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WO2012067264A1 - Process for producing olefin oxide - Google Patents

Process for producing olefin oxide Download PDF

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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
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WO
WIPO (PCT)
Prior art keywords
hydrogen peroxide
titanosilicate
olefin
component
reactor
Prior art date
Application number
PCT/JP2011/077117
Other languages
French (fr)
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/en

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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.

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Abstract

The present invention is intended to provide a process for producing an olefin oxide, by which a production amount of the olefin oxide per unit weight of a catalyst can be increased. The present invention relates to 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): (a) a solvent, (b) a titanosilicate, and (c) an aluminosilicate (containing no titanium), wherein the component (b) is preferably a titanosilicate with a pore structure in which each pore has a ring structure containing 12 or more oxygen atoms.

Description

DESCRIPTION
PROCESS FOR PRODUCING OLEFIN OXIDE
[0001]
Technical Field
The present application is filed claiming the priority of Japanese Patent Application No. 2010-258577 filed on November 19, 2010 under the Paris Convention, the entire content of which is incorporated herein by reference.
The present invention relates to a process for
producing an olefin oxide.
[0002]
Background Art
There is known, 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 .
For example, 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.
[0003]
Patent Document 1: JP-A-2003-327581 (refer to Examples) [0004]
Summary of Invention
In production of an olefin oxide, a larger and larger production amount of an olefin oxide per unit weight of a catalyst is desirable.
[0005]
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.
[1] 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) :
(a) a solvent,
(b) a titanosilicate, and
(b) an aluminosilicate containing no titanium.
[2] The process defined in the paragraph [1], wherein the liquid phase is a solvent mixture containing at least one kind of a water-soluble organic solvent and water.
[3] The process defined in the paragraph [2], wherein the water-soluble organic solvent contains a nitrile solvent.
[4] The process defined in any one of the paragraphs [1] to [3] , wherein the component (b) is a titanosilicate with a pore structure which has a ring containing 12 or more oxygen atoms .
[5] The process defined in any one of the paragraphs [1] to [3] , wherein the component (b) is at least one kind of titanosilicate selected from the group consisting of Ti-MWW, Ti-MWW precursors and silylated Ti-MWW.
[6] The process defined in any one of the paragraphs [1] to [5] , wherein the olefin is propylene, and the olefin oxide is propylene oxide.
In the following description, the reaction of the olefin with the hydrogen peroxide described in the
paragraph [1] is optionally referred to as "the present reaction", and the process for producing the olefin oxide is optionally referred to as "the present production
process".
[0006]
According to the present invention, there is provided a process for producing an olefin oxide of which the
production amount per unit weight of a catalyst is
increased.
[0007]
Description of Embodiments
Firstly, the above-described components (a) , (b) and (c) for use in the present production process will be described prior to the description of the present
production process by the use of these components. [0008]
(c) Aluminosilicate
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
Committee and published by Kyoritsu Shuppan Co., Ltd. on March 15, 1984] . A typical aluminosilicate is represented by the formula: xMI]: 20. yAl203. zSi02 [wherein M∑I 20 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 (Si02) , aluminum oxide (A1203) and a metal oxide (MIT 20) .
[0009]
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. A
crystalline aluminosilicate, if used, may have a
crystalline structure of tetragonal system, orthorhombic system, cubic system or hexagonal system, or a structure of layer silicate mineral, or a porous crystalline structure, or a structure of a regular mesoporous substance.
Aluminosilicates containing no titanium among these
aluminosilicates are easily available from the market.
[0010]
Herein, .specific examples of the aluminosilicate containing no titanium will be explained below.
Examples of an aluminosilicate as a layer silicate mineral include clay minerals such as kaolinite and
montmorillonite .
Known examples of the aluminosilicate with a porous crystalline structure include mordenite, β-zeolite, A type zeolite, faujasite type zeolite, ferrierite, chabazite and ZSM-5 type zeolite. As the faujasite type zeolite, there are known zeolites called X type zeolite and Y type zeolite.
Known examples of the regular mesoporous substance as the aluminosilicate are mesoporous aluminosilicates such as MCM-41, MCM-48, FSM-16 and SBA-15.
In any of these aluminosilicates, 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. In this connection, the component (c) to be used in the present invention has no titanium ion bonded to its ion-exchange site.
[0011]
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. Preferable examples of the aluminosilicate readily available from the market include mordenite, β-Zeolites, A type zeolites, faujasite type zeolites, ferrierite, chabazite and - SM-5 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
preferable is an aluminosilicate containing potassium.
[0012]
As described above, 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. Examples of 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; β-zeolites; and mordenite.
[0013]
The component (c) for use in the present production process may be produced by a known process; or a
commercially available aluminosilicate may be directly used as the component (c) . Otherwise, 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) . Further, powdery aluminosilicate obtained by pulverizing a molded aluminosilicate may be used. In this case, a binder or the like for use in molding of the aluminosilicate is required to contain no titanium. [0014]
(b) Titanosilicate
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
tetrahedrally-coordinated titanium atom (or Ti) and has a porous structure. 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
wavelength range of from 200 to 400 nm (for example, refer to Chemical Communications, 2002,. 1026-1027 and Fig. 2) . This UV visible . spectrum can be measured by a diffused reflection method using a UV visible spectrophotometer equipped with a diffuse reflection device.
[0015]
The component (b) for use in the present production process is preferably a titanosilicate with a pore
structure which has a ring containing 12 or more oxygen atoms. 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.
[0016]
The following titanosilicates 1 to 5 are given as the above-described titanosilicate.
1. 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,
1995); 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).
2. 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.
3. A layer titanosilicate which has pores each having a ring structure containing 12 oxygen atoms:
e.g., Ti-MWW precursors (cf., European Laid-Open Patent ■ Publication No. 1731515A1); Ti-YNU-1 (cf., Angewandte
Chemie International Edition 43, 236-240, 2004); Ti-MCM-36 (cf., Catalysis Letters 113, 160-164, 2007); and Ti-MCM-56 (cf., Microporous and Mesoporous Materials 113, 435-444, 2008) .
4. A mesoporous titanosilicate:
e.g., Ti-MCM-41 (cf., Microporous Materials 10, 259-271, 1997); Ti-MCM-48 (cf., Chemical Communications, 145-146, 1996); and Ti-SBA-15 (cf., Chemistry of Materials 14, 1657- 1664, 2002) .
5. A silylated titanosilicate:
e.g., silylated titanosilicates obtained by further
silylating the above-listed titanosilicates 1 to 4, such as silylated Ti-MWW, etc.
[0017]
The above-described "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.
[0018]
Examples of the above-described layer titanosilicate include
a layer precursor of a crystalline titanosilicate;
a titanosilicate obtained by expanding interlayers. of a crystalline titanosilicate; and
a 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.
[0019]
Among the above-listed titanosilicates , the
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.
[0020] The above-described mesoporous titanosilicate is a generic name for titanosilicates which have regular
mesopores. Regular mesopores mean a structure having mesopores regularly and repetitively arrayed therein.. Such mesopores have pore diameters of from 2 to 10 nm.
[0021]
The above-described silylated titanosilicate is obtained, for example, by treating any of the
titanosilicates 1 to 4 with a silylating agent. Examples of the silylating agent are 1 , 1 , 1 , 3 , 3 , 3-hexamethyl- disilazane, trimethylchlorosilane, etc. (cf., European Laid-Open Patent Publication No. EP1488853A1) .
[0022]
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.
[0023]
J 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. In this regard, 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.
[0024]
(a) Solvent
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. As 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. When the solvent mixture of water/organic solvent is used as the component (a) , 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
preferable among the nitrile solvents is acetnitirile .
When the solvent mixture of water/organic solvent is used as the component (a) , 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.
[0025]
Present Production Process
Having described the specific examples of the
components (a) , (b) and (c) for use in the present
production process, then, the present production process will be described below.
[0026]
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) . In this step, the olefin is reacted with hydrogen peroxide in the liquid phase by dissolving the olefin in the component (a) which contains hydrogen peroxide
dissolved therein.
[0027]
A mode for carrying out the present production process may be a batch process, a semi-batch process or a
continuous process. 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. However, a reactor for use in a . continuous process is desirable from the viewpoint of commercial production advantage. Herein, an embodiment of the present production process by way of the continuous process with the use of a slurry reactor will be described below. In this regard, the slurry reactor will be
optionally referred to simply as "the reactor" in the description set forth below.
[0028]
Firstly, the slurry reactor is charged with the
components (a) , (b) and (c) . In this regard, when the solvent to be charged in the slurry reactor is, for example, an organic solvent alone such as acetonitrile or the like, water is by-produced along with proceeding of the present reaction, so that a solvent mixture of water/organic
solvent will be present in a reaction system of the present production process along with the proceeding of the present invention. 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.
[0029]
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.
Preferable among these modes in view of simplicity of the operation 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. In particular, 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.
[0030] An amount of the component (b) for use in the present production process may be appropriately selected in
accordance with the type of the component (b) to be used. However, as described above, this amount is typically from 1/10 to 1/1,000 of the mass of the component (a) .
[0031]
An amount of the component (c) for use in the present production process may be appropriately selected in
accordance with the type of the component (c) to be used. However, this amount is preferably 0.01 to 10 times, more preferably 0.1 to 5 times, larger than the mass of the component (b) .
[0032]
As described above, 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 hydrogen peroxide concentration in the hydrogen peroxide solution or aqueous solution is
preferably from 1 to 80% by mass, more preferably from 5 to 70% by mass.
[0033]
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
commercially available aqueous hydrogen peroxide solution may be purified to be used in the present production process. Otherwise, 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. As the hydrogen peroxide precursor, hydrogen and oxygen may be used in combination; or oxygen and a derivative of anthrahydroquinone may be used in combination. In case of the use of a hydrogen peroxide precursor, it is preferable to previously charge a part of the component (a) in the reactor. To produce hydrogen peroxide from hydrogen. and oxygen in the reaction system for the present reaction, for example, 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. By doing so, 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. On the other hand, to produce hydrogen peroxide from oxygen and an anthrahydroquinone derivative in combination in a reaction system for the present reaction, 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
anthrahydroquinone, 2-ethylanthrahydroquinone , 2- amylanthrahydroquinone and the like.
[0034]
Any olefin having a carbon-carbon double bond in the molecule may be used in the present production process. Preferably, 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 C2-C6 non-cyclic olefin, more preferably propylene. Propylene oxide produced by
subjecting propylene to the present production process is very useful as a raw material for use in production of various industrial materials,, and therefore, the present production process which enables advantageous production of propylene oxide is industrially very valuable.
[0035]
In the present production process, a molar ratio of hydrogen peroxide to be used relative to an amount of the olefin (i.e., hydrogen peroxide : olefin) is preferably from 50 : 1 to 1 : 50, more preferably from 10 : 1 to 1 : 10.
[0036]
A reaction temperature in the present reaction may be suitably selected within a range of 10 to 100°C, in
accordance with the type of an olefin to be used, or the types of the components (b) and (c) to be used. 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.
[0037]
A reaction pressure in the present reaction is
preferably from 0.1 to 20 MPa, more preferably from 1 to 10 MPa, in terms of gauge pressure. To control a reaction pressure within this range in the present reaction, 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
catalyst. In case where, for example, propylene suitable as an olefin is used, the propylene is diluted with an inert gas and is then fed into a slurry reactor, so as to control the reaction pressure. In this case, a diluting degree of the propylene with a diluting gas may be
controlled in accordance with conditions such as the mass of the propylene and a reaction scale. In this regard, 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. [0038]
The foregoing description is about the case of using the hydrogen peroxide precursor in the present production process. Next, description is made on another embodiment of the present production process wherein the component (a) , an olefin and hydrogen peroxide are continuously fed into a slurry reactor in which the components (b) and (c) have been previously charged. The slurry reactor to be used is provided with a supply port through which the component (a) , the olefin and hydrogen peroxide (hereinafter, these
materials being collectively referred to as "materials for the present reaction"), -are fed into the reactor. In this case, separate supply ports may be provided to feed the component (a), the olefin and iiydrogen peroxide,
respectively; or 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. In this connection, 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
resultant olefin oxide from the reactor. Further, a
suitable stirring means may be provided in the reactor so as to bring the olefin and hydrogen peroxide into
sufficient contact with each other within the reactor. 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. Preferably, the outlet port for drawing the reaction
mixture is provided with a suitable filter in . order to prevent the components (b) and (c) from leaking from the reactor.
[0039]
To sufficiently react the olefin with hydrogen
peroxide within the reactor, 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.
[0040]
Other Steps
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.
[0041]
The foregoing descriptions are about the embodiments of the present production process, with the use of the slurry reactors. 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.
[0042]
By the present production process, a production amount of an olefin oxide per unit mass of a catalyst (i.e., a titanosilicate as the component (b) ) is increased.
Therefore, a larger amount of the olefin oxide can be produced in the presence of a smaller amount of the
catalyst. Exhibition of this effect is found, for example, in the case of the above-described continuous production process for the olefin oxide with the use of the slurry reactor: that is, in this case, the activity of the catalyst for producing the olefin oxide is not markedly lowered, even if the materials for the present production have been fed into the reactor over a long period of time. As a result, the catalyst can be continuously used over a longer period of time. In the case of the batch type production, an amount of a catalyst to be used relative to an amount of an olefin to be used can be extremely
decreased. According to the present invention, 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.
[0043]
According the present production process, there can be produced a secondary effect that 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. In this regard, these selectivities can be calculated by molar conversion. This effect exhibited by the present
production process which comprises the step of reacting an olefin and hydrogen peroxide in the presence of the above- described components (a) , (b) and (c) has never been easily anticipated from the conventional knowledge. In other words, this effect is based on the present inventor's own finding .
[0044]
Examples
The present invention will be described in more detail by way of Examples thereof which however should not be construed as limiting the scope of the present invention in any way.
[0045]
Synthesis 1
(Preparation of Ti-M W Precursor as Titanosilicate )
An autoclave was charged with piperidine (899 g) , pure water (2,402 g) , tetra-n-butylorthotitanate (TBOT) (112 g) , boric acid (565 g) and fumed silica (cab-o-sil M7D) (410 g) at room temperature under an atmosphere of air, and these materials were stirred to form a gel. The resulting gel was aged for 1.5 hours. After that, the autoclave was sealed up. An internal temperature of the autoclave was raised to about 160°C over 8 hours while the gel was being further stirred; and .then, the internal temperature was maintained at the same temperature for 120 hours, to thereby carry out a hydrothermal synthesis. Thus, a suspended solution was obtained.
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.
[0046]
The white powder a (135 g) obtained as above,
piperidine (300 g) and pure water (600 g) were charged in an autoclave at room temperature under an atmosphere of air and were1" 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) . As a result of analyses, 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
containing 12 or more oxygen atoms. 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
optionally referred to as the Ti-MWW precursor b ) . As a result of the measurement thereof by the ICP emission photospectrometry, a titanium content of the Ti-MWW
precursor b was 1.61% by mass.
[0047]
Example 1
An autoclave with a volume of 0.3 L used as the reactor was charged with a solution of water/acetonitrile (= 20/80 in mass ratio) (69 g) as the component (a), the titanosilicate (or the Ti-MWW precursor b ) (0.5 g) as the component (b) obtained in Synthesis 1 and Molecular Sieves 3A (containing no titanium, manufactured by NACALAI TESQUE, ING.) (0.2 g) as the component (c) and was then sealed up. Into this autoclave, a nitrogen gas, a solution of hydrogen peroxide/water/acetonitrile (= 7/13/80 in mass ratio) and propylene were fed at rates of 60 L/hour, 114 g/hour and 23 g/hour, respectively, for continuous production, while a • reaction mixture containing a reaction product (i.e., propylene oxide) was being drawn out through a filter from the reactor. 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. After 2.5 hours had passed since the start of the reaction, the reaction mixture drawn out of the reactor was sampled (the first sampling) . After that, 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. 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%. In this connection, 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%;
and a conversion of hydrogen peroxide, 96.6%.
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.
[0048]
Example 2
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.
As a result of the analysis of Sample 2, a PO
production amount per unit mass of the titanosilicate was - found to be 436 mmol-PO/g-titanosilicate per hour; a
propylene-based selectivity, 99.8%; a hydrogen peroxide- based selectivity, > 99%; and a conversion of hydrogen peroxide, 90.6%.
As a result of the analysis of Sample 1," a PO
production amount per unit mass of the titanosilicate was found to be 426 mmol-PO/g-titanosilicate per hour; a
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.
[0049]
Example 3
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.
As a result of the analysis of Sample 2, a PO
production amount per unit mass of the titanosilicate was found to be 415 mmol-PO/g-titanosilicate per hour; a
propylene-based selectivity, 99.8%; a hydrogen peroxide- based selectivity, 95.4%; and a conversion of hydrogen peroxide, 89.1%.
As a result of the analysis of Sample 1, a PO
production amount per unit mass of the titanosilicate was found to be 435 mmol-PO/g-titanosilicate per hour; a
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.
[0050] Example 4
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.
As a result of the analysis of Sample 2, a PO
production amount per unit mass of the titanosilicate was found to be 404 mmol-PO/g-titanosilicate per hour; a
propylene-based selectivity, 99.8%; a hydrogen peroxide- based selectivity, > 99%; and a conversion of hydrogen peroxide, 83.5%.
As a result of the analysis of Sample 1, a PO
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
selectivity, 93.0%; and a conversion of hydrogen peroxide, 95.7%.
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.
[0051]
Comparative Example 1
A titanosilicate was used as a catalyst according to the production process of Patent Document l,.and the
production process for olefin oxide was carried out in the absence of aluminosilicate . An autoclave with a volume of 0.3 L was used as the reactor and was charged with a solution of water/acetnitri-le (= 20/80 in mass ratio) (69 g) as the component (a) and the titanosilicate (the Ti-MWW precursor b) (0.5 g) as the component (b) obtained in
Synthesis 1, and was then sealed up. Into this autoclave, a nitrogen gas, a solution of hydrogen
peroxide/water/acetonitrile (= 7/13/80 in mass ratio) and propylene were fed at rates of 60 L/hour, 114 g/hour and 23 g/hour, respectively, for continuous production, while a reaction mixture containing a reaction product (i.e., propylene oxide) was being drawn out through a filter from the reactor. 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. After 2.5 hours had passed since the start of the reaction, the reaction mixture drawn out of the reactor was sampled (the first sampling) . After that, the present production process was further continued, and the second sampling was conducted after 14 hours had passed since the start of the reaction. As a result of the analysis of Sample 2, a PO
production amount per unit mass of the titanosilicate. was found to be 394 mmol-PO/g-titanosilicate per hour; a propylene-based selectivity, 99.1%; a hydrogen peroxide- based selectivity, 93.1%; and a conversion of hydrogen peroxide, 82.7%.
On the other hand, as a result of the analysis of Sample 1, 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%.
[0052]
The propylene oxide production amounts (or PO
production amounts) of Examples 1 to 4 and Comparative Example 1, found after 14 hours had passed, are summarized in Table 1.
[0053]
Table 1
Figure imgf000036_0001
[0054]
Industrial Applicability The present invention can be employed for production of olefin oxides, particularly propylene oxide, useful as raw materials for various industrial materials.

Claims

1. 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) :
(a) a solvent,
(b) a titanosilicate, and
(c) an aluminosilicate (containing no titanium) .
2. The process according to Claim 1, wherein the
component (a) is a solvent containing at least one kind of a water-soluble organic solvent and water.
3. The process according to Claim 2, wherein the water- soluble organic solvent is a nitrile solvent.
4. The process according to any one of Claims 1 to 3, wherein the component (b) is a titanosilicate with a pore structure in which each pore has a ring structure
containing 12 or more oxygen atoms.
5. The process according to any one of Claims 1 to 3, wherein the component (b) is at least one kind of
titanosilicate selected from the group consisting of Ti-MWW, Ti-MWW precurusors and silylated Ti-MWW.
6. The process according to any one of Claims 1 to 5, wherein the olefin is propylene, and the olefin oxide is propylene oxide.
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