RU2005129708A - Получение и применение каталитической композиции - Google Patents
Получение и применение каталитической композиции Download PDFInfo
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- RU2005129708A RU2005129708A RU2005129708/04A RU2005129708A RU2005129708A RU 2005129708 A RU2005129708 A RU 2005129708A RU 2005129708/04 A RU2005129708/04 A RU 2005129708/04A RU 2005129708 A RU2005129708 A RU 2005129708A RU 2005129708 A RU2005129708 A RU 2005129708A
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- 239000000203 mixture Substances 0.000 title claims 16
- 230000003197 catalytic effect Effects 0.000 title claims 3
- 238000000034 method Methods 0.000 claims 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 8
- 239000010953 base metal Substances 0.000 claims 6
- 150000002736 metal compounds Chemical class 0.000 claims 6
- 239000000463 material Substances 0.000 claims 4
- 229910052751 metal Inorganic materials 0.000 claims 4
- 239000002184 metal Substances 0.000 claims 4
- 150000002739 metals Chemical class 0.000 claims 4
- 229910052759 nickel Inorganic materials 0.000 claims 4
- 239000000725 suspension Substances 0.000 claims 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 3
- 238000010438 heat treatment Methods 0.000 claims 3
- 229910052750 molybdenum Inorganic materials 0.000 claims 3
- 239000011733 molybdenum Substances 0.000 claims 3
- 229910052760 oxygen Inorganic materials 0.000 claims 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 2
- 239000003513 alkali Substances 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 238000001125 extrusion Methods 0.000 claims 2
- 239000010703 silicon Substances 0.000 claims 2
- 229910052710 silicon Inorganic materials 0.000 claims 2
- 239000007787 solid Substances 0.000 claims 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 2
- 229910052721 tungsten Inorganic materials 0.000 claims 2
- 239000010937 tungsten Substances 0.000 claims 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 239000000654 additive Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- -1 ammonium ions Chemical class 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- 238000000975 co-precipitation Methods 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 238000000151 deposition Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 230000005070 ripening Effects 0.000 claims 1
- 238000005486 sulfidation Methods 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
-
- 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Claims (14)
1. Способ получения каталитической композиции общей формулы, в расчете на оксиды:
в которой Х представляет собой, по меньшей мере, один неблагородный металл группы VIII,
М представляет собой, по меньшей мере, один неблагородный металл группы VIB,
Z представляет собой один или несколько элементов, выбранных из алюминия, кремния, магния, титана, циркония, бора и цинка,
О представляет собой кислород,
одно из b и с представляет собой целое число 1, и
d, e и другое из b и с представляет собой, каждое, число больше 0, так что мольное соотношение b:c находится в интервале от 0,5:1 до 5:1, мольное соотношение d:c находится в интервале от 0,1:1 до 50:1, и мольное соотношение е:с находится в интервале от 3,6:1 до 108:1,
который включает нагревание композиции общей формулы
в которой а представляет собой число больше 0, и X, M, Z, O, b, c, d и е являются такими, как определено выше,
при температуре в интервале от 100 до 600°С,
где композиция общей формулы II находится в форме суспензии или извлекается из суспензии, необязательно, после созревания при температуре в интервале от 20 до 95°С в течение не менее 10 мин, причем указанная суспензия получена (со)осаждением при температуре и в течение периода времени, достаточных для получения композиции II, по меньшей мере, одного соединения неблагородного металла группы VIII, по меньшей мере, одного соединения неблагородного металла группы VIB, по меньшей мере, одного тугоплавкого оксидного материала и щелочного соединения в протонной жидкости, причем, по меньшей мере, одно из соединений металлов находится частично в твердом сстоянии и частично в растворенном состоянии.
2. Способ по п.1, который включает нагревание композиции II при температуре, не превышающей 350°С, особенно не превышающей 300°С.
3. Способ по п.1, в котором соосаждение проводят при температуре в интервале от 25 до 95°С в течение периода времени в интервале от 10 мин до 2 ч при концентрации щелочи от 0,2 моль на моль металлов М+Х в расчете на оксиды до 50 моль на моль металлов М+Х в расчете на оксиды и с начальной концентрацией суспензии в интервале от 2 до 40 мас.% номинального содержания твердых веществ.
4. Способ по п.1, в котором щелочным соединением является аммиак или материал, который генерирует ионы аммония в используемой протонной жидкости.
5. Способ по п.3 или 4, в котором концентрация щелочи находится в интервале от 0,75 до 5 моль азота на моль металлов М+Х в расчете на оксиды.
6. Способ по п.1 или 2, в котором композиция общей формулы I дополнительно проходит любую одну или несколько из следующих стадий способа, выполняемых в любом подходящем порядке: охлаждение; необязательное выделение; сушка; формование, предпочтительно, экструзией без использования экструзионных добавок; прокаливание; сульфидирование.
7. Объемная металлоксидная каталитическая композиция, полученная способом по любому из пп.1-6.
8. Каталитическая композиция общей формулы I по п.1, которая получена способом осаждения, в котором тугоплавкий оксидный материал в количестве в интервале от 15 до 40 мас.% в расчете на оксиды осаждают, по меньшей мере, с одним соединением неблагородного металла группы VIII и, по меньшей мере, с одним соединением неблагородного металла группы VIB.
9. Композиция по п.8, в которой металлы Х и М представляют собой один вариант из никеля и молибдена, никеля и вольфрама и никеля, молибдена и вольфрама.
10. Композиция по п.9, которая является рентгенографически аморфной.
11. Композиция по п.10, которая имеет рентгенограмму, на которой выше 2и=15° имеется местный максимум, имеющий полную характеристическую ширину при половине максимума выше 2,5° при каждом из значений 2и в интервале от 25,5 до 28,0°, значений 2и в интервале от 33,6 до 34,6° и значений 2и в интервале от 59,8 до 62,2°, и отсутствует отображение или местный максимум, имеющий полную характеристическую ширину при половине максимума 2,5° или ниже.
12. Композиция по п.10 или 11, в которой Х представляет собой никель, М представляет собой молибден, Z представляет собой кремний, мольное соотношение Х:М составляет 1:1, и тугоплавкий оксидный материал осажден с соединениями металлов в количестве в интервале от 15 до 30 предпочтительно до 25 мас.%.
13. Способ получения композиции по п.8, который содержит нагревание композиции общей формулы
в которой а представляет собой число больше 0, и X, M, Z, O, b, c, d и е являются такими, как определено в п. 1,
при температуре в интервале от 100 до 600°С.
14. Применение композиции по любому из пп.7-13, при необходимости формованной или сульфидированной, в гидрообработке.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP03251094 | 2003-02-24 | ||
| EP03251094.3 | 2003-02-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| RU2005129708A true RU2005129708A (ru) | 2006-03-10 |
| RU2338591C2 RU2338591C2 (ru) | 2008-11-20 |
Family
ID=32892985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| RU2005129708/04A RU2338591C2 (ru) | 2003-02-24 | 2004-02-24 | Получение и применение каталитической композиции |
Country Status (13)
| Country | Link |
|---|---|
| US (3) | US7544285B2 (ru) |
| EP (1) | EP1608464B1 (ru) |
| JP (1) | JP2006518663A (ru) |
| KR (1) | KR20050100006A (ru) |
| CN (2) | CN1809418A (ru) |
| AR (1) | AR043242A1 (ru) |
| BR (1) | BRPI0407773B1 (ru) |
| CA (1) | CA2516695C (ru) |
| RU (1) | RU2338591C2 (ru) |
| TW (1) | TW200425950A (ru) |
| UA (2) | UA89613C2 (ru) |
| WO (1) | WO2004073859A1 (ru) |
| ZA (2) | ZA200506570B (ru) |
Families Citing this family (97)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060058174A1 (en) * | 2004-09-10 | 2006-03-16 | Chevron U.S.A. Inc. | Highly active slurry catalyst composition |
| US7678730B2 (en) * | 2004-09-10 | 2010-03-16 | Chevron Usa Inc. | Hydroprocessing bulk catalyst and uses thereof |
| US7737073B2 (en) * | 2004-09-10 | 2010-06-15 | Chevron U.S.A. Inc. | Hydroprocessing bulk catalyst and uses thereof |
| US7737072B2 (en) * | 2004-09-10 | 2010-06-15 | Chevron Usa Inc. | Hydroprocessing bulk catalyst and uses thereof |
| US7678731B2 (en) * | 2004-09-10 | 2010-03-16 | Chevron Usa Inc. | Hydroprocessing bulk catalyst and uses thereof |
| US7648941B2 (en) * | 2004-09-22 | 2010-01-19 | Exxonmobil Research And Engineering Company | Bulk bimetallic catalysts, method of making bulk bimetallic catalysts and hydroprocessing using bulk bimetallic catalysts |
| CN1326613C (zh) * | 2004-11-11 | 2007-07-18 | 宁波华实纳米材料有限公司 | 高产率制备碳纳米管的复合金属氧化物催化剂及其制备方法 |
| BRPI0610670B1 (pt) | 2005-04-11 | 2016-01-19 | Shell Int Research | método para produzir um produto bruto, catalisador para produzir um produto bruto, e, método para fabricar um catalisador |
| EP1874896A1 (en) | 2005-04-11 | 2008-01-09 | Shell International Research Maatschappij B.V. | Method and catalyst for producing a crude product having a reduced nitroge content |
| JP2008536002A (ja) * | 2005-04-11 | 2008-09-04 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | 原油生成物を製造するためのシステム、方法及び触媒 |
| EP3556462A1 (en) | 2005-10-26 | 2019-10-23 | Exxonmobil Research And Engineering Company | Hydroprocessing using bulk bimetallic catalysts |
| PL3078417T3 (pl) * | 2005-10-26 | 2021-12-27 | Albemarle Netherlands B.V. | Kompozycja katalizatora nieosadzonego na nośniku i sposób jej wytwarzania |
| US8062508B2 (en) | 2005-10-26 | 2011-11-22 | Exxonmobil Research And Engineering Company | Hydroprocessing using bulk bimetallic catalysts |
| CA2627404C (en) * | 2005-10-26 | 2014-05-27 | Albemarle Netherlands Bv | A bulk catalyst comprising metal oxidic particles and a process for the manufacture thereof |
| KR101373988B1 (ko) * | 2005-10-26 | 2014-03-12 | 알베마를 네덜란드 비.브이. | 니켈 텅스텐 금속 산화 입자를 포함하는 벌크 촉매 |
| KR101353846B1 (ko) * | 2005-10-26 | 2014-01-20 | 알베마를 네덜란드 비.브이. | 8족 금속 및 몰리브덴을 포함하는 벌크 수소화공정 촉매,그의 제조 및 용도 |
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| CN1753731A (zh) | 2006-03-29 |
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| CN100581650C (zh) | 2010-01-20 |
| CA2516695A1 (en) | 2004-09-02 |
| ZA200506569B (en) | 2007-02-28 |
| KR20050100006A (ko) | 2005-10-17 |
| UA89613C2 (ru) | 2010-02-25 |
| US8088706B2 (en) | 2012-01-03 |
| CA2516695C (en) | 2011-11-29 |
| US8664146B2 (en) | 2014-03-04 |
| BRPI0407773A (pt) | 2006-02-14 |
| AR043242A1 (es) | 2005-07-20 |
| US7544285B2 (en) | 2009-06-09 |
| US20040182749A1 (en) | 2004-09-23 |
| ZA200506570B (en) | 2006-07-26 |
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