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WO2013147163A1 - Procédé de fabrication de particules de dioxyde de titane - Google Patents

Procédé de fabrication de particules de dioxyde de titane Download PDF

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Publication number
WO2013147163A1
WO2013147163A1 PCT/JP2013/059541 JP2013059541W WO2013147163A1 WO 2013147163 A1 WO2013147163 A1 WO 2013147163A1 JP 2013059541 W JP2013059541 W JP 2013059541W WO 2013147163 A1 WO2013147163 A1 WO 2013147163A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
aluminum chloride
titanium dioxide
dioxide particles
oxygen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2013/059541
Other languages
English (en)
Japanese (ja)
Inventor
薫 櫻井
一哉 米田
広喜 今井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ishihara Sangyo Kaisha Ltd
Original Assignee
Ishihara Sangyo Kaisha Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ishihara Sangyo Kaisha Ltd filed Critical Ishihara Sangyo Kaisha Ltd
Priority to JP2014508097A priority Critical patent/JP6049696B2/ja
Publication of WO2013147163A1 publication Critical patent/WO2013147163A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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

Definitions

  • the present invention relates to a method for producing titanium dioxide particles.
  • Titanium dioxide particles are mainly used as a white pigment in many fields.
  • the titanium dioxide particles are produced by oxidizing titanium tetrachloride gas with oxygen gas at a temperature of 900 to 1600 ° C., and 0.01 to 10% by weight of aluminum chloride in terms of aluminum oxide based on the generated titanium dioxide particles.
  • This aluminum chloride is solid at room temperature and has a melting point of 192.4 ° C. (anhydride), but exhibits sublimation properties from 160 ° C.
  • Patent Document 1 a method in which solid aluminum chloride is added to liquid titanium tetrachloride, heated and azeotroped, and aluminum chloride gas is present in titanium tetrachloride gas.
  • Patent Document 2 a method in which solid aluminum chloride is directly heated and sublimated to generate aluminum chloride gas.
  • Patent Document 1 since solid aluminum chloride is added to liquid titanium tetrachloride and vaporized, it is difficult to accurately control the content of aluminum chloride gas in the titanium tetrachloride gas. There is a problem that the quality of the product tends to vary.
  • the method of Patent Document 2 has a problem that, since solid aluminum chloride is sublimated, it is difficult to control the flow rate of the aluminum chloride gas, and the aluminum chloride gas is diluted for transportation by the carrier gas.
  • the present inventors have made various studies in order to facilitate the flow rate control of the aluminum chloride gas and to reduce the carrier gas.
  • the aluminum chloride gas can be transported by the pressure, the flow rate of the aluminum chloride gas can be controlled by controlling the pressure, and titanium dioxide particles with little variation in quality can be obtained by using the aluminum chloride gas with a controlled flow rate.
  • the present invention has been completed.
  • the present invention includes (1) a step 1 in which solid aluminum chloride is liquefied under heat and pressure and then vaporized to produce aluminum chloride gas, and (2) in the presence of the aluminum chloride gas produced in step 1 above. And a process 2 for reacting titanium tetrachloride gas with oxygen and / or water.
  • the present invention is a method for producing titanium dioxide particles, and since the flow rate of aluminum chloride gas can be controlled by controlling the pressure and temperature, titanium dioxide particles with little variation in quality can be produced.
  • the present invention is a method for producing titanium dioxide particles, comprising: (1) liquefying solid aluminum chloride under heat and pressure and then evaporating to produce aluminum chloride gas; (2) in step 1 above; A step 2 of reacting the titanium tetrachloride gas with oxygen and / or water in the presence of the produced aluminum chloride gas;
  • the above-mentioned step 1 is a step of producing aluminum chloride gas.
  • Solid aluminum chloride is put in a heat and pressure resistant container, and the inside of the container is heated and pressurized so as to be in a liquid state so as not to sublimate the aluminum chloride.
  • corrosion resistance can be achieved by using a metal with excellent corrosion resistance such as tantalum or Hastelloy, or by coating glass or ceramics on the surface of various metal materials. It is preferable to produce a pressure vessel or piping using the provided one.
  • solid aluminum chloride is put into a heat and pressure resistant container and pressurized.
  • the aluminum chloride is liquefied (melted).
  • This liquid aluminum chloride is in a vapor-liquid equilibrium state under heat and pressure, and if it is further heated under a constant pressure, or depressurized under a constant temperature with a pressure adjustment mechanism, etc., the equilibrium state shifts and vaporizes (evaporates). Therefore, the aluminum chloride gas can be taken out of the container and introduced into the reactor in the next step 2.
  • the temperature in the container may be any condition as long as aluminum chloride is liquefied (melted) without sublimation, preferably 190 to 230 ° C, more preferably 195 to 220 ° C, and further preferably 200 to 210 ° C.
  • the pressure can be controlled by pressurizing with a gas such as oxygen or nitrogen.
  • the pressure in the container is preferably controlled to 0.23 megapascals or more, more preferably 0.25 to 0.4 megapascals, and even more preferably 0.27 to 0.35 megapascals.
  • AlCl 3 As aluminum chloride, the chemical formula AlCl 3 and the like are known, and there are an anhydride and a hexahydrate. An anhydride is preferred.
  • step 2 is a process for producing titanium dioxide particles.
  • the aluminum chloride gas produced in step 1 is introduced into the reactor, and in the presence of the aluminum chloride gas, titanium tetrachloride gas and oxygen and / or React with water.
  • a gas obtained by mixing the aluminum chloride gas and the titanium tetrachloride gas and an oxygen-containing gas are introduced into a reaction apparatus to react the titanium tetrachloride gas with oxygen.
  • Titanium tetrachloride is a colorless to pale yellow liquid represented by the chemical formula TiCl 4 and having a melting point of ⁇ 25 ° C. and a boiling point of 136.4 ° C. Titanium tetrachloride gas obtained by evaporating liquid titanium tetrachloride is introduced into the reactor, while oxygen-containing gas such as oxygen and air is introduced to oxidize titanium tetrachloride.
  • the titanium tetrachloride gas is preferably mixed with aluminum chloride gas before being introduced into the reactor to form a mixed gas, and more preferably mixed immediately before the reactor.
  • a mixed gas of titanium tetrachloride and aluminum chloride and an oxygen-containing gas such as oxygen and air are separately introduced into the reactor.
  • the reactor may be of any shape, but for example, if it is a tubular reactor, a horizontal type is preferable.
  • the titanium tetrachloride gas and oxygen are contained from the side of the tube entrance or from the side near the tube entrance.
  • Gas may be introduced, and aluminum chloride gas may also be introduced from the inlet of the pipe, from the side near the inlet of the pipe, or from the side in the middle of the pipe.
  • the position where such a side gas introduction part is provided is not particularly limited, but the lower part of the pipe is preferable if it is provided near the entrance, and the upper part is preferable if it is in the middle of the pipe.
  • a mixed gas of titanium tetrachloride and aluminum chloride it is preferably introduced from the lower part of the side surface in the vicinity of the inlet of the tube.
  • the oxidation reaction temperature is usually preferably 700 to 1600 ° C, more preferably 800 to 1200 ° C, and still more preferably 900 to 1100 ° C.
  • rutile type titanium dioxide particles can be produced at the above temperature.
  • the amount of aluminum chloride gas introduced can be set as appropriate. For example, it is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight in terms of aluminum oxide with respect to the produced titanium dioxide particles. More preferred is 0.5 to 2.5% by weight.
  • titanium dioxide particles can be produced by reacting titanium tetrachloride with water in the step 2 to hydrolyze titanium tetrachloride.
  • the aluminum chloride gas, titanium tetrachloride gas, fuel gas, and oxygen-containing gas are introduced into a reactor, and water and titanium tetrachloride gas generated by combustion of the fuel gas and oxygen-containing gas are used. And hydrolytically react.
  • Water can be produced in the reactor by the reaction of oxygen-containing gas and fuel gas.
  • oxygen-containing gas oxygen, air, or the like can be used.
  • fuel gas methane, ethane, propane, butane, hydrogen or the like can be used.
  • the aluminum chloride gas, titanium tetrachloride gas, fuel gas and oxygen-containing gas are introduced into the reaction apparatus, and the water obtained in the reaction apparatus and the titanium tetrachloride gas are subjected to a thermal hydrolysis reaction.
  • the titanium tetrachloride gas is preferably mixed with aluminum chloride gas before being introduced into the reactor to form a mixed gas, and more preferably mixed immediately before the reactor.
  • the reactor may have any shape, but for example, a tubular reactor is preferable, and in this case, titanium tetrachloride gas, fuel gas, and oxygen-containing gas are introduced from the lower part of the tube, Aluminum chloride gas may be introduced from any of the lower part of the pipe, the middle of the pipe, or the upper part of the pipe. When a mixed gas of titanium tetrachloride and aluminum chloride is used, it is preferably introduced from the lower part of the pipe.
  • the hydrolysis temperature is usually preferably 700 to 1600 ° C, more preferably 800 to 1200 ° C, and still more preferably 900 to 1100 ° C. Titanium dioxide in which rutile type and anatase type are usually mixed can be produced at the above temperature.
  • the amount of aluminum chloride gas introduced can be set as appropriate. For example, it is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight in terms of aluminum oxide with respect to the produced titanium dioxide particles. More preferred is 0.5 to 2.5% by weight.
  • the titanium dioxide particles produced in this way are separated from chlorine gas, hydrochloric acid gas and other gases and recovered.
  • the recovered titanium dioxide particles may be surface-treated with an inorganic material such as silica, alumina, titania or tin oxide, or an organic material such as siloxane, coupling agent or organic acid, if necessary.
  • an inorganic material such as silica, alumina, titania or tin oxide, or an organic material such as siloxane, coupling agent or organic acid, if necessary.
  • As the surface treatment there are a wet method in which titanium dioxide particles are in a slurry state and a treatment agent is added to perform a coating treatment, and a dry method in which a treatment agent is mixed and coated in a dry powder state, and any method can be used.
  • the titanium dioxide particles produced in this way can be used as white pigments, infrared reflectors, ultraviolet shielding agents, catalysts, photocatalysts, catalyst carriers, raw materials for composite materials, and
  • Example 1 Solid aluminum chloride was placed in a melting tank (heat-resistant pressure-resistant vessel) schematically shown in FIG. 1 and liquefied at a temperature of 200 to 210 ° C. and a pressure of 0.30 megapascal. Next, aluminum chloride was vaporized from the melting tank through a pressure adjusting mechanism and introduced into a preheated titanium tetrachloride gas supply pipe to produce a mixed gas of titanium tetrachloride and aluminum chloride immediately before the reactor. The mixing amount of the aluminum chloride gas was adjusted to 1% by weight in terms of aluminum oxide with respect to the produced titanium dioxide particles.
  • a melting tank heat-resistant pressure-resistant vessel
  • the above mixed gas and preheated oxygen were continuously introduced through another inlet and rapidly mixed, and reacted at a temperature of about 900 ° C. to 1100 ° C. to produce titanium dioxide particles.
  • the obtained titanium dioxide particles were discharged from the reactor into a cooling conduit and quenched to obtain a titanium dioxide pigment.
  • Example 2 In the same manner as in Example 1, aluminum chloride was placed in a melting tank to be liquefied and then vaporized.
  • the above-mentioned aluminum chloride gas, titanium tetrachloride gas, propane gas, and oxygen gas are separately introduced into the reactor and brought into contact with water produced by the combustion of propane gas and oxygen gas to heat and hydrolyze the titanium tetrachloride gas.
  • Titanium dioxide particles were obtained by decomposition reaction.
  • the amount of aluminum chloride gas introduced was adjusted to 2% by weight in terms of aluminum oxide with respect to the produced titanium dioxide particles.
  • the present invention is a method for producing titanium dioxide particles, which can produce titanium dioxide particles with little variation in quality, and can be used for white pigments, infrared reflectors, ultraviolet shielding agents, catalysts, photocatalysts, catalyst carriers, raw materials for composite materials, etc. Can be used.

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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)
PCT/JP2013/059541 2012-03-30 2013-03-29 Procédé de fabrication de particules de dioxyde de titane Ceased WO2013147163A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2014508097A JP6049696B2 (ja) 2012-03-30 2013-03-29 二酸化チタン粒子の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012079190 2012-03-30
JP2012-079190 2012-03-30

Publications (1)

Publication Number Publication Date
WO2013147163A1 true WO2013147163A1 (fr) 2013-10-03

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JP (1) JP6049696B2 (fr)
TW (1) TW201406663A (fr)
WO (1) WO2013147163A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB987335A (en) * 1962-03-20 1965-03-24 Aluminium Lab Ltd Method of evaporating aluminium trihalides
JP2001039704A (ja) * 1998-06-25 2001-02-13 Ishihara Sangyo Kaisha Ltd 金属酸化物の製造方法
JP2010505007A (ja) * 2006-09-18 2010-02-18 トロノックス エルエルシー 二酸化チタン顔料の作成工程
JP2010509163A (ja) * 2006-11-02 2010-03-25 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 低下した塩化物を有する二酸化チタン粒子の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB987335A (en) * 1962-03-20 1965-03-24 Aluminium Lab Ltd Method of evaporating aluminium trihalides
JP2001039704A (ja) * 1998-06-25 2001-02-13 Ishihara Sangyo Kaisha Ltd 金属酸化物の製造方法
JP2010505007A (ja) * 2006-09-18 2010-02-18 トロノックス エルエルシー 二酸化チタン顔料の作成工程
JP2010509163A (ja) * 2006-11-02 2010-03-25 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 低下した塩化物を有する二酸化チタン粒子の製造方法

Also Published As

Publication number Publication date
JP6049696B2 (ja) 2016-12-21
TW201406663A (zh) 2014-02-16
JPWO2013147163A1 (ja) 2015-12-14

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