WO2012067264A1 - Procédé de production d'un oxyde d'oléfine - Google Patents

Procédé de production d'un oxyde d'oléfine Download PDF

Info

Publication number
WO2012067264A1
WO2012067264A1 PCT/JP2011/077117 JP2011077117W WO2012067264A1 WO 2012067264 A1 WO2012067264 A1 WO 2012067264A1 JP 2011077117 W JP2011077117 W JP 2011077117W WO 2012067264 A1 WO2012067264 A1 WO 2012067264A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrogen peroxide
titanosilicate
olefin
component
reactor
Prior art date
Application number
PCT/JP2011/077117
Other languages
English (en)
Inventor
Fumikazu Yamashita
Michio Yamamoto
Original Assignee
Sumitomo Chemical Company, Limited
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 Sumitomo Chemical Company, Limited filed Critical Sumitomo Chemical Company, Limited
Publication of WO2012067264A1 publication Critical patent/WO2012067264A1/fr

Links

Classifications

    • 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
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/7088—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride

Definitions

  • the present invention relates to a process for
  • a process for producing an olefin oxide for example, which comprises a step of reacting an olefin with hydrogen peroxide in the presence of a titanosilicate .
  • Patent Document 1 discloses a process for producing propylene oxide, which comprises the steps of feeding propylene and hydrogen peroxide into a reactor charged with titanisilicate (or Ti-MWW) and a solvent mixture of acetonitrile and water, and reacting propylene with hydrogen peroxide within the reactor to produce the propylene oxide.
  • titanisilicate or Ti-MWW
  • solvent mixture of acetonitrile and water
  • Patent Document 1 JP-A-2003-327581 (refer to Examples) [0004]
  • the present invention is accomplished as a result of the present inventor's intensive researches to solve the above-described problem. That is, the present invention provides the following.
  • a process for producing an olefin oxide comprising a step of reacting an olefin with hydrogen peroxide in a liquid phase in the presence of the following components (a) , (b) and (c) :
  • liquid phase is a solvent mixture containing at least one kind of a water-soluble organic solvent and water.
  • component (b) is at least one kind of titanosilicate selected from the group consisting of Ti-MWW, Ti-MWW precursors and silylated Ti-MWW.
  • paragraph [1] is optionally referred to as “the present reaction”
  • the process for producing the olefin oxide is optionally referred to as “the present production
  • the component (c) i.e., an aluminosilicate ⁇ for use in the present production process is a compound obtained by substituting a part of a silicon atom in silicon dioxide or a silicate with an aluminum atom [Reference Document 1: "Kagaku Daijiten 1", p445, eddited by the Editorial
  • a typical aluminosilicate is represented by the formula: xM I]: 2 0. yAl 2 0 3 . zSi0 2 [wherein M ⁇ I 2 0 represents an oxide of one kind or two or more kinds of metals, each of which is a divalent metal ion; and x, y and z represent amounts of a metal oxide, aluminum oxide and silicon dioxide contained in this aluminosilicate, respectively] .
  • Such an aluminosilicate is a composite oxide which contains silicon dioxide (Si0 2 ) , aluminum oxide (A1 2 0 3 ) and a metal oxide (M IT 2 0) .
  • the component (c) for use in the present production process contains no titanium.
  • the wording of "containing no titanium” herein used means that, when contents of a silicon atom and an aluminum atom in the aluminosilicate are determined by the ICP emission spectrometry, a content of a titanium atom is found to be below the lower limit for detection by this analysis.
  • This aluminosilicate may be a naturally-produced substance or an artificially-produced substance.
  • the component (c) may be either an amorphous aluminosilicate or a crystalline aluminosilicate.
  • crystalline aluminosilicate if used, may have a
  • aluminosilicates are easily available from the market.
  • an aluminosilicate as a layer silicate mineral examples include clay minerals such as kaolinite and
  • aluminosilicate with a porous crystalline structure examples include mordenite, ⁇ -zeolite, A type zeolite, faujasite type zeolite, ferrierite, chabazite and ZSM-5 type zeolite.
  • zeolites As the faujasite type zeolite, there are known zeolites called X type zeolite and Y type zeolite.
  • aluminosilicate examples include mesoporous aluminosilicates such as MCM-41, MCM-48, FSM-16 and SBA-15.
  • At least one kind of cation such as monovalent ion, polyvalent metal ion or ammonium ion is bonded to a part or a whole of its ion- exchange site; and a hydrogen ion also may be bonded to a part of its ion-exchange site.
  • the component (c) to be used in the present invention has no titanium ion bonded to its ion-exchange site.
  • the component (c) for use in the present production process may be an aluminosilicate produced by any of the known processes or a commercially available aluminosilicate, while the latter aluminosilicate is preferred.
  • aluminosilicate readily available from the market include mordenite, ⁇ -Zeolites, A type zeolites, faujasite type zeolites, ferrierite, chabazite and - SM-5 type zeolites.
  • a type zeolites More preferable among those are A type zeolites; still more preferable is an aluminosilicate containing an alkali metal or an alkali earth metal; far still more preferable is an aluminosilicate containing a metal selected from the group consisting of lithium, sodium, potassium, magnesium and calcium; and particularly
  • an aluminosilicate containing potassium is preferable.
  • the component (c) for use in the present production process is an aluminosilicate containing no titanium. More preferably, the component (c) is an- aluminosilicate containing no transition metal as well as titanium.
  • the wording of "containing no transition metal" herein used means that a content of a transition metal is found to be below the lower limit for detection, when the aluminosilicate is analyzed by the above-described ICP emission spectrometry. ,An aluminosilicate containing no transition metal as well as titanium, particularly an aluminosilicate containing no transition metal and
  • containing an alkali metal or an alkali earth metal can be readily selected from the commercially available products.
  • the commercially available products are A type zeolites such as Molecular Sieves 3A, Molecular Sieves 4A and Molecular Sieves 5A; faujasite type zeolites such as Molecular Sieves 13X; ⁇ -zeolites; and mordenite.
  • the component (c) for use in the present production process may be produced by a known process; or a
  • aluminosilicate may be directly used as the component (c) .
  • an aluminosilicate molded and formed with the use of a binder or the like into a desired shape may be used as the component (c) .
  • powdery aluminosilicate obtained by pulverizing a molded aluminosilicate may be used.
  • a binder or the like for use in molding of the aluminosilicate is required to contain no titanium.
  • the component (b) for use in the present production process is a titanosilicate which exhibits a catalytic ability in the present reaction.
  • Titanosilicate is a generic name for silicates any of which has a
  • the titanosilicate has a substantially tetrahedrally-coordinated titanium atom and shows a highest absorption peak within a wavelength range of from 210 to 230 nm in a UV visible absorption spectrum within a
  • This UV visible . spectrum can be measured by a diffused reflection method using a UV visible spectrophotometer equipped with a diffuse reflection device.
  • the component (b) for use in the present production process is preferably a titanosilicate with a pore
  • the titanosilicate with a pore structure herein referred to is a titanosilicate with a structure which has a ring composed of a Si-0 bond and/or a Ti-0 bond as a pore entrance. This pore may be a half-cup-like pore called side pocket.
  • the wording of "the ring containing 12 or more oxygen . atoms" means that the number of oxygen atoms contained in the ring structure is 12 or more, when the ring structure of the section of the narrowest portion of the pore (b-1) or the ring structure of the pore entrance (b-2) is observed.
  • the pore structure which has a ring containing 12 or more oxygen atoms, of the titanosilicate is acknowledged generally by analyzing an X-ray diffraction pattern.
  • titanosilicates 1 to 5 are given as the above-described titanosilicate.
  • a crystalline titanosilicate which has pores each having a ring structure containing 12 or more oxygen atoms e.g., Ti-Beta having a BEA structure, identified in the structure codes of the International Zeolite Association
  • IZA cf., Journal of Catalysis 199, 41-47, 2001
  • Ti-ZSM- 12 having a TW structure cf., Zeolites 15, 236-242,
  • Ti-MOR having a MOR structure (cf., The Journal of Physical Chemistry B 102, 9297-9303, 1998); Ti-ITQ-7 having an ISV structure (cf., Chemical Communications, 761-762, 2000); Ti-MCM-68 having a MSE structure (cf., Chemical Communications, 6224-6226, 2008); and Ti-MWW having a MWW structure (cf., Chemistry Letters, 774-775, 2000).
  • a crystalline titanosilicate which has pores each having a ring structure containing 14 oxygen atoms e.g., Ti-UTD-1 having a DON structure (cf., Studies in Surface Science and Catalysis 15, 519-525, 1995) , etc.
  • a layer titanosilicate which has pores each having a ring structure containing 12 oxygen atoms:
  • Ti-MWW precursors cf., European Laid-Open Patent ⁇ Publication No. 1731515A1
  • Ti-YNU-1 cf., Angewandte
  • Ti-MCM-41 cf., Microporous Materials 10, 259-271, 1997
  • Ti-MCM-48 cf., Chemical Communications, 145-146, 1996
  • Ti-SBA-15 cf., Chemistry of Materials 14, 1657- 1664, 2002
  • silylated titanosilicates obtained by further
  • silylating the above-listed titanosilicates 1 to 4 such as silylated Ti-MWW, etc.
  • ring structure containing 14 oxygen atoms means that the number of oxygen atoms in the above-described ring structure (b-1) or (b-2) is 14.
  • a titanosilicate obtained by expanding interlayers. of a crystalline titanosilicate
  • titanosilicate having a layer structure.
  • Whether or not a titanosilicate has a layer structure can be determined by electron microscopic observation or measurement of an X-ray diffraction pattern.
  • the above- described layer precursor of the crystalline titanosilicate is, for example, a titanosilicate having a layer structure, and this titanosilicate can be formed into a crystallized titanosilicate when subjected to a dehydration condensation treatment.
  • a layer titanosilicate which has pores each having a ring structure containing 12 or more oxygen atoms can be easily determined from the structure of a corresponding crystalline titanosilicate.
  • titanosilicates 1 to 3 and the silylated titanosilicates obtained from the same titanosilicates have pores with pore diameters of from 0.6 to 1.0 nm.
  • the pore diameters can be determined generally by analyses of X-ray diffraction patterns.
  • mesopores Regular mesopores mean a structure having mesopores regularly and repetitively arrayed therein. Such mesopores have pore diameters of from 2 to 10 nm.
  • silylated titanosilicate is obtained, for example, by treating any of the
  • titanosilicates 1 to 4 with a silylating agent examples include 1 , 1 , 1 , 3 , 3 , 3-hexamethyl- disilazane, trimethylchlorosilane, etc. (cf., European Laid-Open Patent Publication No. EP1488853A1) .
  • Ti-MW As the component (b) for use .in the present production process, Ti-MW , a Ti-MWW precursor and silylated Ti-MWW (obtained by silylating Ti-MWW) are preferable among the above-exemplified titanosilicates, and a Ti-MWW precursor is more preferable.
  • the component (b) for use in the present production process may be activated by bringing the titanosilicate into contact with an oxygen peroxide solution to thereby treat the titanosilicate with hydrogen peroxide.
  • the hydrogen peroxide solution for use in this treatment with hydrogen peroxide is preferably a solution having a hydrogen peroxide concentration of from 0.0001 to 50% by mass.
  • a solvent for use in this hydrogen peroxide solution is not limited. However, preferably, this solvent is water or the same one as the component (a) for use in the present reaction as will be described later.
  • the component (a) for use in the present production process is water or a solvent mixture of water and an organic solvent (or a solvent mixture of water/organic solvent) , and the use of the solvent mixture of
  • water/organic solvent is preferred.
  • the organic solvent there is used an organic solvent which is selected from the group consisting of alcohol solvents, ketone solvents, nitrile solvents, ether solvents, ester solvents, aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents and which is inert to hydrogen peroxide.
  • the organic solvent may comprise two or more kinds of such organic solvents. in combination.
  • this organic solvent is preferably a water-soluble organic solvent which is miscible with water. More preferable among the water- soluble solvents are nitrile solvents. Particularly
  • nitrile solvents acetnitirile .
  • a mixing ratio of water to the organic solvent in this solvent mixture is preferably from 90 : 10 to 0.01 : 99.99, more preferably from 50 : 50 to 0.1 : 99.9, still more preferably from 40 : 60 to 5 : 95, in terms of a mass ratio of water to the organic solvent.
  • the present production process comprises a step of reacting an olefin with hydrogen peroxide in a liquid phase in the presence of the above-described components (a) , (b) and (c) .
  • the olefin is reacted with hydrogen peroxide in the liquid phase by dissolving the olefin in the component (a) which contains hydrogen peroxide
  • a mode for carrying out the present production process may be a batch process, a semi-batch process or a
  • a reactor for use in the present production process is specifically a slurry reactor, a stirring tank, a fixed-bed reactor or the like, and thus is not particularly limited.
  • a reactor for use in a . continuous process is desirable from the viewpoint of commercial production advantage.
  • an embodiment of the present production process by way of the continuous process with the use of a slurry reactor will be described below.
  • the slurry reactor will be described below.
  • the reactor optionally referred to simply as "the reactor” in the description set forth below.
  • An amount of the component (a) to be used in the present production process may be determined, taken a production amount of such by-produced water also into consideration. This amount is preferably 10 to 10,000 times, more preferably 20 to 1,000 times, in terms of mass, larger than an amount of the component (b) to be used.
  • a mode for carrying out the present production process may be optionally selected, insofar as an olefin and hydrogen peroxide can be brought into contact with each other in the presence of the components (a) , (b) and (c) within a slurry reactor: that is,
  • the components (b) and (c) may be previously charged in the slurry reactor, and the component (a) may be fed into the reactor together with an olefin and hydrogen peroxide; or
  • a part of the component (a) may be charged in a slurry reactor together with the components (b) and (c) , and the rest of the component (a) may be fed into the reactor together with an olefin and hydrogen peroxide; or
  • hydrogen peroxide may be charged in a slurry reactor together with the components (a) , (b) and (c) , and then, an olefin may be fed into the reactor.
  • the mode of charging the slurry reactor with the components (b) and (c) is the mode of charging the slurry reactor with the components (b) and (c) , and then feeding the component (a) , the olefin and hydrogen peroxide into the slurry reactor.
  • the present production process is carried out in safety, usually by using hydrogen peroxide as a solution such as an aqueous solution, and it is therefore preferable to feed a part of the component (a) together with hydrogen peroxide into the slurry reactor.
  • An amount of the component (b) for use in the present production process may be appropriately selected in
  • this amount is typically from 1/10 to 1/1,000 of the mass of the component (a) .
  • An amount of the component (c) for use in the present production process may be appropriately selected in
  • this amount is preferably 0.01 to 10 times, more preferably 0.1 to 5 times, larger than the mass of the component (b) .
  • hydrogen peroxide is fed into the slurry reactor, preferably in the form of a solution (i.e., a hydrogen peroxide solution) , particularly in the form of an aqueous solution (i.e., an aqueous hydrogen peroxide solution).
  • a solution i.e., a hydrogen peroxide solution
  • an aqueous solution i.e., an aqueous hydrogen peroxide solution
  • a hydrogen peroxide concentration in the hydrogen peroxide solution or aqueous solution is
  • the hydrogen peroxide may be a commercially available one in the form of an aqueous hydrogen peroxide solution (hydrogen peroxide water) , which may be directly used in the present production process . If needed, such a
  • aqueous hydrogen peroxide solution may be purified to be used in the present production process.
  • a precursor of hydrogen peroxide (or a hydrogen peroxide precursor) may be fed into a slurry reactor, and hydrogen peroxide may be produced from the hydrogen peroxide precursor in a reaction system for the present reaction.
  • hydrogen peroxide precursor hydrogen and oxygen may be used in combination; or oxygen and a derivative of anthrahydroquinone may be used in combination.
  • a noble metal catalyst is charged in the slurry reactor together with the components (b) and (c) , and then, hydrogen and oxide are fed into the reactor together with an olefin.
  • an action of the noble metal catalyst causes production of hydrogen peroxide from hydrogen and oxygen in the ' reaction system for the present reaction.
  • Hydrogen and/or oxygen to be used herein may be diluted with a suitable inert gas such as a nitrogen gas or a rare gas: for example, air may be used as oxygen diluted with an inert gas.
  • the noble metal catalyst for use in production of hydrogen peroxide . from hydrogen and oxygen is preferably a palladium- containing noble metal catalyst, more preferably a noble metal catalyst which contains .
  • a palladium metal (or a zero- valent palladium) .
  • a palladium metal as it is may be used as the noble metal catalyst, or a palladium metal may be supported on a suitable carrier (e.g., activated carbon or the like) for use as the noble metal catalyst.
  • the anthrahydroquinone derivative is charged in a slurry reactor together with, for example, the components (b) and (c) , and then, oxygen is fed into the reactor together with an olefin. By doing so, the anthrahydroquinone derivative is reacted with oxygen in the reaction system to produce a corresponding anthraquinone derivative together with hydrogen peroxide. Examples of the anthraquinone derivative are
  • Any olefin having a carbon-carbon double bond in the molecule may be used in the present production process.
  • an olefin having 2 to 30 carbon atoms in total is used.
  • This olefin may be a chain (or non-cyclic) olefin (e.g., an alkene such as ethylene, propylene, butene, hexene or the like) or a cyclic olefin (e.g., a cycloalkene. such as cyclohexene, cyclooctene, cyclodecene, or the like) .
  • This olefin is preferably a C 2 -C 6 non-cyclic olefin, more preferably propylene.
  • a molar ratio of hydrogen peroxide to be used relative to an amount of the olefin is preferably from 50 : 1 to 1 : 50, more preferably from 10 : 1 to 1 : 10.
  • a reaction temperature in the present reaction may be suitably selected within a range of 10 to 100°C, in
  • This reaction temperature is preferably from 30 to 100°C.
  • the reaction temperature may be controlled with a suitable temperature-controlling means provided on the slurry reactor. Otherwise, the olefin and hydrogen peroxide (or a hydrogen peroxide precursor) may be controlled at desired temperatures with a suitable temperature-controlling means and then may be fed into the. slurry reactor.
  • a reaction pressure in the present reaction is
  • an inert gas which will give no significant influence on proceeding of the present reaction may be fed into the slurry reactor.
  • an inert gas which will give no significant influence on proceeding of the present reaction may be fed into the slurry reactor.
  • examples of such an inert gas include alkanes such as methane, ethane and propane, carbon dioxide, etc., in addition to nitrogen and the rare gas (e.g., argon, etc.) which already have been exemplified as the diluting gas for use in the production of hydrogen peroxide from hydrogen and oxygen by the action of the noble metal
  • the propylene is diluted with an inert gas and is then fed into a slurry reactor, so as to control the reaction pressure.
  • a diluting degree of the propylene with a diluting gas may be
  • a reaction pressure in the present reaction is determined in consideration of a pressure-proofing capacity of a reactor to be used, such as a slurry reactor.
  • materials being collectively referred to as "materials for the present reaction" are fed into the reactor.
  • separate supply ports may be provided to feed the component (a), the olefin and iiydrogen peroxide,
  • s single supply port may be provided to feed a mixture of the materials for the present reaction which have been previously mixed with one another.
  • a suitable mixer may be provided in front of the supply port of the slurry reactor so as to previously mix the materials for the present reaction.
  • the reactor is further provided with an outlet port for drawing the
  • suitable stirring means may be provided in the reactor so as to bring the olefin and hydrogen peroxide into
  • the materials for the present reaction are continuously fed into the reactor to thereby react the olefin with hydrogen peroxide in a liquid phase within the reactor, so as to produce an olefin oxide.
  • the resultant olefin oxide is drawn out usually as a reaction mixture together with a part of the component (a), from the reactor.
  • the outlet port for drawing the reaction is provided.
  • a residence time for the materials for the present production within the reactor may be appropriately controlled.
  • the residence time is, for example, from about 5 to about 120 minutes. To control the residence time within this range, rates of feeding the materials for the present reaction through the supply ports and a rate of drawing the reaction mixture from the outlet port are controlled.
  • the reaction mixture drawn out from the reactor after the present production process is likely to contain a side product in addition to the intended olefin oxide and non- reacted products (i.e., non-reacted olefin, etc.) of the materials for the present reaction.
  • the intended olefin oxide can be separated from this reaction mixture by a known purifying method, for example, distillation or the like.
  • Each of the slurry reactors may be changed to a fixed bed reactor to carry out the above- described continuous reaction mode; or each of the slurry reactors may be changed to a stirring tank to carry out a batch type reaction mode wherein the present production process is conducted without drawing the reaction mixture during the reaction.
  • a production amount of an olefin oxide per unit mass of a catalyst i.e., a titanosilicate as the component (b) .
  • an amount of the catalyst to be used relative to an amount of the olefin to be used can be extremely decreased. Therefore, a cost for the catalyst can be reduced, and a scale of a reactor to be used in the present production process can be reduced.
  • an olefin oxide can be produced, while a selectivity for olefin oxide based on an olefin, determined from a ratio of a production amount of an olefin oxide to a consumption amount of an olefin (i.e., an olefin-based selectivity) and a selectivity for olefin oxide based on hydrogen peroxide, determined from a ratio of a production amount of an olefin oxide to a consumption amount of hydrogen peroxide (i.e., a hydrogen peroxide- based selectivity) are both improved to higher levels.
  • these selectivities can be calculated by molar conversion. This effect exhibited by the present
  • This suspended solution was filtered to separate a solid (a filter cake) .
  • This filter cake was then washed with water until a pH of the filtrate had reached about 10.
  • the filter cake was then dried at 50°C until no decrease in mass had been observed, to obtain a solid a (515 g) .
  • This solid a (75 g) was admixed with 2M nitric acid (3,750 mL), and this mixture was heated until reflux of the solvent took place, and was then maintained for 20 hours under the reflux of the solvent.
  • the resulting reaction mixture was cooled and was then filtered to obtain a filter cake. .
  • the filter cake was washed with water until a pH of the filtrate showed almost neutrality.
  • the filter cake washed with water was dried in vacuum at 150°C until no decrease in mass was observed. Thus, white powder a (61 g) was obtained.
  • This white powder a was confirmed to be a Ti- WW precursor with a pore structure in which each pore had a ring structure containing 12 or more oxygen atoms, from the X-ray diffraction pattern and the UV visible absorption spectrum of the white powder a .
  • the obtained white powder a (60 g) was calcined at 530°C for 6 hours to obtain powder (Ti-MWW) (54 g) ..
  • This powder a was confirmed to be Ti-MWW with a pore structure in which each pore had a ring structure containing 12 or more oxygen atoms, from the X-ray diffraction pattern and the UV visible absorption spectrum of the powder a.
  • the above-described operation was further carried out twice to obtain total 162 g of Ti-MWW.
  • piperidine (300 g) and pure water (600 g) were charged in an autoclave at room temperature under an atmosphere of air and were 1 " then stirred to form a gel.
  • the autoclave was sealed up after the gel had been aged for 1.5 hours therein.
  • An internal temperature of the autoclave was raised to about 160°C over 4 hours while the gel was being stirred.
  • the internal temperature of the autoclave was maintained at the same temperature for 24 hour to thereby carry out a hydrothermal treatment of the gel. Thus, a suspended solution was obtained.
  • This suspended solution was filtered to separate a filter cake (a solid b) .
  • This filter cake was then washed with water until a pH of the filtrate had reached about 9.
  • the washed solid b was then dried at 150°C in vacuum until no decrease in mass was observed, to obtain white powder b (141 g) .
  • this white powder b showed a similar X-ray diffraction pattern to that of the Ti-MWW precursor and thus was confirmed to have a pore structure in which each pore had a ring structure
  • This white powder b was also confirmed to be a titanosilicate from the result of the measurement of the UV visible absorption spectrum thereof (hereinafter, this Ti-MWW precursor being
  • Ti-MWW precursor b optionally referred to as the Ti-MWW precursor b .
  • a titanium content of the Ti-MWW is optionally referred to as the Ti-MWW precursor b .
  • precursor b was 1.61% by mass.
  • the inside of the reactor was controlled at 60°C in reaction temperature and at 2.0 MPa in reaction pressure (or gauge pressure) , and a residence time for the raw materials for use in the present production within the reactor was set at 36 minutes, during which the reaction mixture (95 mL) within the reactor was adjusted so that an mount of the Ti-MWW precursor b as the component (b) might be 0.5 g, and an amount of the Molecular Sieves 3A as the component (c) , 0.2 g.
  • the reaction mixture drawn out of the reactor was sampled (the first sampling) .
  • the present production process was further continued, and the second sampling was conducted after 14 hours had passed since the start of the reaction.
  • the reaction mixture obtained by the first sampling was called Sample 1; and the reaction mixture obtained by the second sampling was called Sample 2.
  • Sample 2 As a result of the analysis of Sample 2 by gas chromatography, a production amount of propylene oxide (or PO) (a PO production amount) per unit mass of the
  • titanosilicate was found to be 443 mmol-PO/g-titanosilicate per hour; a propylene-based selectivity, 99.8%; and a hydrogen peroxide-based selectivity, higher than 99% (a hydrogen peroxide-based selectivity > 99%).
  • a conversion of hydrogen peroxide was found to be 93.2%.
  • Sample 1 was analyzed by the same method. As a result, a PO production amount per unit mass of the titanosilicate (or the catalyst) was found to be 435 mmol- PO/g-titanosilicate per hour; a propylene-based selectivity, 99.6%; and a hydrogen peroxide-based selectivity, 96.5%;
  • Propylene oxide can be separated from the reaction mixture obtained by the production process in this Example, by an operation, for example, distillation or the like.
  • Example 1 The same tests as in Example 1 were conducted except for. the use of Molecular Sieves 4A (containing no titanium, manufactured by ACALAI TESQUE, ING. ) in place of Molecular Sieves 3A used in Example 1.
  • Molecular Sieves 4A containing no titanium, manufactured by ACALAI TESQUE, ING.
  • propylene-based selectivity 99.8%
  • a hydrogen peroxide- based selectivity > 99%
  • a conversion of hydrogen peroxide 90.6%
  • Propylene-based selectivity 99.7%; a hydrogen peroxide- based selectivity, 92.9%; and a conversion of hydrogen peroxide, 96.6%.
  • Propylene oxide can be separated from the reaction mixtures obtained by the production process in this Example, by an operation, for example, distillation or the like.
  • Example 1 The same tests as in Example 1 were conducted except for the use of Molecular Sieves 13X (containing no titanium, manufactured by NACALAI TESQUE, ING. ) in place of Molecular Sieves 3A used in Example 1.
  • Molecular Sieves 13X containing no titanium, manufactured by NACALAI TESQUE, ING.
  • propylene-based selectivity 99.8%
  • a hydrogen peroxide- based selectivity 95.4%
  • a conversion of hydrogen peroxide 89.1%.
  • propylene-based selectivity c 99.6% ; a hydrogen peroxide- based selectivity, 93.8%; and a conversion of hydrogen peroxide, 96.2%.
  • Propylene oxide can be separated from the reaction mixtures obtained by the production process in this Example, by an operation, for example, distillation or the like.
  • Example 1 The same tests as in Example 1 were conducted except for the use of Molecular Sieves 5A (containing no titanium, manufactured by NACALAI TESQUE, ING. ) in place of Molecular Sieves 3A used in Example 1.
  • Molecular Sieves 5A containing no titanium, manufactured by NACALAI TESQUE, ING.
  • propylene-based selectivity 99.8%
  • a hydrogen peroxide- based selectivity > 99%
  • a conversion of hydrogen peroxide 83.5%
  • titanosilicate production amount per unit mass of titanosilicate was found to be 420 mmol-PO/g-titanosilicate per hour; a propylene- based selectivity, 99.5%; a hydrogen peroxide-based
  • Propylene oxide can be separated from the reaction mixtures obtained by the production process in this Example, by an operation, for example, distillation or the_ like.
  • a titanosilicate was used as a catalyst according to the production process of Patent Document l,.and the
  • the inside of the reactor was controlled at 60°C in reaction temperature and at 2.0 MPa in reaction pressure (or gauge pressure) , and a residence time for the raw materials for use in the present production within the reactor was set at 36 minutes, during which the reaction mixture (95 mL) within the reactor was adjusted so that an amount of the Ti-MWW precursor b as the component (b) might be 0.5 g.
  • a production activity for PO per unit mass of the titanosilicate was found to be 437 mmol-PO/g-titanosilicate per hour; a propylene-based selectivity, 99.5%; a hydrogen peroxide-based selectivity, 96.0%; and a conversion of hydrogen peroxide, 94.9%.
  • the propylene oxide production amounts (or PO)
  • the present invention can be employed for production of olefin oxides, particularly propylene oxide, useful as raw materials for various industrial materials.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Epoxy Compounds (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Cette invention vise à pourvoir à un procédé de production d'oxyde d'oléfine qui permet d'augmenter la quantité d'oxyde d'oléfine produite par unité de poids du catalyseur. Le procédé de production d'un oxyde d'oléfine selon l'invention comprend une étape de mise en réaction d'une oléfine avec du peroxyde d'hydrogène en phase liquide en présence des composants (a), (b) et (c) suivants : (a) un solvant, (b) un silicate de titane, et (c) un aluminosilicate (ne contenant pas de titane), le composant (b) étant, de préférence, un silicate de titane ayant une structure poreuse où chaque pore a une structure annulaire contenant 12 atomes d'oxygène ou plus.
PCT/JP2011/077117 2010-11-19 2011-11-17 Procédé de production d'un oxyde d'oléfine WO2012067264A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010-258577 2010-11-19
JP2010258577A JP2012106967A (ja) 2010-11-19 2010-11-19 酸化オレフィンの製造方法

Publications (1)

Publication Number Publication Date
WO2012067264A1 true WO2012067264A1 (fr) 2012-05-24

Family

ID=45418738

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/077117 WO2012067264A1 (fr) 2010-11-19 2011-11-17 Procédé de production d'un oxyde d'oléfine

Country Status (2)

Country Link
JP (1) JP2012106967A (fr)
WO (1) WO2012067264A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5412122A (en) * 1993-12-23 1995-05-02 Arco Chemical Technology, L.P. Epoxidation process
US5525563A (en) * 1993-07-12 1996-06-11 Degussa Aktiengesellschaft Structured catalyst including microporous oxides of silicon, aluminum and titianium
JP2003327581A (ja) 2002-03-04 2003-11-19 Sumitomo Chem Co Ltd プロピレンオキサイドの製造方法
EP1489075A1 (fr) * 2002-03-04 2004-12-22 Sumitomo Chemical Company, Limited Procede de preparation d'oxyde de propylene
EP1488853A1 (fr) 2002-03-04 2004-12-22 Sumitomo Chemical Company, Limited Procede permettant d'ameliorer un catalyseur de silicate de titane cristallin a structure mww
EP1731515A1 (fr) 2004-03-22 2006-12-13 Sumitomo Chemical Company, Limited PROC D DE FABRICATION D’OXYDE DE PROPYL&Egra ve;NE
JP2010258577A (ja) 2009-04-22 2010-11-11 Renesas Electronics Corp 補間型ａ／ｄ変換器
WO2010130610A1 (fr) * 2009-05-12 2010-11-18 Basf Se Procédé de production d'oxyde de propylène

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5525563A (en) * 1993-07-12 1996-06-11 Degussa Aktiengesellschaft Structured catalyst including microporous oxides of silicon, aluminum and titianium
US5412122A (en) * 1993-12-23 1995-05-02 Arco Chemical Technology, L.P. Epoxidation process
JP2003327581A (ja) 2002-03-04 2003-11-19 Sumitomo Chem Co Ltd プロピレンオキサイドの製造方法
EP1489075A1 (fr) * 2002-03-04 2004-12-22 Sumitomo Chemical Company, Limited Procede de preparation d'oxyde de propylene
EP1488853A1 (fr) 2002-03-04 2004-12-22 Sumitomo Chemical Company, Limited Procede permettant d'ameliorer un catalyseur de silicate de titane cristallin a structure mww
EP1731515A1 (fr) 2004-03-22 2006-12-13 Sumitomo Chemical Company, Limited PROC D DE FABRICATION D’OXYDE DE PROPYL&Egra ve;NE
JP2010258577A (ja) 2009-04-22 2010-11-11 Renesas Electronics Corp 補間型ａ／ｄ変換器
WO2010130610A1 (fr) * 2009-05-12 2010-11-18 Basf Se Procédé de production d'oxyde de propylène

Non-Patent Citations (15)

* Cited by examiner, † Cited by third party
Title
"Kagaku Daijiten 1", 15 March 1984, KYORITSU SHUPPAN CO., LTD., pages: 445
ANGEWANDTE CHEMIE INTERNATIONAL EDITION, vol. 43, 2004, pages 236 - 240
CATALYSIS LETTERS, vol. 113, 2007, pages 160 - 164
CHEMICAL COMMUNICATIONS, 1996, pages 145 - 146
CHEMICAL COMMUNICATIONS, 2002, pages 1026 - 1027
CHEMICAL COMMUNICATIONS, 2008, pages 6224 - 6226
CHEMICAL COMMUNICATIONS, vol. 7, no. 6, 2000, pages 1 - 762
CHEMISTRY LETTERS, 2000, pages 774 - 775
CHEMISTRY OF MATERIALS, vol. 14, 2002, pages 1657 - 1664
JOURNAL OF CATALYSIS, vol. 199, 2001, pages 41 - 47
MICROPOROUS AND MESOPOROUS MATERIALS, vol. 113, 2008, pages 435 - 444
MICROPOROUS MATERIALS, vol. 10, 1997, pages 259 - 271
STUDIES IN SURFACE SCIENCE AND CATALYSIS, vol. 15, 1995, pages 519 - 525
THE JOURNAL OF PHYSICAL CHEMISTRY B, vol. 102, no. 9, 1998, pages 297 - 9303
ZEOLITES, vol. 15, 1995, pages 236 - 242

Also Published As

Publication number Publication date
JP2012106967A (ja) 2012-06-07

Similar Documents

Publication Publication Date Title
Wu et al. A novel titanosilicate with MWW structure: III. Highly efficient and selective production of glycidol through epoxidation of allyl alcohol with H2O2
Hulea et al. Styrene oxidation with H2O2 over Ti-containing molecular sieves with MFI, BEA and MCM-41 topologies
EP0659685B1 (fr) Procédé d'époxydation et catalyseur à cet effet
AU711847B2 (en) Process for the direct oxidation of olefins to olefin oxides
EP3541747B1 (fr) Tamis moléculaire cit-13 à substitution aluminium
WO2002028774A2 (fr) Catalyseur au silicate de titane de type mww cristallin utilise pour la production de composes oxydes, procede de production dudit catalyseur et procede pour produire un compose oxyde au moyen dudit catalyseur
Bhaumik et al. Ammoximation of ketones catalyzed by titanium-containing ethane bridged hybrid mesoporous silsesquioxane
US9908108B2 (en) High-silica AFX framework type zeolites
EP3464180B1 (fr) Zéolites de type cadre afx à haute teneur en silice
KR20080003893A (ko) 산소 존재 하에서 올레핀 화합물의 에폭시화를 위한 촉매및 에폭시화 방법
WO2010032879A2 (fr) Procédé de production de composé oxydé
EP3743380B1 (fr) Tamis moléculaire ssz-110, sa synthèse et son utilisation
US20130005999A1 (en) Method for regenerating titanosilicate catalysts
US20130079534A1 (en) Method for producing olefin oxide
CN110562998B (zh) 微孔沸石、其合成方法及其用途
WO2011096459A1 (fr) Procédé de production d'oxyde de propylène
WO2012067264A1 (fr) Procédé de production d'un oxyde d'oléfine
CN112138724B (zh) 加氢烷基化催化剂及其方法
US20040034258A1 (en) Crystalline MWW-type titanosilicate catalyst for producing oxidized compound, production process for the catalyst, and process for producing oxidized compound by using the catalyst
Wu et al. MWW-type titanosilicate: Novel preparation and high efficiency in the epoxidation of various alkenes
WO2010087519A1 (fr) Procédé de fabrication d'oxyde de propylène à l'aide d'un catalyseur de métal noble déposé sur du charbon actif silylaté
NL1039507C2 (nl) Werkwijze voor het produceren van een edelmetaal-katalysator.
NL1039506C2 (nl) Werkwijze voor het produceren van een edelmetaal-katalysator.
Tatsumi et al. Ti-MWW and related materials as efficient oxidation catalysts

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11802166

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11802166

Country of ref document: EP

Kind code of ref document: A1