000 claims abstract description 92
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
- 239000007787 solid Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000002737 fuel gas Substances 0.000 claims description 9
- 238000002309 gasification Methods 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 229910001882 dioxygen Inorganic materials 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000012463 white pigment Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- -1 heated Chemical compound 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/07—Producing by vapour phase processes, e.g. halide oxidation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
本發明有關二氧化鈦粒子之製造方法。 The present invention relates to a method for producing titanium dioxide particles.
二氧化鈦粒子主要作為白色顏料而使用於多方面。該二氧化鈦粒子係使四氯化鈦氣體在900~1600℃之溫度下以氧氣進行氧化而製造，在相對於生成之二氧化鈦粒子以氧化鋁換算為0.01~10重量%之氯化鋁氣體存在下進行氧化反應時，可效率良好地製造金紅石型二氧化鈦粒子。該氯化鋁在常溫為固體，熔點為192.4℃(無水物)，自160℃開始顯示昇華性。因此，二氧化鈦粒子之製造中，將固體氯化鋁中添加於液體四氯化鈦中，加熱且經供沸之四氯化鈦氣體中使氯化鋁氣體存在之方法為已知(參照專利文獻1)。且，將固體氯化鋁直接加熱並昇華而發生氯化鋁氣體之方法亦為已知(參照專利文獻2)。 Titanium dioxide particles are mainly used as a white pigment in various aspects. The titanium dioxide particles are produced by oxidizing titanium tetrachloride gas at a temperature of 900 to 1600 ° C with oxygen, and are carried out in the presence of aluminum chloride gas in an amount of 0.01 to 10% by weight based on the amount of alumina produced. In the oxidation reaction, rutile-type titanium oxide particles can be efficiently produced. The aluminum chloride was solid at normal temperature, and had a melting point of 192.4 ° C (anhydrous), and showed sublimation from 160 ° C. Therefore, in the production of titanium dioxide particles, a method in which solid aluminum chloride is added to liquid titanium tetrachloride, heated, and aluminum chloride gas is present in a boiling titanium tetrachloride gas is known (refer to the patent literature). 1). Further, a method of directly heating and sublimating solid aluminum chloride to generate aluminum chloride gas is also known (refer to Patent Document 2).
〔專利文獻1〕特表2010-509163號公報 [Patent Document 1] Special Table 2010-509163
〔專利文獻2〕特表2010-505007號公報 [Patent Document 2] Special Table 2010-505007
以專利文獻1之方法，於液體四氯化鈦中添加固體氯化鋁，由於經氣化，故難以正確地控制四氯化鈦氣體中之氯化鋁氣體含量，因此，有所製造之二氧化鈦粒子品質容易產生偏差之問題。且，以專利文獻2之方法，由於使固體氯化鋁昇華，故難以控制氯化鋁氣體之流量，為利用載氣進行輸送，故有氯化鋁氣體被稀釋等之問題。 According to the method of Patent Document 1, solid aluminum chloride is added to liquid titanium tetrachloride, and since it is vaporized, it is difficult to accurately control the aluminum chloride gas content in the titanium tetrachloride gas, and therefore, the manufactured titanium oxide is produced. Particle quality is prone to bias problems. Further, in the method of Patent Document 2, since the solid aluminum chloride is sublimated, it is difficult to control the flow rate of the aluminum chloride gas, and the carrier gas is transported, so that the aluminum chloride gas is diluted.
因此，本發明人等為了實現氯化鋁氣體之流量控制容易化、實現載氣之減少化而進行各種研究之結果，發現將固體氯化鋁於加熱加壓下進行液化，接著，氣化時，可利用壓力進行氯化鋁氣體之輸送，且利用壓力控制可控制氯化鋁氣體之流量，而且使用流量控制之氯化鋁氣體時，可獲得品質偏差較少的二氧化鈦粒子，因而完成本發明。 Therefore, the inventors of the present invention conducted various studies in order to facilitate the flow rate control of the aluminum chloride gas and reduce the carrier gas, and found that the solid aluminum chloride was liquefied under heat and pressure, and then, when vaporized. The pressure can be used for the transportation of the aluminum chloride gas, and the flow rate of the aluminum chloride gas can be controlled by the pressure control, and when the flow rate controlled aluminum chloride gas is used, the titanium dioxide particles having less quality deviation can be obtained, thereby completing the present invention. .
亦即，本發明係一種二氧化鈦粒子之製造方法，包含(1)使固體氯化鋁在加熱加壓下液化，接著使其氣化而製造氯化鋁氣體之步驟1；(2)在以前述步驟1製造之氯化鋁氣體存在下，使四氯化鈦氣體與氧及/或水 反應之步驟2。 That is, the present invention is a method for producing titanium dioxide particles, comprising: (1) step 1 of liquefying solid aluminum chloride under heat and pressure, followed by gasification to produce aluminum chloride gas; (2) in the foregoing Step 1 in the presence of aluminum chloride gas to make titanium tetrachloride gas with oxygen and / or water Step 2 of the reaction.
本發明係二氧化鈦粒子之製造方法，由於可利用壓力及溫度之控制而控制氯化鋁氣體之流量，故可製造品質偏差較少之二氧化鈦粒子。 The present invention is a method for producing titanium dioxide particles, and since the flow rate of the aluminum chloride gas can be controlled by the control of pressure and temperature, it is possible to produce titanium dioxide particles having a small variation in quality.
圖1為氯化鋁熔解槽之概視圖。 Figure 1 is a schematic view of an aluminum chloride melting tank.
本發明係一種二氧化鈦粒子之製造方法，包含(1)使固體氯化鋁在加熱加壓下液化，接著使其氣化而製造氯化鋁氣體之步驟1；(2)在以前述步驟1所製造之氯化鋁氣體存在下，使四氯化鈦氣體與氧及/或水反應之步驟2。 The present invention relates to a method for producing titanium dioxide particles, comprising: (1) step 1 of liquefying solid aluminum chloride under heat and pressure, followed by gasification to produce aluminum chloride gas; (2) in the aforementioned step 1 Step 2 of reacting titanium tetrachloride gas with oxygen and/or water in the presence of produced aluminum chloride gas.
前述步驟1係製造氯化鋁氣體之步驟，係將固體氯化鋁放入耐熱耐壓容器內，對容器內進行加熱加壓，以不使氯化鋁昇華之方式使其處於液體狀態。所用之耐壓容器或配管類之材質並未特別限制，但較好使用以鉭或哈氏合金(Hastelloy)為代表之耐腐蝕性優異之金屬，或使用於各種金屬材質表面被覆玻璃或陶瓷等而賦予耐腐蝕性者製作耐壓容器或配管類。 The above step 1 is a step of producing aluminum chloride gas by placing the solid aluminum chloride in a heat-resistant pressure-resistant container, and heating and pressurizing the inside of the container so as to be in a liquid state without sublimating the aluminum chloride. The material of the pressure-resistant container or the piping to be used is not particularly limited, but a metal excellent in corrosion resistance such as yttrium or Hastelloy or a surface coated with various metal materials such as glass or ceramic is preferably used. A pressure vessel or piping is produced by imparting corrosion resistance.
具體而言，首先，將固體氯化鋁放入耐熱耐壓容器中，進行加壓。接著，將容器加熱升溫至特定溫度時，氯化鋁層液化(熔解)。此液體氯化鋁在加熱加壓下會成為氣液平衡狀態，在一定壓力下進一步加熱、或藉由壓力調整機構等於一定溫度下減壓時，由於脫離平衡狀態而氣化(蒸發)，故氯化鋁氣體可取出至容器外，可導入至隨後之步驟2之反應裝置中。 Specifically, first, solid aluminum chloride is placed in a heat-resistant pressure vessel and pressurized. Next, when the vessel is heated and heated to a specific temperature, the aluminum chloride layer is liquefied (melted). The liquid aluminum chloride will be in a gas-liquid equilibrium state under heating and pressure, and further heated under a certain pressure, or when the pressure adjusting mechanism is equal to a certain temperature, the gas is degassed (evaporated) due to the equilibrium state. The aluminum chloride gas can be taken out of the vessel and introduced into the subsequent reaction apparatus of step 2.
容器內之溫度只要不使氯化鋁昇華而使其液化(熔解)之條件即可，較好為190~230℃，更好為195~220℃，又更好為200~210℃。 The temperature in the container may be liquefied (melted) as long as the aluminum chloride is not sublimed, and is preferably 190 to 230 ° C, more preferably 195 to 220 ° C, and even more preferably 200 to 210 ° C.
壓力可藉氧、氮等氣體之加壓並控制。容器內之壓力較好控制至0.23MPa以上，更好為0.25~0.4MPa，又更好為0.27~0.35MPa。 The pressure can be controlled by the pressure of oxygen, nitrogen and the like. The pressure in the vessel is preferably controlled to 0.23 MPa or more, more preferably 0.25 to 0.4 MPa, and even more preferably 0.27 to 0.35 MPa.
作為氯化鋁，已知有化學式AlCl3等，有無水物及六水合物，以無水物較佳。 As aluminum chloride, a chemical formula of AlCl 3 or the like is known, and an anhydride and a hexahydrate are preferable, and an anhydride is preferable.
接著，步驟2係二氧化鈦粒子之製造步驟，將前述步驟1製造之氯化鋁氣體導入反應裝置中，在氯化鋁氣體存在下，使四氯化鈦氣體與氧及/或水反應。 Next, step 2 is a step of producing titanium dioxide particles, and the aluminum chloride gas produced in the above step 1 is introduced into a reaction apparatus to react titanium tetrachloride gas with oxygen and/or water in the presence of aluminum chloride gas.
作為較佳之樣態1，係將使前述氯化鋁氣體與四氯化鈦氣體混合之氣體與含氧氣體一起導入反應裝置中，使四氯化鈦氣體與氧反應。 Preferably, the gas in which the aluminum chloride gas and the titanium tetrachloride gas are mixed is introduced into the reaction apparatus together with the oxygen-containing gas to cause the titanium tetrachloride gas to react with oxygen.
四氯化鈦係以化學式TiCl4表示，為熔點-25℃、沸點136.4℃之無色至淺黃色液體。將液體四氯化鈦蒸發所成之四氯化鈦氣體導入反應裝置中，另一方面，導入 氧、大氣等之含氧氣體，使四氯化鈦氧化。四氯化鈦氣體在導入反應裝置之前，較好與氯化鋁氣體混合成為混合氣體，更好即將導入反應裝置之前進行混合。四氯化鈦與氯化鋁之混合氣體與氧、大氣等之含氧氣體係分別導入反應裝置中。 Titanium tetrachloride is represented by the chemical formula TiCl 4 and is a colorless to pale yellow liquid having a melting point of -25 ° C and a boiling point of 136.4 ° C. The titanium tetrachloride gas obtained by evaporating the liquid titanium tetrachloride is introduced into the reaction apparatus, and on the other hand, an oxygen-containing gas such as oxygen or the atmosphere is introduced to oxidize titanium tetrachloride. The titanium tetrachloride gas is preferably mixed with aluminum chloride gas to form a mixed gas before being introduced into the reaction apparatus, and is preferably mixed before being introduced into the reaction apparatus. A mixed gas of titanium tetrachloride and aluminum chloride and an oxygen-containing system such as oxygen and the atmosphere are introduced into the reaction device, respectively.
反應裝置可為任何形狀，但例如若為管狀反應器時，較好為橫型，此情況下，係自管的入口或自管的入口附近之側面導入四氯化鈦氣體及含氧氣體，氯化鋁氣體亦自管的入口或自管的入口附近之側面或者亦可自在管中途之側面導入。上述之側面氣體導入部設置位置並未特別限制，若設在入口附近而較好為管之下部，若為管之中途則較好為上部。使用四氯化鈦與氯化鋁之混合氣體之情況時，較好自管的入口附近的側面下部導入。 The reaction apparatus may be of any shape, but for example, in the case of a tubular reactor, it is preferably horizontal, in which case titanium tetrachloride gas and oxygen-containing gas are introduced from the inlet of the tube or from the side near the inlet of the tube. The aluminum chloride gas is also introduced from the inlet of the tube or from the side near the inlet of the tube or from the side in the middle of the tube. The position at which the side gas introduction portion is not particularly limited is preferably a lower portion of the tube in the vicinity of the inlet, and preferably an upper portion in the middle of the tube. When a mixed gas of titanium tetrachloride and aluminum chloride is used, it is preferably introduced from the lower side of the side near the inlet of the tube.
氧化反應溫度通常較好為700~1600℃之溫度，更好為800~1200℃，又更好為900~1100℃。以上述溫度通常可製造金紅石型二氧化鈦粒子。 The oxidation reaction temperature is usually preferably from 700 to 1600 ° C, more preferably from 800 to 1200 ° C, and even more preferably from 900 to 1100 ° C. Rutile-type titanium dioxide particles can usually be produced at the above temperatures.
氯化鋁氣體之導入量可適當設定，例如相對於生成之二氧化鈦粒子，換算為氧化鋁，較好為0.01~10重量%，更好為0.1~5重量%，又更好為0.5~2.5重量%。 The amount of introduction of the aluminum chloride gas can be appropriately set, for example, in terms of alumina, preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, still more preferably 0.5 to 2.5 by weight, based on the produced titanium oxide particles. %.
且，作為較佳之樣態2，於前述步驟2中，使四氯化鈦與水反應，使四氯化鈦加熱水解，亦可製造二氧化鈦粒子。 Further, as a preferred aspect 2, in the above step 2, titanium tetrachloride is reacted with water to thermally hydrolyze titanium tetrachloride, and titanium dioxide particles can also be produced.
具體而言，將前述氯化鋁氣體、四氯化鈦氣體、燃料氣體及含氧氣體導入反應裝置中，使藉由前述燃料氣體與 含氧氣體之燃燒所生成之水與四氯化鈦氣體進行加熱水解反應。 Specifically, the aluminum chloride gas, the titanium tetrachloride gas, the fuel gas, and the oxygen-containing gas are introduced into the reaction device to cause the fuel gas and the fuel gas to The water produced by the combustion of the oxygen-containing gas is subjected to a heat hydrolysis reaction with the titanium tetrachloride gas.
水可藉由含氧氣體與燃料氣體反應而在反應裝置內製造。作為含氧氣體，可使用氧氣、大氣等。作為燃料氣體，可使用甲烷、乙烷、丙烷、丁烷、氫等。因此，於反應裝置中，導入前述氯化鋁氣體、四氯化鈦氣體、燃料氣體及含氧氣體，於反應裝置內使所得水與四氯化鈦氣體進行加熱水解反應。四氯化鈦氣體較好在導入反應裝置之前與氯化鋁氣體混合作成混合氣體，更好在即將導入反應裝置之前混合。 Water can be produced in the reaction apparatus by reacting an oxygen-containing gas with a fuel gas. As the oxygen-containing gas, oxygen, the atmosphere, or the like can be used. As the fuel gas, methane, ethane, propane, butane, hydrogen, or the like can be used. Therefore, in the reaction apparatus, the aluminum chloride gas, the titanium tetrachloride gas, the fuel gas, and the oxygen-containing gas are introduced, and the obtained water and the titanium tetrachloride gas are heated and hydrolyzed in the reaction apparatus. The titanium tetrachloride gas is preferably mixed with aluminum chloride gas to form a mixed gas before being introduced into the reaction apparatus, and is preferably mixed just before introduction into the reaction apparatus.
反應裝置可為任何形狀，但例如若為管狀反應器時，較好為豎型，此情況下，係自管的下部導入四氯化鈦氣體、燃料氣體及含氧氣體，氯化鋁氣體亦可自管的下部、管的中途或管的上部任一處導入。使用四氯化鈦與氯化鋁之混合氣體之情況時，較好自管的下部導入。 The reaction apparatus may be of any shape, but for example, in the case of a tubular reactor, it is preferably vertical. In this case, titanium tetrachloride gas, fuel gas and oxygen-containing gas are introduced from the lower portion of the tube, and aluminum chloride gas is also introduced. It can be introduced from the lower part of the tube, the middle of the tube or the upper part of the tube. When a mixed gas of titanium tetrachloride and aluminum chloride is used, it is preferably introduced from the lower portion of the tube.
水解溫度通常較好為700~1600℃之溫度，更好為800~1200℃，又更好為900~1100℃。以上述溫度通常可製造混合有金紅石型與銳鈦礦型之二氧化鈦。 The hydrolysis temperature is usually preferably from 700 to 1600 ° C, more preferably from 800 to 1200 ° C, and even more preferably from 900 to 1100 ° C. Titanium dioxide mixed with rutile type and anatase type can be usually produced at the above temperature.
氯化鋁氣體之導入量可適當設定，例如相對於生成之二氧化鈦粒子，換算為氧化鋁，較好為0.01~10重量%，更好為0.1~5重量%，又更好為0.5~2.5重量%。 The amount of introduction of the aluminum chloride gas can be appropriately set, for example, in terms of alumina, preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, still more preferably 0.5 to 2.5 by weight, based on the produced titanium oxide particles. %.
將如此製造之二氧化鈦粒子與氯氣、氯化氫氣體及其他氣體分離並回收。回收之二氧化鈦粒子亦可依據需要，以二氧化矽、氧化鋁、氧化鈦、氧化錫等無機 物、矽氧烷、偶合劑、有機酸等之有機物進行表面處理。表面處理有將二氧化鈦粒子作成漿料狀態，添加處理劑進行被覆處理之濕式法，以乾粉狀態混合處理劑進行被覆處理之乾式法，任一方法均可使用。如此製造之二氧化鈦粒子可使用於白色顏料、紅外線反射劑、紫外線遮蔽劑、觸媒、光觸媒、觸媒擔體、複合材料之原料等。 The titanium dioxide particles thus produced are separated from chlorine gas, hydrogen chloride gas, and other gases and recovered. The recovered titanium dioxide particles may also be inorganic, such as cerium oxide, aluminum oxide, titanium oxide or tin oxide, as needed. The organic matter such as a substance, a siloxane, a coupling agent, an organic acid or the like is subjected to surface treatment. The surface treatment may be a dry method in which the titanium oxide particles are in a slurry state, a wet treatment method in which a treatment agent is added to the coating treatment, and a coating treatment in a dry powder state is carried out, and any method may be used. The titanium dioxide particles thus produced can be used as a white pigment, an infrared reflecting agent, an ultraviolet shielding agent, a catalyst, a photocatalyst, a catalyst carrier, a raw material of a composite material, and the like.
以下利用實施例對本發明更具體說明，但本發明不受限於該等。 The invention will be more specifically described below by way of examples, but the invention is not limited thereto.
將固體氯化鋁饋入圖1所概視所示之熔解槽(耐熱耐壓容器)中，以200~210℃之溫度、0.30MPa之壓力下液化。接著，經由壓力調整機構自熔解槽使氯化鋁氣化，導入至經預熱之四氯化鈦氣體供給管中，恰在反應裝置之前，製造四氯化鈦與氯化鋁之混合氣體。氯化鋁氣體之混合量相對於生成之二氧化鈦粒子，換算為氧化鋁，調整為1重量%。 The solid aluminum chloride is fed into a melting tank (heat-resistant pressure vessel) as generally shown in Fig. 1, and liquefied at a temperature of 200 to 210 ° C and a pressure of 0.30 MPa. Next, aluminum chloride is vaporized from the melting tank through a pressure adjusting mechanism, and introduced into the preheated titanium tetrachloride gas supply pipe, and a mixed gas of titanium tetrachloride and aluminum chloride is produced just before the reaction apparatus. The amount of the aluminum chloride gas blended was adjusted to 1% by weight based on the amount of the titanium oxide particles produced.
於反應裝置中，前述之混合氣體與預熱之氧通過不同入口連續導入並迅速混合，在約900℃~1100℃之溫度反應，製造二氧化鈦粒子。所得二氧化鈦粒子自反應裝置以冷卻導管排出，經急冷獲得二氧化鈦顏料。 In the reaction apparatus, the mixed gas and the preheated oxygen are continuously introduced through different inlets and rapidly mixed, and reacted at a temperature of about 900 ° C to 1100 ° C to produce titanium oxide particles. The obtained titanium oxide particles were discharged from a reaction apparatus through a cooling duct, and quenched to obtain a titanium dioxide pigment.
與實施例1同樣，於熔解槽內饋入氯化鋁並使之液化，接著使之氣化。於反應裝置中，分別導入前述氯化鋁氣體、四氯化鈦氣體、丙烷氣體、氧氣，使四氯化鈦氣體與由丙烷氣體與氧氣燃燒所生成之水接觸進行加熱水解反應獲得二氧化鈦粒子。氯化鋁氣體之導入量，相對於生成之二氧化鈦粒子，換算為氧化鋁，調整為2重量%。 In the same manner as in Example 1, aluminum chloride was fed into the melting tank and liquefied, followed by gasification. In the reaction apparatus, the aluminum chloride gas, titanium tetrachloride gas, propane gas, and oxygen gas are introduced, respectively, and the titanium tetrachloride gas is brought into contact with water generated by combustion of propane gas and oxygen gas to carry out heat hydrolysis reaction to obtain titanium dioxide particles. The amount of introduction of the aluminum chloride gas was adjusted to 2% by weight in terms of alumina based on the produced titanium oxide particles.
實施例1、2中，由於可控制氯化鋁氣體之流量，故可製造品質偏差較少之二氧化鈦粒子。 In Examples 1 and 2, since the flow rate of the aluminum chloride gas can be controlled, it is possible to produce titanium dioxide particles having a small variation in quality.
本發明係二氧化鈦粒子之製造方法，可製造品質偏差較少之二氧化鈦粒子，而可使用於白色顏料、紅外線反射劑、紫外線遮蔽劑、觸媒、光觸媒、觸媒擔體、複合材料之原料等。 The present invention relates to a method for producing titanium dioxide particles, which can produce titanium dioxide particles having a small variation in quality, and can be used for a white pigment, an infrared reflecting agent, an ultraviolet shielding agent, a catalyst, a photocatalyst, a catalyst carrier, a raw material of a composite material, and the like.
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