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WO1996004989A1 - Procede de preparation d'un catalyseur a base d'argent - Google Patents

Procede de preparation d'un catalyseur a base d'argent Download PDF

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Publication number
WO1996004989A1
WO1996004989A1 PCT/US1994/008950 US9408950W WO9604989A1 WO 1996004989 A1 WO1996004989 A1 WO 1996004989A1 US 9408950 W US9408950 W US 9408950W WO 9604989 A1 WO9604989 A1 WO 9604989A1
Authority
WO
WIPO (PCT)
Prior art keywords
process according
silver
catalyst
support
cesium
Prior art date
Application number
PCT/US1994/008950
Other languages
English (en)
Inventor
Nabil Rizkalla
Original Assignee
Scientific Design Company, Inc.
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 Scientific Design Company, Inc. filed Critical Scientific Design Company, Inc.
Priority to GB9606642A priority Critical patent/GB2297278B/en
Priority to AU75583/94A priority patent/AU7558394A/en
Priority to DE4481119T priority patent/DE4481119T1/de
Priority to JP50724896A priority patent/JP3748888B2/ja
Priority to NL9420033A priority patent/NL9420033A/nl
Priority to CA002196059A priority patent/CA2196059C/fr
Priority to PCT/US1994/008950 priority patent/WO1996004989A1/fr
Publication of WO1996004989A1 publication Critical patent/WO1996004989A1/fr

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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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • 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
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid

Definitions

  • the present invention relates generally to a supported silver catalyst useful for the vapor-phase oxidation of ethylene to ethylene oxide. More particularly, the present invention relates to a method of preparing an improved supported silver catalyst post impregnated with cesium.
  • Related Art The use of supported silver catalysts for the oxidation of ethylene to ethylene oxide has been long known in the art. Additionally, over the years various promoting metals have been added to further enhance performance. In particular, the use of alkali metals has been disclosed in various amounts and added by different methods. A very extensive review of the patent literature is given in G.B. No. 2,043,481A. Such disclosures have been somewhat inconsistent in their teachings, as can be seen by comparing U.S. Pat. No. 2,238,474 in which sodium and lithium hydroxides were suggested as promoters and potassium and cesium were shown to be poisons to U.S Pat. No. 2,671,764 where rubidium and cesium sulfates were suggested as promoting compounds.
  • alkali metals were suggested generally in the earlier disclosures, it is also generally true that more recent workers in the field have considered potassium, rubidium, and cesium as the preferred alkali metals.
  • the series of patents to Nielson, et al. in which these materials were used in small amounts co- deposited with the silver — U.S. Pat. Nos. 3,962,136; 4,010,115, and 4,012,425.
  • Still more recently the art has emphasized synergistic combinations of the alkali metals. For example, see G.B. No. 2,043,481A cited above and U.S. Pat. Nos. 4,212,772 or 4,226,782.
  • the alkali metals may be used to rejuvenate used catalysts, as for example U.S. Pat. Nos. 4,123,385; 4,033,903; 4,177,169; and 4,186,106.
  • the art teaches that the alkali metals may be deposited either before the silver 96/04989 PC17US94/08950
  • alkali metal was suggested to be in quite a wide range in the older art. It was often indicated that large quantities, e.g. up to several per cent of an alkali metal could be used. More recently, the art generally has taught that small quantities of alkali metals produce the optimum effect no matter when the silver and the alkali metals were deposited. Kilty in U.S. Pat. No. 4,207,210 related the optimum amount of alkali metal to the surface area of the support. Exceptions to the above include patents issued to ICI which teach the use of large amounts of sodium alone (G.B. No. 1,560,480) and potassium in combination with smaller amounts of rubidium and cesium (U.S. Pat. No. 4,226,782). However, the art generally teaches that the optimum will be found in substantially lower quantities, perhaps on the order of 50-500 ppm by weight.
  • the "activated" catalyst is then impregnated with a cesium solution and dried in air at 130*C for 3 hours.
  • the use of the inert atmosphere during the activation step produced a catalyst that was more selective, but much less stable, i.e., the catalyst lost its activity fairly quickly resulting in shorter run length for a given end of run temperature.
  • Cesium now appears to be the preferred alkali metal.
  • Various sources of cesium are catalogued in the prior art, for example, cesium hydroxide, cesium nitrate, cesium chloride, cesium chlorate, cesium bicarbonate, cesium carbonate, and other anion functionalities such as formates, acetates and the like.
  • U.S. Pat. No. 4,374,260 discloses the coprecipitation of silver and cesium salt, such as the carbonate from a silver carboxylate/amino complex.
  • U. S. Pat No's 4,350,616 and 4,389,338 both show the deposition of CsC0 3 onto activated silver catalyst from alcohol solution where the silver was derived from aqueous silver salt solution.
  • U. S. Pat. No's 4,066,575 and 4,033,903 disclose the preparation of silver catalyst from both aqueous and non aqueous salt solutions and subsequent treatment of the activated silver catalyst with post deposition of an alkali metal salt such as cesium and anions including carbonate from lower alcohol and preferably from aqueous solutions.
  • an alkali metal salt such as cesium and anions including carbonate from lower alcohol and preferably from aqueous solutions.
  • U.S. Pat. No. 4,342,667 discloses the post deposition of cesium on to silver catalyst derived from aqueous solutions.
  • the present preparation is characterized as being substantially anhydrous with post disposition of cesium.
  • one aspect of the present invention is a catalyst prepared by the process of impregnating a porous support having a low surface area with a hydrocarbon solution of a silver salt of an organic acid which is substantially free of water and acid.
  • the impregnated support is subjected to a low temperature activation in an atmosphere containing less oxygen than air, preferably an inert atmosphere, by heating at a temperature not exceeding 300*C preferably in the range of 250*C to SOO'C on a moving belt.
  • the activation produces a support containing the activated silver.
  • the catalyst is made by impregnating a porous support, preferably having a surface area in the range of 0.2 to 2.0 m 2 /g, with a hydrocarbon solution of a silver salt of an organic acid.
  • the solution should be substantially free of both water and acid as this aspect has been shown to be especially beneficial to catalyst performance and hence preferred.
  • the impregnated support is activated as described above.
  • an alkali metal preferably cesium
  • Stability as that term is used herein relates to the temperature in the catalyst bed in operation as a function of time (time trend) .
  • the activated silver catalyst is an anhydrous post impregnated with an alkali metal, preferably cesium, to produce a finished catalyst by immersing the support in a circulating stream of the alkali metal in an anhydrous solvent such as ethanol.
  • an alkali metal preferably cesium
  • the optimum amount of alkali metal(s) added will be selected to optimize catalyst performance and will be dependent upon the surface area of the support chosen. That is, more alkali metal will be used on supports which have larger surface area than on those having relatively small surface area.
  • the catalyst of the present invention may be employed under oxidizing conditions typical to the art for preparing ethylene oxide by the vapor phase oxidation of ethylene with improved results, especially catalyst stability.
  • inert as used herein means any gaseous material under the conditions of activation which does not react with silver or any other component of the silver impregnated support.
  • Preferred inert material include nitrogen, helium and carbon dioxide, but other specific material include neon, argon, and the like may be used.
  • the limitation of oxygen during the activation is of principal concern.
  • FIG. 1 is a scanning electron micrograph of a silver catalyst in which the silver was deposited by heating in air at 500'C.
  • FIG. 2 is a scanning electron micrograph of a silver catalyst in which the silver was deposited by heating in air at 300"C.
  • FIG. 3 is a scanning electron micrograph of a silver catalyst in which the silver was deposited by heating in an inert atmosphere at 500*C.
  • FIG. 4 is a scanning electron micrograph of a silver catalyst in which the silver was deposited by heating in an inert atmosphere at 300 * C.
  • FIG. 5 is a scanning electron micrograph of a silver catalyst in which the silver was deposited by heating in an inert atmosphere at 300 ⁇ C and thereafter used about 1000 hours in an ethylene oxide reactor.
  • FIG. 6 is a scanning electron micrograph of a silver catalyst in which the silver was deposited by heating in air at 500"C and thereafter used about 1000 hours in an ethylene oxide reactor.
  • the catalyst of the present invention may contain from 3 to 25 wt% silver on the support.
  • Preferred catalysts prepared in accordance with this invention contain up to about 20% by weight of silver, expressed as metal, deposited upon the surface and throughout the pores of a porous refractory support. Silver contents higher than 20% by weight of total catalyst are effective, but result in catalysts which are unnecessarily expensive. Silver contents, expressed as metal, of about 5-13% based on weight of total catalyst are preferred, while silver contents of 8-12% are especially preferred.
  • Catalysts may be made with supports comprising alumina, silica, silica-alumina or combinations thereof.
  • Preferred supports are those containing principally alpha-alumina, particularly those containing up to about 15 wt% silica.
  • Especially preferred supports have a porosity of about 0.1- 1.0 cc/g and preferably about 0.2-0.7 cc/g.
  • Preferred supports also have a relatively low surface area, i.e. about 0.2-2.0 m 2 /g, preferably 0.4-1.6 m 2 /g and most preferably 0.5-1.3 m 2 /g as determined by the BET method. See J. A. Chem. Soc. 60, 309-16 (1938) . Porosities are determined by the mercury porosimeter method; see Drake and Ritter, "Ind. Eng. Chem. Anal. Ed.,” 17, 787 (1945). Pore and pore diameter distributions are determined from the surface area and apparent porosity measurements.
  • the supports are desirably formed into regularly shaped pellets, spheres, rings, etc.
  • the support particles used have "equivalent diameters" in the range from 3-10 mm and preferably in the rang of 4-8 mm, which are usually compatible with the internal diameter of the tubes in which the catalyst is placed. "Equivalent diameter” is the diameter of a sphere having the same external surface (i.e. neglecting surface within the pores of the particle) to volume ratio as the support particles being employed.
  • the silver is added to the support by immersion of the support into a solution containing a silver salt of an organic acid which is substantially free of water and said acid.
  • the silver containing liquid penetrates by absorption, capillary action and/or vacuum into the pores of the support.
  • a single immersion or a series of immersions, with or without intermediate drying, may be used, depending in part upon the concentration of the silver salt in the solution.
  • suitable impregnating solutions will generally contain from 5-50 wt% silver, expressed as metal, but supplied as silver salts of acids. The exact concentrations employed, of course, will depend upon, among other factors, the desired silver content, the nature of the support, the viscosity of the liquid, and solubility of the acid silver salt.
  • Impregnation of the selected support is achieved in a conventional manner.
  • the support material is placed in the silver solution until all of the solution is absorbed by the support.
  • the quantity of the silver solution used to impregnate the porous support is no more than is necessary to fill the pore volume of the porous support.
  • the impregnating solution is characterized as a substantially water free and acid free organic solution of a silver salt of an organic acid, such as the neo acids (particularly those having at least seven carbon atoms) disclosed in U.S. Patent No. 4,864,042 which is incorporated herein in its entirety.
  • a hydrocarbon solvent is employed, such as toluene, cyclohexane, xylene, ethyl benzene, cumene or nonene which would normally be water free. Since water is considered to be detrimental to the preparation of silver catalysts when the method of the invention is used, it should be present in no more than about 0.1 vol% in the silver impregnating solution, preferably less than about 0.01 vol%.
  • the support is then activated in the low temperature process as described, preferably on a moving belt in the atmosphere as specified.
  • the silver impregnated support is activated in an inert atmosphere such as nitrogen, carbon dioxide or helium, at a temperature below 300*C as recited and for limited periods, preferably of from about one to ten minutes.
  • the support may be impregnated with the alkali metal if desired. It is the purpose of alkali metal to modify the catalyst and raise selectivity while leaving the improved stability intact. When used the amount of the alkali metal on the finished catalyst is generally similar to those employed heretofore.
  • the alkali metals of the periodic table include sodium, lithium, potassium, rubidium and cesium. For purposes of the present invention, the latter three alkali metals are particularly preferred, especially cesium, although sodium and lithium are not necessarily excluded.
  • the alkali metal salts are dissolved in alcohol solutions, preferably substantially free of water.
  • the improvement from the use of cesium salt in a pure alcohol solvent, substantially free of water is believed to relate to the relatively poor solubility of cesium salt in alcohol.
  • the cesium compound although poorly soluble, remains evenly distributed through the solvent during evaporization and drying, hence is more evenly distributed over the silver catalyst.
  • Active catalyst may also be obtained when using the present activation followed by deposition of cesium from alcohol-solution.
  • the alkali metal impregnated catalysts are dried rapidly, e.g. one to two minutes at high temperature, e.g. at least 100 * C up to 800*C, preferably around 200 * C to 600 "C. This may be readily achieved by using a moving belt as described herein. The drying may be conducted in air or an inert gas.
  • Catalysts prepared by the procedures above have improved performance, especially stability, for use in the production of ethylene oxide by the vapor phase oxidation of ethylene with molecular oxygen. These usually involve reaction temperatures of about 150"C to 400°C, usually about 200"C to 300"C, and reaction pressures in the range of from 0.5 to 35 bar.
  • Reactant feed mixtures contain 0.5 to 20 % ethylene and 3 to 15 % oxygen, with the balance comprising comparatively inert materials including such substances as nitrogen, carbon dioxide, methane, ethane, argon and the like.
  • the catalyst prepared by the process of the present invention has a different silver particle size and dispersion than catalysts prepared by conventional processes.
  • the support impregnated with the silver solution is subjected to an elevated temperature in the presence of a gas containing oxygen, normally air. This results in very fine silver particles and is shown in FIG.
  • the catalysts with the finer silver particle dispersion lose their selectivity during use (over about 1000 hours) .
  • the same catalysts having the 110-125 pp ⁇ 2 initial dispersion end up with a silver dispersion of about 1-2 pp ⁇ 2 as shown in FIG. 5 which is a SEM of a catalyst having an initial dispersion of 110-125 pp ⁇ 2 after about 1000 hours in an ethylene oxide reactor.
  • a catalyst having the lower initial dispersion of about 10-25 pp ⁇ 2 ends up with a silver particle dispersion of 25 pp ⁇ 2 as shown in FIG. 6.
  • the finished catalysts are then tested for activity and selectivity by crushing and placing 36 grams in a micro reactor consisting of a 1/4 inch stainless steel tube which is heated in a salt bath.
  • a feed mixture of 7% oxygen, 8% C0 2 , 15% C 2 H , 70% N 2 is passed over the catalyst with a gas space velocity of 5500 hr -1 .
  • the pressure is maintained at 300 psig (21.69 bar) and the temperature between 200*C and 300 ⁇ C as required to maintain an outlet concentration of 1.5 vol% (160 Kg per hour per m 3 of catalyst) ethylene oxide.
  • the activity of the catalyst is expressed as the temperature necessary to maintain the outlet concentration at 1.50 vol% ethylene oxide, the lower the temperature, the more active the catalyst.
  • the selectivity of the catalyst is expressed as the mole% of the total ethylene converted to ethylene oxide at the outlet concentration of 1.50 vol% ethylene.
  • the stability of the catalyst is measured by the increase in temperature required to maintain the ethylene oxide productivity.
  • the support used for this preparation was obtained from Norton Company and was made primarily of ⁇ -alumina in the form of 5/16 inch cylinders.
  • the support has a surface area of 0.55 m 2 /g, pore volume of .3 cc/g, and medium pore diameter of 1.5 ⁇ .
  • the deposition of the silver was induced by heating the impregnated support to a temperature that did not exceed 300° on a moving belt in a stream of nitrogen.
  • the residence time of the catalyst in the heated zone was two minutes.
  • the catalyst was then impregnated for two hours at room temperature in an anhydrous ethanolic solution that contained 525 ppm cesium bicarbonate.
  • the catalyst was superficially dried by a stream of nitrogen followed by heating on a moving belt at 200*C.
  • a catalyst was prepared in substantially the same manner and using the same support as Example 1 except that the initial calcination was carried out in a gas stream of nitrogen containing 2.5% oxygen. After 100 hours in the reactor the selectivity was 82.0% and the reactor temperature was 228*C.
  • EXAMPLE 3 (Comparative) The support used for this preparation was obtained from Norton Company and was made primarily of ⁇ -alumina in the form of 5/16 inch cylinders. The support has a surface area of 0.55 m 2 /g, pore volume of .3 cc/g, and medium pore diameter of 1.5 ⁇ . A 95 parts of a cumene solution of silver neodecanoate, containing 26 wt% silver, was added to 225 parts of the hot support and the mixture was mixed for 20 minutes. The catalyst was prepared using activation with air at 500 ' C and was impregnated with cesium hydroxide solution in water/alcohol solvent, which was subsequently dried with vacuum. The catalyst was tested under the same condition as in example 1. After 150 hours of reaction time the selectivity to ethylene oxide was 80.9% and the reaction temperature was 232*C. The catalyst's performance did not improve with longer reaction time.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
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Abstract

Préparation d'un catalyseur perfectionné à base d'argent, destiné à l'oxydation de l'éthylène à l'aide d'oxygène moléculaire, consistant à imprégner un support poreux avec un sel d'argent d'un néoacide, à soumettre le support imprégné à une activation à basses températures en le chauffant à une température comprise entre 250 et 300 °C, sur un tapis roulant, dans une atmosphère contenant moins d'oxygène que l'air, puis à imprégner le support avec un métal alcalin, de préférence du césium.
PCT/US1994/008950 1994-08-09 1994-08-09 Procede de preparation d'un catalyseur a base d'argent WO1996004989A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
GB9606642A GB2297278B (en) 1994-08-09 1994-08-09 Process for preparing silver catalyst
AU75583/94A AU7558394A (en) 1994-08-09 1994-08-09 Process for preparing silver catalyst
DE4481119T DE4481119T1 (de) 1994-08-09 1994-08-09 Verfahren zur Herstellung eines Silberkatalysators
JP50724896A JP3748888B2 (ja) 1994-08-09 1994-08-09 銀触媒の調製法
NL9420033A NL9420033A (nl) 1994-08-09 1994-08-09 Werkwijze voor de bereiding van een zilver-katalysator.
CA002196059A CA2196059C (fr) 1994-08-09 1994-08-09 Procede de preparation d'un catalyseur a base d'argent
PCT/US1994/008950 WO1996004989A1 (fr) 1994-08-09 1994-08-09 Procede de preparation d'un catalyseur a base d'argent

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1994/008950 WO1996004989A1 (fr) 1994-08-09 1994-08-09 Procede de preparation d'un catalyseur a base d'argent

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AU (1) AU7558394A (fr)
CA (1) CA2196059C (fr)
DE (1) DE4481119T1 (fr)
GB (1) GB2297278B (fr)
NL (1) NL9420033A (fr)
WO (1) WO1996004989A1 (fr)

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WO2004002954A3 (fr) * 2002-06-28 2004-08-19 Shell Oil Co Procede permettant d'ameliorer la selectivite d'un catalyseur, et processus d'epoxydation d'une olefine
US7102022B2 (en) 2002-06-28 2006-09-05 Shell Oil Company Method for the start-up of an epoxidation process and a process for the epoxidation of an olefin
WO2006133183A3 (fr) * 2005-06-07 2007-08-09 Shell Oil Co Catalyseur, procede de preparation de ce catalyseur, et procede pour produire un oxyde d'olefine, un 1,2-diol, un ether de 1,2-diol, ou une alcanolamine
US7348444B2 (en) 2003-04-07 2008-03-25 Shell Oil Company Process for the production of an olefin oxide
US20110094120A1 (en) * 2009-10-28 2011-04-28 The Dow Chemical Company Device to dry catalyst roaster conveyor belt and method of using same
US8008515B2 (en) 2006-05-02 2011-08-30 Nippon Shokubai Co., Ltd. Catalyst for partial oxidation of olefin, preparation method thereof, and process for preparing alkylene oxide
US8148555B2 (en) 2003-06-26 2012-04-03 Shell Oil Company Method for improving the selectivity of a catalyst and a process for the epoxidation of an olefin
US8921586B2 (en) 2008-05-07 2014-12-30 Shell Oil Company Process for the production of an olefin oxide, a 1,2-diol, a 1,2-diol ether, a 1,2-carbonate, or an alkanolamine
US9346774B2 (en) 2008-05-07 2016-05-24 Shell Oil Company Process for the start-up of an epoxidation process, a process for the production of ethylene oxide, a 1,2-diol, a 1,2-diol ether, a 1,2-carbonate, or an alkanolamine
US10532989B2 (en) 2007-05-09 2020-01-14 Shell Oil Company Epoxidation catalyst, a process for preparing the catalyst, and a process for the production of an olefin oxide, a 1,2-diol, a 1,2-diol ether, a 1,2-carbonate, or an alkanolamine
US11801493B2 (en) 2016-12-02 2023-10-31 Shell Usa, Inc. Methods for conditioning an ethylene epoxidation catalyst and associated methods for the production of ethylene oxide

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BE1017795A3 (fr) * 2005-12-22 2009-07-07 Shell Int Research Procede d'installation d'un catalyseur d'epoxydation dans un reacteur, procede de preparation d'un oxyde d'olefine ou d'un produit chimique derivable d'un oxyde d'olefine, et reacteur approprie pour un tel procede.
US7459589B2 (en) 2005-12-22 2008-12-02 Shell Oil Company Process for the preparation of an alkylene glycol
US7750170B2 (en) 2005-12-22 2010-07-06 Shell Oil Company Process for mixing an oxidant having explosive potential with a hydrocarbon
TW201705868A (zh) * 2015-07-01 2017-02-16 艾迪科股份有限公司 擔持體、乙烯去除劑及保鮮劑

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004002954A3 (fr) * 2002-06-28 2004-08-19 Shell Oil Co Procede permettant d'ameliorer la selectivite d'un catalyseur, et processus d'epoxydation d'une olefine
US7102022B2 (en) 2002-06-28 2006-09-05 Shell Oil Company Method for the start-up of an epoxidation process and a process for the epoxidation of an olefin
US7485597B2 (en) 2002-06-28 2009-02-03 Shell Oil Company Method for improving the selectivity of a catalyst and a process for the epoxidation of an olefin
KR100980123B1 (ko) 2002-06-28 2010-09-03 셀 인터나쵸나아레 레사아치 마아츠샤피 비이부이 촉매 선택성을 향상시키는 방법 및 올레핀 에폭시화 방법
US7348444B2 (en) 2003-04-07 2008-03-25 Shell Oil Company Process for the production of an olefin oxide
US8148555B2 (en) 2003-06-26 2012-04-03 Shell Oil Company Method for improving the selectivity of a catalyst and a process for the epoxidation of an olefin
US8084390B2 (en) * 2005-06-07 2011-12-27 Shell Oil Company Catalyst, a process for preparing the catalyst and a process for the production of an olefin oxide, a 1,2-diol, a 1,2 diol ether, or an alkanolamine
WO2006133183A3 (fr) * 2005-06-07 2007-08-09 Shell Oil Co Catalyseur, procede de preparation de ce catalyseur, et procede pour produire un oxyde d'olefine, un 1,2-diol, un ether de 1,2-diol, ou une alcanolamine
US8357825B2 (en) 2005-06-07 2013-01-22 Shell Oil Company Process for the production of a 1,2-diol, a 1,2-diol ether, or an alkanolamine
US8357813B2 (en) 2005-06-07 2013-01-22 Shell Oil Company Process for the production of an olefin oxide
US8008515B2 (en) 2006-05-02 2011-08-30 Nippon Shokubai Co., Ltd. Catalyst for partial oxidation of olefin, preparation method thereof, and process for preparing alkylene oxide
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JPH10503709A (ja) 1998-04-07
GB2297278B (en) 1998-05-20
DE4481119T1 (de) 1996-11-21
NL9420033A (nl) 1996-06-03
GB2297278A (en) 1996-07-31
CA2196059A1 (fr) 1996-02-22
JP3748888B2 (ja) 2006-02-22
CA2196059C (fr) 2004-11-16
AU7558394A (en) 1996-03-07
GB9606642D0 (en) 1996-06-05

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