AU2007338499B2 - Method for the production of titanium dioxide by oxygenating titanium tetrachloride - Google Patents
Method for the production of titanium dioxide by oxygenating titanium tetrachloride Download PDFInfo
- Publication number
- AU2007338499B2 AU2007338499B2 AU2007338499A AU2007338499A AU2007338499B2 AU 2007338499 B2 AU2007338499 B2 AU 2007338499B2 AU 2007338499 A AU2007338499 A AU 2007338499A AU 2007338499 A AU2007338499 A AU 2007338499A AU 2007338499 B2 AU2007338499 B2 AU 2007338499B2
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- AU
- Australia
- Prior art keywords
- flow
- reactor
- titanium tetrachloride
- tubular reactor
- titanium dioxide
- 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.)
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 23
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 title claims abstract description 18
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 230000001706 oxygenating effect Effects 0.000 title abstract 2
- 238000001816 cooling Methods 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 27
- 239000007789 gas Substances 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims description 22
- 239000000049 pigment Substances 0.000 abstract description 9
- 238000009826 distribution Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract 2
- 238000009991 scouring Methods 0.000 abstract 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000725 suspension Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
-
- 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
Landscapes
- 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
The invention relates to the production of titanium dioxide by oxygenating titanium tetrachloride and then cooling the titanium dioxide particle-gas mixture while adding scouring particles in a cooling section, the gas-particle flow being made to rotate. According to the invention, the titanium tetrachloride is introduced into the axial oxygen-containing flow on the cross-sectional plane of the tubular reactor, but not in the radial direction. The flow velocity of the oxygen-containing gas exceeds 20 m/s, particularly reaching at least 40 m/s. The method according to the invention makes it possible to effectively remove accumulated TiO from the internal wall and the cooling section of the tubular reactor, thus increasing the cooling performance, and produce a TiO pigment which has a narrow grain size distribution.
Description
1 Method for manufacturing titanium dioxide by oxidising titanium tetrachloride 5 Field of the invention The invention relates to the manufacture of titanium dioxide by oxidising titanium tetrachloride and subsequently cooling the titanium dioxide particle/gas mixture in a cooling section, where the gas/particle flow is caused to rotate. 10 Technological background of the invention A commercially applied method for manufacturing titanium dioxide pigment, known as the 15 chloride process, is based on titanium tetrachloride (TiCl 4 ) being converted into titanium dioxide and chlorine gas in a tubular reactor using a preheated, oxidising gas, such as oxygen, air, etc., and certain additives. The oxidation reaction is highly exothermic, meaning that the reaction mixture displays temperatures of more than 1,500 0 C following complete conversion. In a downstream reactor cooling section, the TiO 2 pigment particles formed are 20 cooled to below roughly 400 0 C and separated from the gas flow. Cooling directly after the completion of particle formation must take place rapidly in order to prevent further particle growth. To this end, the tubular reactor or the reactor cooling section is externally cooled with water from this point onwards. However, the transfer of heat to the cooling water is severely impeded by the accumulation 25 of TiO 2 pigment particles on the inner wall of the tubular reactor or the reactor cooling section. According to US 2,721,626, scrub solids are introduced into the reactor cooling section for this reason, with the intention of detaching pigment accumulating on the inner walls. The scrub solids used in this patent are abrasive particles, such as quartz sand or aggregated TiO 2 particles with particle sizes of roughly 0.15 to 6.35 mm. The scrub solids are 30 introduced into the TiO 2 /gas suspension at one or more points in the reactor cooling section. Because of their weight, the scrub solids begin to concentrate in the lower one-third of the tube circumference in the horizontal reactor cooling section just a short time after being added. While this area of the inner wall is thoroughly cleaned of adhering pigment, the higher 35 areas of the circumference are insufficiently cleaned, and the cooling of the gas suspension is inadequate. In order nevertheless to achieve sufficient heat transfer, it is standard practice 2 to substantially increase the amount of scrub solids added. This increases the burden on the system for manufacturing, adding and eliminating the scrub solids, thus giving rise to higher costs for energy consumption and maintenance, among other things. 5 US 6,419,893 81 describes a method for more efficient removal of the TiO 2 deposits on the inner wall of the reactor cooling section. According to US 6,419,893 B1, at least a partial area of the reactor cooling section is provided with ribs that run in helical fashion on the inner wall and serve as guide elements, as a result of which the scrub solids are guided through the cooling section in a helical flow. The ribs are arranged at an angle of 20 to 60. 10 US 2006/0133989 Al discloses a reactor cooling section of helical overall design that is said to achieve improved cleaning of the inner wall by the scrub solids. DE 1 259 851 discloses a method for manufacturing titanium dioxide by reaction in the gas 15 phase, where part of the gaseous reaction components is introduced tangentially into the reactor. This method is designed, on the one hand, to reduce the formation of deposits on the reactor walls by tangential introduction of one reaction component and, on the other hand, to achieve rapid thorough mixing of the reaction components by generating a back flow (so-called "swirl flow"). The swirl flow is further intensified by the cross-section of the reactor 20 expanding conically in the direction of flow. However, swirl flow leads to residence times of different length for the individual particles in the reactor. A narrow particle size distribution is important for the quality of a titanium dioxide pigment, particularly for the tinting strength (TS). However, for generating a narrow particle size distribution, not rapid thorough mixing of the reaction components is of primary importance, 25 but a narrow residence time distribution of the TiO 2 particles in the reactor, meaning that any kind of swirl flow in the reactor should be avoided. Summary of the invention 30 The present invention seeks to indicate a method, constituting an improvement compared to the prior art, for, on the one hand, effectively freeing the inner wall of the tubular reactor and the reactor cooling section of TiO 2 deposits with the help of scrub solids, thereby achieving a better cooling performance, and, on the other hand, producing a TiO 2 pigment with a narrow particle size distribution. 35 In accordance with one aspect the present invention provides a method for manufacturing 3 titanium dioxide particles in a cylindrical tubular reactor by reacting titanium tetrachloride and an axially introduced, oxygen-bearing gas and subsequently cooling the particles, whereby the titanium tetrachloride is introduced into the tubular reactor in the cross-sectional plane of the tubular reactor, but not in the radial direction, and whereby the flow velocity of the 5 oxygen-bearing gas is more than 20 m/s, particularly at least 40 m/s. According to another aspect the present invention provides a method for manufacturing titanium dioxide particles in a cylindrical tubular reactor by reacting titanium tetrachloride and an axially introduced, oxygen-bearing gas and subsequently introducing a flow of scrub 10 solids and cooling the titanium dioxide particles, wherein the titanium tetrachloride is introduced into the tubular reactor in the cross sectional plane of the tubular reactor, but not in the radial direction, and whereby the flow velocity of the oxygen-bearing gas is more than 20 m/s. 15 Further advantageous embodiments of the invention are described in the sub-claims. Description of the invention The invention is explained by means of Figures 1, 2, and 3 without these being intended as a 20 restriction. Figure 1 is a schematic side view of the tubular reactor. Figure 2 is a cross-sectional view taken along sectional lines 2-2 of Fig. 1 for one embodiment of the invention and Figure 3 is a cross-sectional view taken along sectional lines 2-2 of Fig. 1 for an alternate embodiment of the invention. 25 Here and below, the term tubular reactor is taken to mean the part of the reactor in which the TiCl 4 oxidation reaction and TiO 2 particle formation take place (see Fig. 1, (10)). The reactor cooling section is taken to be the downstream part of the tubular reactor, where the reaction is arrested by rapid cooling and the gas suspension is further cooled. Various additives and 30 gases, such as aluminium chloride, chlorine, nitrogen, alkali salts, etc., are customarily introduced into the reactor together with the TiCl 4 . Here and below, the term 'TiCl4" is to be taken to mean the oxygen-free flow consisting essentially of TiC 4 . The term "02" is to be taken to mean the oxygen-bearing gas flow, here and below. 35 The invention is based on the knowledge that a major part of the heat is dissipated at the start of the reactor cooling section, where the high temperature of the TiO 2 /gas suspension 4 generates a high, driving temperature gradient towards the inner wall of the tube. The abrasive action of the scrub solids in this area can be substantially improved by causing the scrub solids flow, or the entire flow, to rotate. This rotation and centrifugal force distribute the scrub solids over the entire circumference of the tube, simultaneously pressing them against 5 the wall, as a result of which the latter is cleaned uniformly and intensively. Referring to Figures 1 to 3, the TiC 4 is preferably introduced into the reactor (10) through nozzles (12). In the framework of the invention, the term nozzles is taken to mean all kinds of feed lines, such as ducts, pipes, etc., and all kinds of nozzles, such as Venturi tubes or Laval nozzles. The reactor (10) is a cylindrical structure and includes a longitudinal axis (14). 10 Oxygen is introduced into the reactor (10) in the direction of axis (14). TiCl 4 is introduced into the reactor (10) through nozzles (12) in a tangential direction, but not in radial direction. Figure 2 illustrates a cross-sectional plane of the reactor (10) having a radius shown by line (16). TiC1 4 is introduced into the reactor (10) in a tangential direction along a path shown by line (18). Line (18) is offset from radius (16) by angle a. 15 The nozzles (12) can be distributed over the circumference of the reactor (10) in a common axial position (Fig. 2). Alternatively, the nozzles (12) can also be axially offset relative to each other. In a further embodiment of the invention, the TiC1 4 can also be introduced into the reactor through a slit-like opening (20) (Fig. 3). In this embodiment, the tangential direction of the 20 flow is brought about by baffle plates (22) in the slit-like opening (20) that are set at a corresponding angle a. According to the invention, the entire flow - reaction mixture and scrub solids - is caused to rotate in the tubular reactor (10) and the reactor cooling section by introducing the added 25 titanium tetrachloride into the tubular reactor (10) tangentially. Owing to its high specific weight, the TiCl 4 introduces substantial tangential momentum into the flow, this being sufficient to generate lasting rotation. Tangential introduction of the TiCl 4 into the tubular reactor (10) means that introduction takes place in the cross-sectional plane of the tubular reactor (10), but at an angle a of > 0 0 to 30 < 90*, preferably 1* to 150, and particularly 50 to 100, relative to the radial direction (Figs. 2 and 3). Surprisingly, back flow (swirl flow) in the reactor (10) can be largely avoided in the method according to the invention, and a uniform residence time thus achieved for all TiO 2 particles 35 in the reactor (10). In contrast to the teaching in DE 1 259 851, this is achieved by the axially introduced 02 flow having a flow velocity of more than 20 m/s, particularly at least 40 m/s, 5 and the tubular reactor (10) having a cylindrical form. Under these conditions it is possible to introduce a high tangential momentum to achieve a high cleaning effect without generating of swirl flow. The momentum ratio (ratio of the products of flow velocity and specific weight) of the tangentially introduced reaction component (TiCl 4 ) to the axially introduced gaseous 5 component (02) is at least about 100. The improvement of heat transfer to the wall of the cooling section, achieved by introducing the TiCl 4 in accordance with the invention, can be further improved if the scrub solids are extensively scattered when introduced into the tubular reactor (10), this bringing about 10 uniform distribution of the scrub solids and, accordingly, uniform cleaning of the reactor wall. The scattering can be achieved by causing the flow of scrub solids to rotate strongly prior to being introduced into the reactor. This rotation can, for example, be achieved by designing the feed port in a form similar to a cyclone, into which the scrub solids flow is introduced tangentially by means of pneumatic conveying. 15 Compared to the methods according to US 6,419,893 B1 and US 2006/0133989 Al, the invention is characterised in that, on the one hand, the entire flow is caused to rotate, and cleaning of the inner wall and cooling of the gas suspension are thus optimised. Moreover, no complex design measures downstream of the point of TiCl 4 introduction are necessary, 20 such as wear-susceptible internal fixtures or a helical design of the entire reactor cooling section. Compared to the method according to DE 1 259 851 the invention is furthermore characterised in that, despite the high tangential momentum of the TiCl 4 flow, swirl flow is largely avoided and TiO 2 pigment particles with a narrow particle size distribution, and thus improved tinting strength (TS), can be manufactured. 25 Example An example of the invention is explained below, without this being intended as a restriction. 12 t/h TiCl 4 are introduced into a tubular reactor with an inside diameter of approx. 0.3 m by 30 means of 10 circular nozzles, and caused to react with preheated oxygen-bearing gas. The nozzles are located at a common axial position on the tubular reactor and distributed evenly over the circumference. All nozzles are set tangentially in the same direction in the cross sectional plane, in such a way that they deviate from the radial direction by 60. Compared to a purely radial layout of the nozzles, this configuration reduces the scrub solids requirement 35 from roughly 2.0 to 1.2 t/h.
6 Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps. 5 The reference in this specification to any prior publication (or information derived from it), or to any matter which is known, is not, and should not be taken as an acknowledgment or admission or any form of suggestion that that prior publication (or information derived from it) or known matter forms part of the common general knowledge in the field of endeavour to 10 which this specification relates.
Claims (10)
1. A method for manufacturing titanium dioxide particles in a cylindrical tubular reactor by reacting titanium tetrachloride and an axially introduced, oxygen-bearing gas and 5 subsequently introducing a flow of scrub solids and cooling the titanium dioxide particles, wherein the titanium tetrachloride is introduced into the tubular reactor in the cross sectional plane of the tubular reactor, but not in the radial direction, and whereby the flow velocity of the oxygen-bearing gas is more than 20 m/s. 10
2. A method according to claim 1, wherein the flow velocity of the oxygen-bearing gas is more than 40 m/s.
3. The method according to claim 1 or claim 2, wherein the titanium tetrachloride is introduced at an angle between > 0 * and < 90*. 15
4. A method according to any one of claims 1 to 3, wherein the titanium tetrachloride is introduced at an angle selected from between 10 and 50 and 50 and 100 relative to the radial direction. 20
5. The method according to claim 1, wherein the titanium tetrachloride is introduced by means of individual nozzles.
6. The method according to claim 5, wherein the nozzles are axially offset relative to each other. 25
7. The method according to any one of claims 1 to 4, wherein the titanium tetrachloride is introduced through a slit-like opening displaying baffle plates deviating from the radial direction. 30
8. The method according to any one of the preceding claims wherein a flow of scrub solids is introduced into a cooling section of the reactor the scrub solids flow is caused to rotate strongly prior to being introduced into the reactor.
9. The method according to any one of the preceding claims wherein the product of flow 35 velocity and specific weight of the TiCl 4 flow is at least 100 times the product of flow velocity and specific weight of the 02 flow. 8
10. A method of manufacturing titanium dioxide particles according to claim 1 substantially as herein described with reference to the example and/or the accompanying figures.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006060988.3 | 2006-12-20 | ||
| DE102006060988 | 2006-12-20 | ||
| DE102007048553.2 | 2007-10-09 | ||
| DE102007048553A DE102007048553A1 (en) | 2006-12-20 | 2007-10-09 | Process for the preparation of titanium dioxide by oxidation of titanium tetrachloride |
| PCT/EP2007/010780 WO2008077476A2 (en) | 2006-12-20 | 2007-12-11 | Method for the production of titanium dioxide by oxygenating titanium tetrachloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU2007338499A1 AU2007338499A1 (en) | 2008-07-03 |
| AU2007338499B2 true AU2007338499B2 (en) | 2012-11-01 |
Family
ID=39431960
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2007338499A Active AU2007338499B2 (en) | 2006-12-20 | 2007-12-11 | Method for the production of titanium dioxide by oxygenating titanium tetrachloride |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP2129626B1 (en) |
| JP (1) | JP5409379B2 (en) |
| CN (1) | CN101547865B (en) |
| AU (1) | AU2007338499B2 (en) |
| DE (1) | DE102007048553A1 (en) |
| MX (1) | MX2009005234A (en) |
| RU (1) | RU2440297C2 (en) |
| SA (1) | SA110320025B1 (en) |
| TW (1) | TWI422527B (en) |
| WO (1) | WO2008077476A2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107720815A (en) * | 2017-11-14 | 2018-02-23 | 黄林海 | A kind of production method of rutile titanium dioxide |
| CN109704397A (en) * | 2019-02-15 | 2019-05-03 | 河南佰利联新材料有限公司 | A method of producing high durable semi-finished product titanium dioxide |
| WO2021212405A1 (en) * | 2020-04-23 | 2021-10-28 | 东华工程科技股份有限公司 | Chlorination process-based titanium dioxide oxidation reactor |
| CN112275247B (en) * | 2020-09-30 | 2022-05-24 | 河南佰利联新材料有限公司 | Combustion ring |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3485584A (en) * | 1965-04-15 | 1969-12-23 | Bayer Ag | Vapour phase oxidation process |
| US3532462A (en) * | 1963-04-27 | 1970-10-06 | Bayer Ag | Method of effecting gas-phase reactions |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1442690A1 (en) * | 1964-01-04 | 1969-04-17 | Bayer Ag | Process for carrying out gas phase reactions |
| BE755089A (en) * | 1969-08-20 | 1971-02-22 | Montedison Spa | REACTOR AND PROCESS FOR THE MANUFACTURE OF TITANIUM DIOXIDE OF PIGMENTAL QUALITY |
| US3663283A (en) * | 1969-10-02 | 1972-05-16 | Richard A Hebert | Process and apparatus for the production of finely-divided metal oxides |
| JPH03252315A (en) * | 1990-02-27 | 1991-11-11 | Osaka Titanium Co Ltd | Production of high-purity titanium oxide |
| PL187022B1 (en) * | 1996-07-25 | 2004-04-30 | Kerr Mcgee Chemical Llc | Method of and apparatus for obtaining titanium dioxide |
| US6350427B1 (en) * | 1999-07-27 | 2002-02-26 | Kerr-Mcgee Chemical Llc | Processes for reacting gaseous reactants containing solid particles |
| US6419893B1 (en) * | 2000-09-18 | 2002-07-16 | Kerr-Mcgee Chemical Llc | Process for producing and cooling titanium dioxide |
| US20020155059A1 (en) * | 2001-04-24 | 2002-10-24 | Tekna Plasma Systems Inc. | Plasma synthesis of titanium dioxide nanopowder and powder doping and surface modification process |
-
2007
- 2007-10-09 DE DE102007048553A patent/DE102007048553A1/en not_active Withdrawn
- 2007-11-19 TW TW096143630A patent/TWI422527B/en not_active IP Right Cessation
- 2007-12-11 JP JP2009541828A patent/JP5409379B2/en active Active
- 2007-12-11 AU AU2007338499A patent/AU2007338499B2/en active Active
- 2007-12-11 CN CN200780044640.0A patent/CN101547865B/en active Active
- 2007-12-11 EP EP07856539.7A patent/EP2129626B1/en active Active
- 2007-12-11 MX MX2009005234A patent/MX2009005234A/en active IP Right Grant
- 2007-12-11 WO PCT/EP2007/010780 patent/WO2008077476A2/en not_active Ceased
- 2007-12-11 RU RU2009127656/05A patent/RU2440297C2/en not_active IP Right Cessation
- 2007-12-12 SA SA110320025A patent/SA110320025B1/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3532462A (en) * | 1963-04-27 | 1970-10-06 | Bayer Ag | Method of effecting gas-phase reactions |
| US3485584A (en) * | 1965-04-15 | 1969-12-23 | Bayer Ag | Vapour phase oxidation process |
Also Published As
| Publication number | Publication date |
|---|---|
| MX2009005234A (en) | 2009-06-05 |
| SA110320025B1 (en) | 2014-06-25 |
| TWI422527B (en) | 2014-01-11 |
| EP2129626B1 (en) | 2019-01-23 |
| AU2007338499A1 (en) | 2008-07-03 |
| WO2008077476A2 (en) | 2008-07-03 |
| CN101547865B (en) | 2013-02-27 |
| JP5409379B2 (en) | 2014-02-05 |
| TW200846288A (en) | 2008-12-01 |
| WO2008077476A3 (en) | 2008-11-20 |
| EP2129626A2 (en) | 2009-12-09 |
| DE102007048553A1 (en) | 2008-06-26 |
| JP2010513196A (en) | 2010-04-30 |
| CN101547865A (en) | 2009-09-30 |
| RU2009127656A (en) | 2011-01-27 |
| RU2440297C2 (en) | 2012-01-20 |
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| FGA | Letters patent sealed or granted (standard patent) |