RU96107879A - EPOXIDATION CATALYST AND METHOD - Google Patents

EPOXIDATION CATALYST AND METHOD

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Publication number
RU96107879A
RU96107879A RU96107879/04A RU96107879A RU96107879A RU 96107879 A RU96107879 A RU 96107879A RU 96107879/04 A RU96107879/04 A RU 96107879/04A RU 96107879 A RU96107879 A RU 96107879A RU 96107879 A RU96107879 A RU 96107879A
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RU
Russia
Prior art keywords
alumina
amount
catalyst
weight
carrier
Prior art date
Application number
RU96107879/04A
Other languages
Russian (ru)
Other versions
RU2126296C1 (en
Inventor
Матуш Марек
Маттиас Анна Мария Местерс Каролус
Эдвард Баффам Джон
Original Assignee
Шелл Интернэшнл Рисерч Маатсхаппий Б.В.
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.)
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Publication date
Priority claimed from US08/118,486 external-priority patent/US5380697A/en
Application filed by Шелл Интернэшнл Рисерч Маатсхаппий Б.В. filed Critical Шелл Интернэшнл Рисерч Маатсхаппий Б.В.
Publication of RU96107879A publication Critical patent/RU96107879A/en
Application granted granted Critical
Publication of RU2126296C1 publication Critical patent/RU2126296C1/en

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Claims (17)

1. Катализатор, пригодный для парофазного эпоксидирования олефинов, не имеющих аллильного водорода, в частности этилена, кислородом, содержащий каталитически эффективное количество серебра и промотирующее количество щелочного металла, нанесенные на носитель, имеющий прочность на раздавливание по крайней мере 2,3 кг и определенную объемную плотность по крайней мере 0,48 кг/л, который включает первый и второй компоненты α- оксида алюминия, при этом первый компонент α- оксида алюминия в форме частиц, имеющих средний размер кристаллита 0,4 - 4 мкм, составляет 95 - 40% от общего веса α- оксида алюминия в носителе и второй компонент α-оксида алюминия, полученный in situ золь-гелевым процессом, составляет остальное количество α-оксида алюминия в носителе.1. A catalyst suitable for vapor-phase epoxidation of olefins without allyl hydrogen, in particular ethylene, with oxygen, containing a catalytically effective amount of silver and a promoting amount of alkali metal supported on a support having a crush strength of at least 2.3 kg and a certain volumetric a density of at least 0.48 kg / l, which includes the first and second components of α-alumina, the first component of α-alumina in the form of particles having an average crystallite size of 0.4 to 4 μm, it accounts for 95 - 40% of the total weight of α-alumina in the support and the second component of α-alumina obtained in situ by the sol-gel process makes up the remaining amount of α-alumina in the support. 2. Катализатор по п.1, отличающийся тем, что первый компонент α-оксида алюминия в носителе включает первую и вторую составляющие, при этом первая составляющая содержится в количестве 10 - 90% по весу первого компонента в форме частиц со средним размером частицы 2,5 - 4 мкм и средним размером кристаллита 1,5 - 2,5 мкм, и вторая составляющая содержится в количестве 90 - 10% по весу первого компонента в форме частиц со средним размером частицы 4 - 10 мкм и средним размером кристаллита 0,4 - 0,8 мкм. 2. The catalyst according to claim 1, characterized in that the first component of α-alumina in the carrier comprises first and second components, while the first component is contained in an amount of 10 - 90% by weight of the first component in the form of particles with an average particle size of 2, 5 to 4 microns and an average crystallite size of 1.5 to 2.5 microns, and the second component is contained in an amount of 90 to 10% by weight of the first component in the form of particles with an average particle size of 4 to 10 microns and an average crystallite size of 0.4 to 0.8 microns. 3. Катализатор по п.1, отличающийся тем, что второй компонент α-оксида алюминия в носителе получен золь-гелевым процессом с внесением затравки. 3. The catalyst according to claim 1, characterized in that the second component of α-alumina in the carrier is obtained by sol-gel process with the introduction of seed. 4. Катализатор по п. 3, отличающийся тем, что полученный золь-гелевым способом оксид алюминия в носителе получен при использовании эффективного количества затравки из α-оксида алюминия с размером частиц менее мкм. 4. The catalyst according to claim 3, characterized in that the sol-gel alumina obtained in the support is obtained using an effective amount of seed from α-alumina with a particle size of less than microns. 5. Катализатор по п.1, отличающийся тем, что носитель дополнительно содержит оксид титана в количестве 0.05 - 1% по весу относительно веса оксида алюминия в носителе. 5. The catalyst according to claim 1, characterized in that the carrier further comprises titanium oxide in an amount of 0.05 - 1% by weight relative to the weight of aluminum oxide in the carrier. 6. Катализатор по п.1, отличающийся тем, что носитель имеет объем пор 0,3 - 0,6 мл/г. 6. The catalyst according to claim 1, characterized in that the carrier has a pore volume of 0.3 - 0.6 ml / g 7. Катализатор по п.1, отличающийся тем, что носитель дополнительно содержит керамический связующий материал в количестве 1 - 3% по весу относительно компонентов оксида алюминия, выраженного в виде α-оксида алюминия. 7. The catalyst according to claim 1, characterized in that the carrier further comprises a ceramic binder in an amount of 1 to 3% by weight relative to the components of aluminum oxide, expressed as α-alumina. 8. Катализатор по п.1, отличающийся тем, что количество серебра находится в диапазоне 1 - 40% и количество щелочного металла составляет 10 - 3000 ч. на 1 млн по весу относительно общего веса катализатора, в пересчете на металл. 8. The catalyst according to claim 1, characterized in that the amount of silver is in the range of 1 - 40% and the amount of alkali metal is 10 - 3000 hours per 1 million by weight relative to the total weight of the catalyst, in terms of metal. 9. Катализатор по п.8, отличающийся тем, что промотор из щелочного металла выбирают из группы, состоящей из калил, рубидия, цезия, лития и их смесей. 9. The catalyst of claim 8, wherein the alkali metal promoter is selected from the group consisting of potassium, rubidium, cesium, lithium, and mixtures thereof. 10. Катализатор по п.1, отличающийся тем, что он дополнительно содержит промотирующее количество рения. 10. The catalyst according to claim 1, characterized in that it further comprises a promoting amount of rhenium. 11. Катализатор по п.10, отличающийся тем, что он дополнительно содержит сопромотор рения, выбранный из группы, состоящей из серы, молибдена, вольфрама, хрома и их смесей. 11. The catalyst of claim 10, characterized in that it further comprises a rhenium co-promoter selected from the group consisting of sulfur, molybdenum, tungsten, chromium and mixtures thereof. 12. Способ получения носителя для катализатора по п.1, включающий стадии: а) образования смеси, содержащей:
(i) по крайней мере, один компонент α-оксида алюминия со средним размером частиц 3 - 8 мкм и средним размером кристаллитов 0,4 - 4 мкм;
(ii) гидратированный предшественник α-оксида алюминия (золь и/или гель) в количестве, достаточном для обеспечения 5 - 60% по весу от общего веса α-оксида алюминия в носителе катализатора:
(iii) выгорающий маттиол в количестве 5 - 40% относительно веса α-оксида алюминия;
(iv) воду в количестве, достаточном для экструдирования вышеприведенной смеси;
в) экструдирование смеси в формованные изделия требуемого вида и
с) обжига для превращения предшественника α-оксида алюминия в α-оксид алюминия с получением носителя для катализатора, в котором частицы α-оксида алюминия со средним размером 3 - 8 мкм и размером кристаллитов 0,4 - 4 мкм распределены в матрице α-оксида алюминия, полученной из материала предшественника.12. The method of obtaining a carrier for the catalyst according to claim 1, comprising the steps of: a) forming a mixture containing:
(i) at least one α-alumina component with an average particle size of 3 to 8 μm and an average crystallite size of 0.4 to 4 μm;
(ii) a hydrated α-alumina precursor (sol and / or gel) in an amount sufficient to provide 5-60% by weight of the total weight of α-alumina in the catalyst carrier:
(iii) burnable matthiol in an amount of 5-40% based on the weight of α-alumina;
(iv) water in an amount sufficient to extrude the above mixture;
C) extruding the mixture into molded products of the desired type and
c) firing to convert the α-alumina precursor to α-alumina to provide a catalyst support in which α-alumina particles with an average size of 3-8 μm and crystallites of 0.4-4 μm are distributed in the α-oxide matrix aluminum derived from the precursor material. 13. Способ по п.12, отличающийся тем, что предшественник α-оксида алюминия в носителе включает бемит. 13. The method according to p. 12, characterized in that the α-alumina precursor in the carrier comprises boehmite. 14. Способ по п.12, отличающийся тем, что предшественник α-оксида алюминия в носителе дополнительно включает тригидрат оксида алюминия. 14. The method of claim 12, wherein the α-alumina precursor in the carrier further comprises alumina trihydrate. 15. Способ по п.12, отличающийся тем, что в предшественник α-оксида алюминия вводят в качестве затравки α-оксид алюминия с размером частиц менее мкм, взятым в количестве, которое составляет 0,2 - 5% по весу относительно общего веса оксида алюминия, определенного в виде α-оксида алюминия, в носителе катализатора. 15. The method according to p. 12, characterized in that in the precursor α-alumina is introduced as a seed α-alumina with a particle size of less than microns, taken in an amount that is 0.2 to 5% by weight relative to the total weight of the oxide aluminum, defined as α-alumina, in a catalyst support. 16. Способ по п. 12, отличающийся тем, что к экструдируемой смеси добавляют оксид титана в количестве 0,5 - 1% по весу относительно общего веса оксида алюминия в составе, выраженного в виде α-оксида алюминия. 16. The method according to p. 12, characterized in that titanium oxide is added to the extrudable mixture in an amount of 0.5 to 1% by weight relative to the total weight of alumina in the composition, expressed as α-alumina. 17. Способ по п. 12, отличающийся тем, что к экструдируемой смеси добавляют керамический связующий материал в количестве, которое составляет 1 - 3% от веса компонентов оксида алюминия, выраженного в виде α-оксида алюминия, в смеси. 17. The method according to p. 12, characterized in that to the extrudable mixture add ceramic binder material in an amount that is 1 to 3% by weight of the components of aluminum oxide, expressed as α-alumina, in the mixture.
RU96107879A 1993-09-08 1994-09-07 Catalyst for vapor-phase epoxidation of olefins and method of production of catalyst carrier RU2126296C1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US08/118486 1993-09-08
US08/118,486 US5380697A (en) 1993-09-08 1993-09-08 Ethylene oxide catalyst and process
US08/118,486 1993-09-08
PCT/EP1994/002996 WO1995007139A1 (en) 1993-09-08 1994-09-07 Epoxidation catalyst and process

Publications (2)

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RU96107879A true RU96107879A (en) 1998-07-20
RU2126296C1 RU2126296C1 (en) 1999-02-20

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EP (1) EP0717659B1 (en)
JP (1) JP3727653B2 (en)
KR (1) KR100336285B1 (en)
CN (1) CN1078818C (en)
AT (1) ATE164784T1 (en)
AU (1) AU680299B2 (en)
BR (1) BR9407417A (en)
CA (1) CA2171213C (en)
CZ (1) CZ72996A3 (en)
DE (1) DE69409536T2 (en)
DK (1) DK0717659T3 (en)
ES (1) ES2114225T3 (en)
FI (1) FI961030A (en)
IN (1) IN190340B (en)
MX (1) MX184168B (en)
MY (1) MY111128A (en)
NO (1) NO960915L (en)
NZ (1) NZ273597A (en)
PH (1) PH30949A (en)
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RU (1) RU2126296C1 (en)
SA (1) SA94150172B1 (en)
SG (1) SG81876A1 (en)
SK (1) SK280987B6 (en)
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