WO2012157535A1 - Process for producing olefin oxide - Google Patents

Process for producing olefin oxide Download PDF

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Publication number
WO2012157535A1
WO2012157535A1 PCT/JP2012/062078 JP2012062078W WO2012157535A1 WO 2012157535 A1 WO2012157535 A1 WO 2012157535A1 JP 2012062078 W JP2012062078 W JP 2012062078W WO 2012157535 A1 WO2012157535 A1 WO 2012157535A1
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WIPO (PCT)
Prior art keywords
catalyst
olefin
oxide
metal
oxygen
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PCT/JP2012/062078
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French (fr)
Inventor
Patricia CONCEPCION
Mercedes BORONAT
Avelino Corma
Fumisato Goto
Kazuo Sadaoka
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Sumitomo Chemical Company, Limited
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Publication of WO2012157535A1 publication Critical patent/WO2012157535A1/en

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    • B01J35/30—
    • 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
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
    • C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
    • C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
    • 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
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates

Definitions

  • the present invention relates to a process for producing an olefin oxide.
  • US 2010/0010243 Al discloses that a method of converting an alkene to an epoxide comprising reacting the alkene with oxygen in the presence of a silver metal nanocube catalyst having a plurality of surface planes that are substantially Ag (100) .
  • the present invention provides a process for producing an olefin oxide related to the following:
  • a process for producing an olefin oxide comprising reacting an olefin with oxygen in the presence of a catalyst, wherein the catalyst comprises silver metal truncated cubes having one or more Ag (100) planes being selectively exposed;
  • a catalyst for producing an olefin oxide which comprises silver metal truncated cubes having one or more Ag (100) planes being selectively exposed.
  • Fig. 1 is the picture of the silver metal truncated cubes obtained in Preparation Example 1 with electron microscope analysis .
  • Fig. 2(a) and (b) are the pictures of the silver metal truncated cubes obtained in Preparation Example 2 with electron microscope analysis.
  • Fig. 2(C) is an imaginary plane containing Ag (100) plane of the silver metal truncated cube obtained in Preparation Example 2, and Ag (100) plane is shown as a diagonal plane.
  • Fig. 3 is the picture of the silver particles obtained in Comparative Preparation Example 1 with electron microscope analysis.
  • the present invention is a process for producing an olefin oxide comprising reacting an olefin with oxygen in the presence of a catalyst, wherein the catalyst comprises silvermetal truncated cubes having one or more Ag (100) planes being selectively exposed.
  • the catalyst can be prepared by reducing Ag + with a reducing agent in the presence of a capping reagent and an alkali metal source.
  • the catalyst can be produced according to the method described in Science, 298, 2176-2179 (2002), Chemical Physics
  • Examples of Ag + include [Ag (NH 3 ) 2 ] + OH " and AgN0 3 .
  • the reducing agent include an organic reducing agent such as glucose and ethylene glycol.
  • capping reagent examples include hexadecyltrimethylammonium bromide (HTAB) and poly (vinylpyrrolidone) .
  • alkali metal source examples include alkali metal hydroxides such as sodiumhydroxide and potassiumhydroxide, alkali metal sulfides such as sodium sulfide, and alkali metal halides such as sodium chloride.
  • the catalyst can also be produced according to the process described in J. Am. Chem. Soc. 2004, 126, 13200-13201 or J. Phys . Chem. B. 2005, 109, 5497-5503 except that an aqueous solution of silver ammonium hydroxide ( [Ag (NH 3 ) 2 ] + OH " ) is prepared in the presence of an alkali metal source.
  • an aqueous solution of silver ammonium hydroxide [Ag (NH 3 ) 2 ] + OH "
  • the catalyst can be produced, for example, by the following steps (a) and (b) :
  • step (b) a step of mixing the aqueous solution of [Ag (NH 3 ) 2 ] + OH ⁇ prepared in the step (a) , glucose and hexadecyltrimethylammonium bromide (HTAB) followed by heating the resultant mixture under stirring .
  • aqueous solution of [Ag (NH 3 ) 2 ] + OH ⁇ prepared in the step (a)
  • glucose and hexadecyltrimethylammonium bromide (HTAB) followed by heating the resultant mixture under stirring .
  • the reaction mixture obtained is usually centrifuged to obtain the catalyst.
  • the catalyst obtained can be dispersed again into water and/or washed with water.
  • the used amount of the alkali metal base in step (a) is usually 0.3 to 0.4 mole relative to 1 mole of silver nitrate.
  • the used amount of ammonia in the step (a) is usually 2 moles or more relative to 1 mole of silver nitrate, and ammonia is usually used in an amount such that pH of the mixture obtained by mixing of ammonia becomes up to 12.5.
  • the used amount of glucose in the step (b) is usually 0.1 to 5 moles relative to 1 mole of silver nitrate, and the used amount of HTAB in the step (b) is usually 1 to 5 moles relative to 1 mole of silver nitrate.
  • the heating temperature in the step (b) is usually 50 to
  • the shape of the catalyst is a truncated cube.
  • the cube has one or more Ag (100) planes being selectively exposed.
  • the ratio of Ag (100) planes to the surface of the silver metal truncated cube is preferably 20% or more and 80% or less, and preferably 40% or more and 80% or less.
  • the ratio can be calculated based on the observation result with an electron microscope analysis.
  • the catalyst may contain an alkali metal element derived from the alkali metal source.
  • the catalyst can contain a small amount of one or more metal elements other than silver and the alkali metal element.
  • the catalyst is preferably supported on a carrier.
  • the carrier is preferably one on which the catalyst can be supported and which does not change in property under the condition of the process of the present invention.
  • the carrier include a metal carbonate, a metal oxide and carbon.
  • the metal carbonate include an alkali metal carbonate, an alkaline earth metal carbonate and a transition metal carbonate, and the .alkaline earth metal carbonate is preferable.
  • Examples of the alkali metal carbonate include sodium carbonate and potassium carbonate .
  • Examples of the alkaline earth metal carbonate include magnesium carbonate, calcium carbonate, strontium carbonate and barium carbonate, and calcium carbonate, strontium carbonate and barium carbonate are preferable.
  • the alkaline earth metal carbonate having a specific surface area of 1 to 70 m 2 /g measured by nitrogen adsorption of the BET method is preferable.
  • the metal carbonate may be used as it is or after fixing particles of the metal carbonate each other using a suitable binder .
  • the metal carbonate may be mixed with a molding agent and molded by extrusion molding, press molding or the like to use the obtained product as the carrier. It is preferred that the metal carbonate is used as it is as the carrier.
  • a metal oxide having a crystal form of a rock salt structure, a corundum structure, a spinel-type structure, a fluorite-type structure, a wurtzite-type structure, a rutile-type structure, a bixbite-type structure, an ilmenite-type structure, a pseudobrookite-type structure or a perovskite-type structure can be used.
  • Examples of the metal oxide having a rock salt structure include TiO, VO, nO and NiO.
  • Examples of the metal oxide having a corundum structure include ⁇ - ⁇ 1 2 0 3 and cc-Fe 2 0 3 .
  • Examples of the metal oxide having a spinel-type structure include ZnAl 2 0 4 , y-Fe 2 0 3 and SnZn 2 0 4 .
  • Examples of the metal oxide having a fluorite-type structure include Zr0 2 and Ce0 2 .
  • Examples of the metal oxide having a wurtzite-type structure include ZnO.
  • Examples of the metal oxide having a rutile-type structure include Sn0 2 , Ti0 2 and Ru0 2 .
  • Examples of the metal oxide having a bixbite-type structure include P ⁇ Fe 2 0 3 .
  • Examples of the metal oxide having an ilmenite-type structure include FeTi0 3 .
  • Examples of the metal oxide having a pseudobrookite-type structure include FeTi0 5 .
  • Examples of the metal oxide having a perovskite-type structure include CaTi0 3 , SrTi0 3 , BaTi0 3 , CaZr0 3 , SrZr0 3 , BaZr0 3 and LaA10 3 .
  • Examples of the carbon include activated carbon, carbon black, graphite and carbon nanotubes, and graphite is preferred.
  • a silicon compound can be also used, and examples thereof include a water-soluble silicate such as sodium metasilicate and potassium metasilicate, and a porous silicate having silica as a main component such as silica gel, zeolite and mesoporous silicate.
  • a water-soluble silicate such as sodium metasilicate and potassium metasilicate
  • a porous silicate having silica as a main component such as silica gel, zeolite and mesoporous silicate.
  • a commercially available carrier may be used as it is, and such a commercially available carrier may also be used after purifying and molding by a well-known method.
  • the used amount of the carrier is preferably 0.1 to 200 parts by mass per 1 part by mass of the catalyst.
  • the catalyst can be activated before using for the process of the present invention.
  • the activation of the catalyst is usually conducted by heating the catalyst prepared in the absence of oxygen.
  • the heating temperature of the activation is usually 150 to 300°C.
  • the process of the present invention comprises reacting an olefin and oxygen in the presence of the above-mentioned catalyst.
  • the process of the present invention can be performed in a batch-wise reactor or a continuous reactor. From the viewpoint of an industrial process, it is preferably performed in a continuous reactor.
  • the amount of the catalyst is preferably 0.00005 mole or more relative to 1 mole of the olefin, and more preferably 0.0001 mole or more in a silver metal equivalent .
  • the upper limit thereof is not limited, and while a larger amount of the olefin oxide can be produced if increasing the amount of the catalyst, the upper limit of the amount of the catalyst is usually adjusted by taking an economic efficiency such as the cost of catalyst into consideration.
  • Oxygen can be used in combination with an inert gas such as nitrogen and carbon dioxide. Air can be used as oxygen.
  • the amount of oxygen can be appropriately adjusted according to the reaction mode (continuous type or batch type) .
  • the amount of oxygen is preferably in the range of 0.01 to 100 moles relative to 1 mole of the olefin, and more preferably in the range of 0.03 to 30 moles.
  • the reaction temperature is preferably in the range of 100°C to 400°C, and more preferably in the range of 120°C to 300°C.
  • olefin means a hydrocarbon having one carbon-carbon double bond, and examples thereof include ethylene, propylene, butene, pentene and hexene, and propylene is preferable.
  • the olefin can be used in combination with an inert organic gas such as a lower alkane such as methane and ethane.
  • Olefin and oxygen gases can be fed in the form of their mixed gas.
  • Olefin and oxygen gases may be fed with diluent gases .
  • diluent gases include nitrogen, methane, ethane, propane, carbon dioxide and rare gases such as argon and helium.
  • the reaction of the olefin and oxygen can be conducted in the presence of a halogen compound, particularly an organic halogenated compound.
  • the halogen compound include the halogen compounds disclosed in Japanese Unexamined Patent Application Publication No. 2008-184456, and it is preferably an organic chlorinated compound.
  • organic chlorinated compound examples include chloroethane, 1, 2-chloroethane, chloromethane and vinyl chloride.
  • the halogen compound is preferably a compound existing in the form of a gas at the temperature and pressure condition in the reaction system of the reaction.
  • the amount of the halogen compound is preferably 1 to 1000 ppm by volume, and more preferably 1 to 500 ppm by volume based on a total volume of the mixed gas other than steam, i.e. a mixed gas composed of oxygen, the olefin and a dilution gas added as necessary.
  • the reaction pressure is not limited, and may be selected from those in reduced pressure conditions to pressurized conditions .
  • the pressure under pressurized conditions is preferable from the viewpoint of allowing sufficient contact of oxygen and the olefin with the catalyst, it may be a reaction pressure selected from the range of 0.01 to 3 Pa in absolute pressure, and is more preferably selected from the range of 0.02 to 2 MPa.
  • the reaction pressure is determined by also taking into consideration the pressure resistibility of the reaction device used in the present productionmethod.
  • the reducedpressure condition means apressure lower than the atmospheric pressure.
  • the pressurized condition means a pressure higher than the atmospheric pressure.
  • the reaction can be carried out in the presence of water.
  • water is preferably changed into steam by heating to use, and a mixed gas obtained by mixing steam, oxygen and the olefin is preferably contacted with the catalyst. It is preferable to use water as steam.
  • the amount of water is preferably in the range of about 0.1 to about 20 moles relative to lmole of the olefin, more preferably in the range of 0.2 to 10 moles, and still more preferably in the range of 0.3 to 8 moles.
  • the above-mentioned “amount of water” indicates an amount of water supplied separately from water contained in air in a case of supplying air as oxygen.
  • the catalyst in a predetermined amount is filled into a reaction tower equipped with a gas supply port and a gas exhaust port.
  • Suitable heating means may be provided in the reaction tower, and the inside of the reaction tower may be raised in temperature up to a predetermined reaction temperature by such heating means.
  • a source gas containing the olefin and oxygen is supplied from the gas supply port into the reaction tower.
  • the olefin and oxygen reacts in the presence of the catalyst, and the olefin oxide is generated.
  • the product gas containing the olefin oxide thus generated is exhausted from the gas exhaust port.
  • the linear velocity of the source gas that is passed through the inside of a reaction tower is determined so as to make a residence time that allows the source gas and the catalyst to sufficiently generate the olefin oxide.
  • heating means being provided in the reaction tower
  • it may be a mode in which the reaction tower may be maintained at ambient temperature, and the source gas may be supplied and then heated up to a predetermined reaction temperature by appropriate heating means, and then supplied into the reaction tower.
  • suitable stirring means is provided in the reaction tower, and a source gas is supplied while stirring the catalyst that is present inside the reaction tower.
  • the olefin oxide thus generated, unreacted olefin and oxygen, and byproducts such as carbon dioxide may be contained in the product gas passing through the reaction tower.
  • an inert gas used for dilution may be incorporated.
  • the olefin oxide, which is the objective can be removed by separation means such as distillation.
  • olefin oxide examples include ethylene oxide, propylene oxide, butene oxide, pentene oxide and hexene oxide.
  • the aqueous solution obtained was diluted with water, and then, 5% (v/v) ammonia water was added dropwise thereto to obtain 25 ml of an aqueous solution of [Ag (NH 3 ) 2 ] + OH ⁇ (concentration: 10 mM) .
  • the resultant mixture was transferred into an autoclave, and the autoclave was closed and heated under stirring at 120°C for 8 hours.
  • the autoclave was cooled down.
  • the reaction mixture was removed from the autoclave and centrifuged. The solid separated was isolated to obtain silver metal truncated cubes.
  • the silver metal truncated cubes obtained were supported on Ti0 2 according to the conventional impregnation procedure followed by filtering, washing and drying.
  • the Ag nominal metal weight in the carrier was around 1%.
  • the obtained catalyst was washed four times with ethanol at 60°C for 40 minutes .
  • the obtained catalyst supported on Ti0 2 is called as CAT-I.
  • the aqueous solution obtained was diluted with water, and then, 1 mM aqueous sodium hydroxide solution was added dropwise thereto to obtain an aqueous solution of [Ag (NH 3 ) 2 ] + OH " (concentration: 9.78 mM) .
  • the resultant mixture was transferred into an autoclave, and the autoclave was closed and heated under stirring at 120°C for 4 hours.
  • the autoclave was cooled down.
  • the reaction mixture was removed from the autoclave and centrifuged.
  • the solid separated was isolated to obtain silver metal truncated cubes.
  • the silver metal truncated cubes obtained were observed with electron microscope, and its result is shown in Fig. 2(a) and (b) .
  • the ratio of Ag (100) planes to the surface of the silver metal truncated cube was calculated based on the observation result with electron microscope, and as the result, the ratio was 49%. In the calculation, it was assumed that the surface including Ag (100) plane was an octagon as shown in Fig.2 (c) , and the diagonal plane was Ag (100). In Fig. 2(c), al was 2 (length) and hi was 1.4 (length), and therefore, the ratio of Ag (100) planes to the surface of the silver metal truncated cube was calculated by the following formula:
  • Ratio (%) (bl) 2 / ⁇ al) 2 X 100
  • the silver metal truncated cubes obtained in Preparation Example 2 were supported on cc-Al 2 0 3 according to the conventional impregnation procedure followed by drying.
  • the Ag nominal metal weight in the carrier was around 1%.
  • the obtained catalyst was washed four times with ethanol at 60°C for 40 minutes .
  • the obtained catalyst supported on a-Al 2 0 3 is called as CAT-II.
  • the silver metal truncated cubes obtained in Preparation Example 2 were supported on CaC0 3 according to the conventional impregnation procedure followed by drying.
  • the Ag nominal metal weight in the carrier was around 1%.
  • the obtained catalyst was washed four times with ethanol at 60°C for 40 minutes .
  • the obtained catalyst supported on CaC0 3 is called as CAT-III.
  • the aqueous solution obtained was mixed with 5.6 mL of deionized water, 3.5 ml of glucose solution (7.5 mM) and then, the resultant mixture was stirred for 2 minutes. To the mixture obtained, 5.72 ml of hexadecyltrimethylammonium bromide solution (50 mM) was added.
  • the resultant mixture was transferred into an autoclave, and the autoclave was closed and heated under stirring at 120°C for 4 hours.
  • the autoclave was cooled down.
  • the reaction mixture was removed from the autoclave and centrifuged.
  • the solid separated was isolated to obtain silver metal particles.
  • the shape of the silver metal particles obtained was not truncated cube but cube.
  • the silver particles obtained in Comparative Preparation Example 1 were supported on ⁇ - ⁇ 1 2 0 3 according to the conventional impregnation procedure followed by drying.
  • the obtained catalyst was washed four times with ethanol at 60°C for 40 minutes.
  • the obtained catalyst supported on ⁇ - ⁇ 1 2 0 3 is called as CAT-IV.
  • the silver particles obtained in Comparative Preparation Example 1 were supported on Ti0 2 according to the conventional impregnation procedure followed by drying.
  • the Ag nominal metal weight in the carrier was around 1%.
  • the obtained catalyst was washed four times with ethanol at 60°C for 40 minutes .
  • the obtained catalyst supported on Ti0 2 is called as CAT-V.
  • Vacuum pressure 1*10 ⁇ 6 mbar during acquisition
  • the catalysts weight was around 150 mg, diluted in CSi in a 1:1 weight ratio.
  • TPSR temperature programmed surface reaction
  • propylene oxide which is useful as an intermediate material of manufactured products, can be produced from propylene and oxygen with superior propylene oxide selectivity (PO/C0 2 ) .

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The present invention relates to a process for producing an olefin oxide comprising reacting an olefin with oxygen in the presence of a catalyst, wherein the catalyst comprises silver metal truncated cubes having one or more Ag (100) planes being selectively exposed.

Description

DESCRIPTION
PROCESS FOR PRODUCING OLEFIN OXIDE Technical Field
The present invention relates to a process for producing an olefin oxide.
Background Art
US 2010/0010243 Al discloses that a method of converting an alkene to an epoxide comprising reacting the alkene with oxygen in the presence of a silver metal nanocube catalyst having a plurality of surface planes that are substantially Ag (100) . Summary of Invention
The present invention provides a process for producing an olefin oxide related to the following:
[1] A process for producing an olefin oxide comprising reacting an olefin with oxygen in the presence of a catalyst, wherein the catalyst comprises silver metal truncated cubes having one or more Ag (100) planes being selectively exposed;
[2] The process according to [1] , wherein the ratio of Ag (100) planes to the surface of the silver metal truncated cube is 20% or more and 80% or less;
[3] The process according to [1] or [2], wherein the catalyst is supported on a carrier;
[4] The process according to any one of [1] to [3], wherein the olefin is propylene and the olefin oxide is propylene oxide; [5] The process according to any one of [1] to [4], wherein silver metal truncated cubes are prepared by reducing Ag+ with a reducing agent in the presence of a capping reagent and an alkali metal source;
[6] A catalyst for producing an olefin oxide which comprises silver metal truncated cubes having one or more Ag (100) planes being selectively exposed.
Brief Description of the Drawings
Fig. 1 is the picture of the silver metal truncated cubes obtained in Preparation Example 1 with electron microscope analysis .
Fig. 2(a) and (b) are the pictures of the silver metal truncated cubes obtained in Preparation Example 2 with electron microscope analysis.
Fig. 2(C) is an imaginary plane containing Ag (100) plane of the silver metal truncated cube obtained in Preparation Example 2, and Ag (100) plane is shown as a diagonal plane.
Fig. 3 is the picture of the silver particles obtained in Comparative Preparation Example 1 with electron microscope analysis.
Description of Embodiments
The present invention is a process for producing an olefin oxide comprising reacting an olefin with oxygen in the presence of a catalyst, wherein the catalyst comprises silvermetal truncated cubes having one or more Ag (100) planes being selectively exposed.
The catalyst can be prepared by reducing Ag+ with a reducing agent in the presence of a capping reagent and an alkali metal source. The catalyst can be produced according to the method described in Science, 298, 2176-2179 (2002), Chemical Physics
Letters 432 (2006) 491-496 or Angew. Chem. Int. Ed. 2005, 44,
2154-2157.
Examples of Ag+ include [Ag (NH3) 2] +OH" and AgN03. Examples of the reducing agent include an organic reducing agent such as glucose and ethylene glycol.
Examples of the capping reagent include hexadecyltrimethylammonium bromide (HTAB) and poly (vinylpyrrolidone) .
Examples of the alkali metal source include alkali metal hydroxides such as sodiumhydroxide and potassiumhydroxide, alkali metal sulfides such as sodium sulfide, and alkali metal halides such as sodium chloride.
The catalyst can also be produced according to the process described in J. Am. Chem. Soc. 2004, 126, 13200-13201 or J. Phys . Chem. B. 2005, 109, 5497-5503 except that an aqueous solution of silver ammonium hydroxide ( [Ag (NH3) 2] +OH") is prepared in the presence of an alkali metal source. Specifically, the catalyst can be produced, for example, by the following steps (a) and (b) :
(a) a step of preparing an aqueous solution of silver ammonium hydroxide ( [Ag (NH3) 2] +OH") by reacting silver nitrate with an alkali metal base in water followed by mixing the resultant mixture with ammonia,
(b) a step of mixing the aqueous solution of [Ag (NH3) 2] +OH~ prepared in the step (a) , glucose and hexadecyltrimethylammonium bromide (HTAB) followed by heating the resultant mixture under stirring .
After the step (b) , the reaction mixture obtained is usually centrifuged to obtain the catalyst. The catalyst obtained can be dispersed again into water and/or washed with water.
The used amount of the alkali metal base in step (a) is usually 0.3 to 0.4 mole relative to 1 mole of silver nitrate.
The used amount of ammonia in the step (a) is usually 2 moles or more relative to 1 mole of silver nitrate, and ammonia is usually used in an amount such that pH of the mixture obtained by mixing of ammonia becomes up to 12.5. The used amount of glucose in the step (b) is usually 0.1 to 5 moles relative to 1 mole of silver nitrate, and the used amount of HTAB in the step (b) is usually 1 to 5 moles relative to 1 mole of silver nitrate.
The heating temperature in the step (b) is usually 50 to
200°C, and preferably 80 to 150°C.
The shape of the catalyst is a truncated cube. The cube has one or more Ag (100) planes being selectively exposed.
The ratio of Ag (100) planes to the surface of the silver metal truncated cube is preferably 20% or more and 80% or less, and preferably 40% or more and 80% or less. The ratio can be calculated based on the observation result with an electron microscope analysis.
The catalyst may contain an alkali metal element derived from the alkali metal source.
The catalyst can contain a small amount of one or more metal elements other than silver and the alkali metal element.
The catalyst is preferably supported on a carrier.
The carrier is preferably one on which the catalyst can be supported and which does not change in property under the condition of the process of the present invention. Examples of the carrier include a metal carbonate, a metal oxide and carbon.
Preferable examples of the metal carbonate include an alkali metal carbonate, an alkaline earth metal carbonate and a transition metal carbonate, and the .alkaline earth metal carbonate is preferable.
Examples of the alkali metal carbonate include sodium carbonate and potassium carbonate . Examples of the alkaline earth metal carbonate include magnesium carbonate, calcium carbonate, strontium carbonate and barium carbonate, and calcium carbonate, strontium carbonate and barium carbonate are preferable. The alkaline earth metal carbonate having a specific surface area of 1 to 70 m2/g measured by nitrogen adsorption of the BET method is preferable.
As the carrier, the metal carbonate may be used as it is or after fixing particles of the metal carbonate each other using a suitable binder . The metal carbonate may be mixed with a molding agent and molded by extrusion molding, press molding or the like to use the obtained product as the carrier. It is preferred that the metal carbonate is used as it is as the carrier.
A metal oxide having a crystal form of a rock salt structure, a corundum structure, a spinel-type structure, a fluorite-type structure, a wurtzite-type structure, a rutile-type structure, a bixbite-type structure, an ilmenite-type structure, a pseudobrookite-type structure or a perovskite-type structure can be used.
Examples of the metal oxide having a rock salt structure include TiO, VO, nO and NiO.
Examples of the metal oxide having a corundum structure include α-Α1203 and cc-Fe203.
Examples of the metal oxide having a spinel-type structure include ZnAl204, y-Fe203 and SnZn204.
Examples of the metal oxide having a fluorite-type structure include Zr02 and Ce02.
Examples of the metal oxide having a wurtzite-type structure include ZnO.
Examples of the metal oxide having a rutile-type structure include Sn02, Ti02 and Ru02.
Examples of the metal oxide having a bixbite-type structure include P~Fe203.
Examples of the metal oxide having an ilmenite-type structure include FeTi03.
Examples of the metal oxide having a pseudobrookite-type structure include FeTi05.
Examples of the metal oxide having a perovskite-type structure include CaTi03, SrTi03, BaTi03, CaZr03, SrZr03, BaZr03 and LaA103.
Examples of the carbon include activated carbon, carbon black, graphite and carbon nanotubes, and graphite is preferred.
As the carrier, a silicon compound can be also used, and examples thereof include a water-soluble silicate such as sodium metasilicate and potassium metasilicate, and a porous silicate having silica as a main component such as silica gel, zeolite and mesoporous silicate.
A commercially available carrier may be used as it is, and such a commercially available carrier may also be used after purifying and molding by a well-known method. The used amount of the carrier is preferably 0.1 to 200 parts by mass per 1 part by mass of the catalyst.
The catalyst can be activated before using for the process of the present invention. The activation of the catalyst is usually conducted by heating the catalyst prepared in the absence of oxygen. The heating temperature of the activation is usually 150 to 300°C.
Next, the process for producing an olefin oxide of the present invention will be illustrated. The process of the present invention comprises reacting an olefin and oxygen in the presence of the above-mentioned catalyst.
The process of the present invention can be performed in a batch-wise reactor or a continuous reactor. From the viewpoint of an industrial process, it is preferably performed in a continuous reactor.
The amount of the catalyst is preferably 0.00005 mole or more relative to 1 mole of the olefin, and more preferably 0.0001 mole or more in a silver metal equivalent . The upper limit thereof is not limited, and while a larger amount of the olefin oxide can be produced if increasing the amount of the catalyst, the upper limit of the amount of the catalyst is usually adjusted by taking an economic efficiency such as the cost of catalyst into consideration.
Oxygen can be used in combination with an inert gas such as nitrogen and carbon dioxide. Air can be used as oxygen. The amount of oxygen can be appropriately adjusted according to the reaction mode (continuous type or batch type) . The amount of oxygen is preferably in the range of 0.01 to 100 moles relative to 1 mole of the olefin, and more preferably in the range of 0.03 to 30 moles.
The reaction temperature is preferably in the range of 100°C to 400°C, and more preferably in the range of 120°C to 300°C.
In this specification, "olefin" means a hydrocarbon having one carbon-carbon double bond, and examples thereof include ethylene, propylene, butene, pentene and hexene, and propylene is preferable.
The olefin can be used in combination with an inert organic gas such as a lower alkane such as methane and ethane. Olefin and oxygen gases can be fed in the form of their mixed gas. Olefin and oxygen gases may be fed with diluent gases . Examples of diluent gases include nitrogen, methane, ethane, propane, carbon dioxide and rare gases such as argon and helium. The reaction of the olefin and oxygen can be conducted in the presence of a halogen compound, particularly an organic halogenated compound. Examples of the halogen compound include the halogen compounds disclosed in Japanese Unexamined Patent Application Publication No. 2008-184456, and it is preferably an organic chlorinated compound. Examples of the organic chlorinated compound include chloroethane, 1, 2-chloroethane, chloromethane and vinyl chloride. The halogen compound is preferably a compound existing in the form of a gas at the temperature and pressure condition in the reaction system of the reaction.
The amount of the halogen compound is preferably 1 to 1000 ppm by volume, and more preferably 1 to 500 ppm by volume based on a total volume of the mixed gas other than steam, i.e. a mixed gas composed of oxygen, the olefin and a dilution gas added as necessary.
The reaction pressure is not limited, and may be selected from those in reduced pressure conditions to pressurized conditions . The pressure under pressurized conditions is preferable from the viewpoint of allowing sufficient contact of oxygen and the olefin with the catalyst, it may be a reaction pressure selected from the range of 0.01 to 3 Pa in absolute pressure, and is more preferably selected from the range of 0.02 to 2 MPa. The reaction pressure is determined by also taking into consideration the pressure resistibility of the reaction device used in the present productionmethod. The reducedpressure conditionmeans apressure lower than the atmospheric pressure. The pressurized condition means a pressure higher than the atmospheric pressure.
The reaction can be carried out in the presence of water. When the reaction is carried out in the presence of water, water is preferably changed into steam by heating to use, and a mixed gas obtained by mixing steam, oxygen and the olefin is preferably contacted with the catalyst. It is preferable to use water as steam.
The amount of water is preferably in the range of about 0.1 to about 20 moles relative to lmole of the olefin, more preferably in the range of 0.2 to 10 moles, and still more preferably in the range of 0.3 to 8 moles. The above-mentioned "amount of water" indicates an amount of water supplied separately from water contained in air in a case of supplying air as oxygen.
Hereinafter, an embodiment of the present production method of a continuous type, which is a favored reaction mode, will be explained.
First, the catalyst in a predetermined amount is filled into a reaction tower equipped with a gas supply port and a gas exhaust port. Suitable heating means may be provided in the reaction tower, and the inside of the reaction tower may be raised in temperature up to a predetermined reaction temperature by such heating means. Subsequently, using a compressor or the like, a source gas containing the olefin and oxygen is supplied from the gas supply port into the reaction tower. By contacting this source gas with the catalyst in the reaction tower, the olefin and oxygen reacts in the presence of the catalyst, and the olefin oxide is generated. Furthermore, the product gas containing the olefin oxide thus generated is exhausted from the gas exhaust port.
The linear velocity of the source gas that is passed through the inside of a reaction tower is determined so as to make a residence time that allows the source gas and the catalyst to sufficiently generate the olefin oxide. Although a case of heating means being provided in the reaction tower has been described in the above embodiment, it may be a mode in which the reaction tower may be maintained at ambient temperature, and the source gas may be supplied and then heated up to a predetermined reaction temperature by appropriate heating means, and then supplied into the reaction tower. It may be a mode in which suitable stirring means is provided in the reaction tower, and a source gas is supplied while stirring the catalyst that is present inside the reaction tower.
The olefin oxide thus generated, unreacted olefin and oxygen, and byproducts such as carbon dioxide may be contained in the product gas passing through the reaction tower. In addition, in a case of using the olefin and oxygen after dilution, an inert gas used for dilution may be incorporated. After having collected this product gas, the olefin oxide, which is the objective, can be removed by separation means such as distillation.
Examples of the olefin oxide include ethylene oxide, propylene oxide, butene oxide, pentene oxide and hexene oxide. Examples
Hereinafter, Examples of the present invention will be described, but the present invention is not to be limited thereto.
Preparation Example 1
To 1 ml of an aqueous silver nitrate solution (concentration:
4.24% (wt/v) , 2 drops of an aqueous sodium hydroxide solution (concentration: 4.24% (wt/v) was added under stirring. A brown precipitate was formed in the resultant mixture. To the mixture, 5% (v/v) ammonia water was added dropwise to obtain an aqueous solution of [Ag (NH3) 2] +OH~.
The aqueous solution obtained was diluted with water, and then, 5% (v/v) ammonia water was added dropwise thereto to obtain 25 ml of an aqueous solution of [Ag (NH3) 2] +OH~ (concentration: 10 mM) .
Five (5) ml of the aqueous solution of [Ag (NH3) 2] +OH" obtained was mixed with 10 ml of glucose solution (7.5 mM) and 3 ml of hexadecyltrimethylammonium bromide solution (50 mM) .
The resultant mixture was transferred into an autoclave, and the autoclave was closed and heated under stirring at 120°C for 8 hours. The autoclave was cooled down. The reaction mixture was removed from the autoclave and centrifuged. The solid separated was isolated to obtain silver metal truncated cubes.
The silver metal truncated cubes obtained were observed with electron microscope, and its result is shown in Fig. 1.
The silver metal truncated cubes obtained were supported on Ti02 according to the conventional impregnation procedure followed by filtering, washing and drying. The Ag nominal metal weight in the carrier was around 1%. The obtained catalyst was washed four times with ethanol at 60°C for 40 minutes . The obtained catalyst supported on Ti02 is called as CAT-I.
Preparation Example 2
To 1 ml of an aqueous silver nitrate solution (concentration: 4.24% (wt/v) , 2 drops of an aqueous sodium hydroxide solution (concentration: 4.24% (wt/v) was added under stirring. A brown precipitate was formed in the resultant mixture. To the mixture, 5% (v/v) ammonia water was added dropwise to obtain an aqueous solution of [Ag(NH3)2]+OH" of which pH was 12.51.
The aqueous solution obtained was diluted with water, and then, 1 mM aqueous sodium hydroxide solution was added dropwise thereto to obtain an aqueous solution of [Ag (NH3) 2] +OH" (concentration: 9.78 mM) .
Five (5) ml of the aqueous solution of [Ag (NH3) 2] +OH" obtained was mixed with 10 ml of glucose solution (7.5 mM) and then, the resultant mixture was stirred for 2 minutes. To the mixture obtained, 3 ml of hexadecyltrimethylammonium bromide solution (50 mM) was added.
The resultant mixture was transferred into an autoclave, and the autoclave was closed and heated under stirring at 120°C for 4 hours. The autoclave was cooled down. The reaction mixture was removed from the autoclave and centrifuged. The solid separated was isolated to obtain silver metal truncated cubes. The silver metal truncated cubes obtained were observed with electron microscope, and its result is shown in Fig. 2(a) and (b) .
The ratio of Ag (100) planes to the surface of the silver metal truncated cube was calculated based on the observation result with electron microscope, and as the result, the ratio was 49%. In the calculation, it was assumed that the surface including Ag (100) plane was an octagon as shown in Fig.2 (c) , and the diagonal plane was Ag (100). In Fig. 2(c), al was 2 (length) and hi was 1.4 (length), and therefore, the ratio of Ag (100) planes to the surface of the silver metal truncated cube was calculated by the following formula:
Ratio (%) = (bl)2/{al)2 X 100
The silver metal truncated cubes obtained in Preparation Example 2 were supported on cc-Al203 according to the conventional impregnation procedure followed by drying. The Ag nominal metal weight in the carrier was around 1%. The obtained catalyst was washed four times with ethanol at 60°C for 40 minutes . The obtained catalyst supported on a-Al203 is called as CAT-II.
The silver metal truncated cubes obtained in Preparation Example 2 were supported on CaC03 according to the conventional impregnation procedure followed by drying. The Ag nominal metal weight in the carrier was around 1%. The obtained catalyst was washed four times with ethanol at 60°C for 40 minutes . The obtained catalyst supported on CaC03 is called as CAT-III.
Comparative Preparation Example 1
To 0.51 g of silver nitrate, 50 ml of deionized water was added, and then, 2 ammonia was added thereto dropwise until pH=ll .2. With the first drop added, a brown precipitate was observed, and then, it was disappeared with the continued drop of ammonia. The solution obtained was diluted with deionized water to obtain 100 ml of a solution' of which ph was 10.8. Ammonia was added thereto until pH=11.2 to obtain an aqueous solution of [Ag(NH3)2]+OH".
The aqueous solution obtained was mixed with 5.6 mL of deionized water, 3.5 ml of glucose solution (7.5 mM) and then, the resultant mixture was stirred for 2 minutes. To the mixture obtained, 5.72 ml of hexadecyltrimethylammonium bromide solution (50 mM) was added.
The resultant mixture was transferred into an autoclave, and the autoclave was closed and heated under stirring at 120°C for 4 hours. The autoclave was cooled down. The reaction mixture was removed from the autoclave and centrifuged. The solid separated was isolated to obtain silver metal particles. The shape of the silver metal particles obtained was not truncated cube but cube.
The silver particles obtained were observed with electron microscope, and its result is shown in Fig. 3.
The silver particles obtained in Comparative Preparation Example 1 were supported on α-Α1203 according to the conventional impregnation procedure followed by drying. The obtained catalyst was washed four times with ethanol at 60°C for 40 minutes. The obtained catalyst supported on α-Α1203 is called as CAT-IV.
The silver particles obtained in Comparative Preparation Example 1 were supported on Ti02 according to the conventional impregnation procedure followed by drying. The Ag nominal metal weight in the carrier was around 1%. The obtained catalyst was washed four times with ethanol at 60°C for 40 minutes . The obtained catalyst supported on Ti02 is called as CAT-V.
Comparative Preparation Example 2
According to the method described in J. Catal., 232 (2005), 85, silver metal supported on CaC03 was prepared. The nominal Ag loading was 5% by weight. The catalyst obtained was calcined in air at 360°C. The obtained catalyst had no Ag (100) plane. The obtained catalyst supported on CaC03 is called as CAT-VI.
Examples 1 to 3 and Comparative Examples 1 to 3
The reaction of propylene and oxygen was conducted using a microreactor connected to a mass spectrometer. The mass analysis was carried out under the following condition:
MODEL: QMG 220 Ml (Telstar)
Filament current: 1.20 mA
Vacuum pressure: 1*10~6 mbar during acquisition
The reactant mixture was 5 ml/min. of propylene (C3H6) , 2.5 ml/min. of oxygen (02) , and 22.5 ml/min. of argon (Ar) , which represent a molar ratio C3H6:02= 2:1. The catalysts weight was around 150 mg, diluted in CSi in a 1:1 weight ratio.
In order to determine the onset temperature of reaction, product distribution and their evolution with the temperature, we performed temperature programmed surface reaction (TPSR) at a rate of 2°C/min. The activation of the catalyst was done under several conditions (argon or 02 at different temperatures) .
The results are shown in Table 1. In Table 1, "PO" means propylene oxide, "C02" means carbon dioxide, and C02 and PO are increment values measured relative to reference values of the reactant mixture. Table 1
Figure imgf000015_0001
Industrial Applicability
According to the present invention, propylene oxide, which is useful as an intermediate material of manufactured products, can be produced from propylene and oxygen with superior propylene oxide selectivity (PO/C02) .

Claims

1. A process for producing an olefin oxide comprising reacting an olefin with oxygen in the presence of a catalyst, wherein the catalyst comprises silver metal truncated cubes having one or more Ag (100) planes being selectively exposed.
2. The process according to claim 1, wherein the ratio of Ag (100) planes to the surface of the silver metal truncated cube is 20% or more and 80% or less.
3. Theprocess according to claim1, wherein the catalyst is supported on a carrier.
4. The process according to claim 1, wherein the olefin is propylene and the olefin oxide is propylene oxide.
5. The process according to claim 1, wherein silver metal truncated cubes are prepared by reducing Ag+ with a reducing agent in the presence of a capping reagent and an alkali metal source .
6. A catalyst for producing an olefin oxide which comprises silver metal truncated cubes having one or more Ag (100) planes being selectively exposed.
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Citations (2)

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Publication number Priority date Publication date Assignee Title
JP2008184456A (en) 2007-01-31 2008-08-14 Sumitomo Chemical Co Ltd Method for producing propylene oxide
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Publication number Priority date Publication date Assignee Title
JP2008184456A (en) 2007-01-31 2008-08-14 Sumitomo Chemical Co Ltd Method for producing propylene oxide
US20100010243A1 (en) 2008-07-09 2010-01-14 The Regents Of The University Of Michigan Epoxidation catalyst and process

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