WO2012137979A1 - Procédé d'obtention d'oxyde de propylène - Google Patents

Procédé d'obtention d'oxyde de propylène Download PDF

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Publication number
WO2012137979A1
WO2012137979A1 PCT/JP2012/059946 JP2012059946W WO2012137979A1 WO 2012137979 A1 WO2012137979 A1 WO 2012137979A1 JP 2012059946 W JP2012059946 W JP 2012059946W WO 2012137979 A1 WO2012137979 A1 WO 2012137979A1
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Prior art keywords
reaction mass
propylene oxide
catalyst
reaction
gas
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PCT/JP2012/059946
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English (en)
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Hideo Kanazawa
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Sumitomo Chemical Company, Limited
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • 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

Definitions

  • the present invention relates to a method for
  • Patent Document 1 specifically describes a method wherein in the process for the production of ethylene oxide, formaldehyde, which is produced as by-products in an
  • aqueous solution is converted into a corresponding salt by a reaction with a bisulfite of an alkali metal, such as sodium bisulfite, and then the corresponding salt is
  • Example 1 Example 1
  • Example 2 Example 2
  • Patent Literature 1 JP-A-7-330746
  • An object of the present invention is to provide a method for obtaining propylene oxide in which the content of
  • acetaldehyde is reduced by enabling the removal of
  • the present invention includes:
  • a method for obtaining propylene oxide (hereinafter sometimes referred to as a first obtaining method of the present invention), which includes steps of:
  • main raw materials of (a) hydrogen peroxide, or hydrogen and oxygen, and (b) propylene in an acetonitrile-containing solvent in the presence of a catalyst, thereby entirely or partially converting
  • the separation/removal step is a step of mixing a hydroxylamine compound in the reactio mass, which is obtained by feeding, as a liquid gas, a reaction mass obtained by reacting the both raw materials into a gas-liquid separator, and separating into a reaction mass as a liquid part and a gas as a gas part under a pressure which is the same as or lower than that obtained in the reaction, thereby entirely or partially converting acetaldehyde contained in the reaction mass into
  • a method for obtaining propylene oxide (hereinafter sometimes referred to as a second obtaining method of the present invention), which includes steps of:
  • raw materials are sometimes referred collectively to as main raw materials
  • main raw materials of (a) hydrogen peroxide, or hydrogen and oxygen, and (b) propylene in an acetonitrile-containing solvent in the presence of a catalyst
  • the recovery step is a step of recovering propylene oxide existing in the reaction mass which is obtained by feeding, as a liquid gas, a reaction mass obtained by reacting the both raw materials into a gas-liquid separator, and separating into a reaction mass as a liquid part and a gas as a gas part under a pressure which is the same as or lower than that obtained in the reaction;
  • separation/removal step is a step of distilling a reaction mass before removing acetaldoxime, and the distillation step includes a step of separating or removing by
  • catalyst is a Ti- WW precursor.
  • Fig. 1. is a flow chart showing an example of an embodiment, in which the processes of the production of propylene oxide are schematically illustrated.
  • the process between (1) and (5) in the flow chart corresponds to the separation/removal step, and the process between (6) and
  • Fig. 2 is a flow chart showing an example of an embodiment, in which the processes of the production of propylene oxide are schematically illustrated.
  • the process between (1) and (4) and the process (6) in the flow chart corresponds to the recovery step, and the process between (5) and (7) in the flow chart corresponds to the
  • An epoxidation reaction is performed in the process between (1) and (3) in the flow chart, and an oximation reaction is performed in the process (5) in the flow chart.
  • the present invention includes both a first obtaining method of the present invention and a second obtaining method of the present invention (hereinafter sometimes referred collectively to as an obtaining method of the present invention) .
  • the first obtaining method of the present invention is a method for obtaining propylene oxide, which includes the steps of:
  • reaction mass which is obtained by reacting main raw materials in an acetonitrile-containing solvent in the presence of a catalyst (the reaction corresponds to the below-defined "epoxidation reaction”) , thereby entirely or partially converting acetaldehyde contained in the reaction mass into acetaldoxime (the reaction corresponds to the below-defined "oximation reaction”) , and then separating or removing the acetaldoxime from the reaction mass; and
  • the second obtaining method of the present invention is a method for obtaining propylene oxide, which includes steps of:
  • examples of the catalyst to be used to react main raw materials in an acetonitrile-containing solvent in the presence of a catalyst include both of (1) a titanosilicate catalyst such as a Ti-MWW precursor and (2) a catalyst obtained by supporting the titanosilicate catalyst and a noble metal catalyst such as palladium on a carrier, and the like.
  • the content of the noble metal in the noble metal catalyst is, for example, within a range from 0.01% by weight to 20% by weight, and preferably from 0.1% by weight to 5% by weight.
  • examples of the "raw material (a)" as one of raw materials to be used in the obtaining method of the present invention include hydrogen peroxide and the like.
  • examples of the "raw material (a)" as one of raw materials to be used in the obtaining method of the present invention include hydrogen, oxygen and the like.
  • the use amount of the noble metal is, for example, 0.00001 part by weight or more, preferably 0.0001 part by weight or more, and more preferably 0.001 part by weight or more, based on 1 part by weight of the titanosilicate catalyst.
  • the existing amount of the "catalyst obtained by supporting a noble metal catalyst such as palladium on a carrier" relative to the "titanosilicate catalyst” is, for example, 100 parts by weight or less, preferably 20 parts by weight or less, and more preferably 5 parts by weight or less, based on 1 part by weight of the titanosilicate catalyst.
  • the titanium silicate catalyst substantially means titanosilicate including tetrahedrally coordinated Ti in which an ultraviolet-visible absorption spectrum in a wavelength range of 200 nm to 400 nm exhibits a maximum absorption peak in a wavelength range of 210 nm to 230 nm (see, for example, Chemical Communications 1026-1027,
  • the ultraviolet-visible absorption spectrum can be measured by a diffuse
  • titanosilicate catalysts catalysts having pores composed of a 10- or more membered oxygen ring since inhibition of contact between reaction raw materials and an active spot in pores may be reduced and limitation of movement of substances in pores may be reduced.
  • pores mean pores composed of Si-0 bonds or Ti-0 bonds.
  • Examples of pores include half-cup shaped pores called a side pocket (i.e., it is not necessary to penetrate primary particles of titanosilicate) and the like
  • 10- or more membered oxygen ring means 10 or more carbon atoms in (a) a cross section of the thinnest area in pores, or (b) a ring structure in a pore inlet. It is generally confirmed by analysis of an X-ray diffraction pattern that the titanosilicate catalyst has pores composed of a 10- or more membered oxygen ring. A known structure can be simply confirmed by comparing with an X-ray
  • titanosilicate catalyst examples include those described in the following 1 to 7 and the like.
  • Crystalline titanosilicate having pores composed of a 10-membered oxygen ring having pores composed of a 10-membered oxygen ring:
  • TS-1 having MFI structure according to the structure code of the International Zeolite Association (IZA) (for example U.S. Patent No. No. 4,410,501), TS-2 having a MEL structure (for example, Journal of Catalysis 130, 440-446, (1991)), Ti-ZSM-48 having a MRE structure (for example, Zeolites 15, 164-170, (1995)), Ti-FER having a FER structure (for example, Journal of Materials Chemistry 8, 1685-1686
  • Crystalline titanosilicate having pores composed of a 12-membered oxygen ring having pores composed of a 12-membered oxygen ring:
  • Ti-Beta having a BEA structure for example, Journal of Catalysis 199, 41-47, (2001)
  • Ti-ZSM-12 having a MTW structure
  • Ti- MOR having a MOR structure
  • Ti-ITQ-7 having a ISV structure
  • Ti-MCM-68 having a MSE structure for example, Chemical Communications 6224-6226, (2008)
  • Ti-MWW having a MWW structure for example,
  • Ti-UTD-1 having a DON structure for example, Studies in Surface Science and Catalysis 15, 519-525, (1995)) and the like.
  • Ti-ITQ-6 for example, Angewandte Chemie International
  • Ti-M W precursor for example, EP1731515A1
  • Ti-YNU-1 for example, Angewandte Chemie International Edition 43, 236- 240, (2004)
  • Ti-MCM-36 for example, Catalysis Letters 113, 160-164, (2007)
  • Ti-MC -56 for example, Microporous and Mesoporous Materials 113, 435-444, (2008)
  • Ti-MCM-41 for example, Microporous Materials 10, 259-271, (1997)
  • Ti-MCM-48 for example, Chemical Communications 145-146, (1996)
  • Ti-SBA-15 for example, Chemistry of
  • layered titanosilicate is a generic term of titanosilicate having a layered structure, for example, a layered precursor of a crystalline titanosilicate, a titanosilicate in which the interlayer distance of the crystalline titanosilicate is increased, and the like. It is possible to confirm that the titanosilicate has a layered structure by an electron microscope or the
  • the "layered precursor” means a titanosilicate which forms a crystalline titanosilicate by performing a treatment such as
  • titanosilicate that the layered titanosilicate has pores composed of a 12- or more membered oxygen ring.
  • the "mesoporous titanosilicate” is a generic term of a titanosilicate having regular mesopores.
  • the regular mesopores mean a structure in which mesopores are regularly repeat-arranged.
  • the "mesopores” mean pores each having a pore diameter of 2 nm to 10 nm.
  • the "silylated titanosilicate” is a compound obtained by treating the titanosilicate described in the above 1 to 4 with a silylating agent.
  • a silylating agent examples include 1, 1, 1, 3, 3, 3-hexamethyldisilazane,
  • a titanosilicate catalyst as a catalyst used to react (i.e., epoxidation reaction) main raw materials in an
  • acetonitrile-containing solvent in the presence of the catalyst is preferably a catalyst which is brought into contact with hydrogen peroxide in advance.
  • concentration of hydrogen peroxide to be brought into contact is, for example, within a range from 0.0001% by weight to 50% by weight.
  • a titanosilicate having pores composed of a 12- or more membered oxygen ring is preferable.
  • Such a titanosilicate may be either a crystal or a layered titanosilicate.
  • Examples of pores composed of a 12- or more membered oxygen ring include Ti- MW , a Ti-MWW precursor and the like.
  • the Ti-MWW precursor may be synthesized by bringing a layered compound (also referred to as an as-synthesized sample) , which is directly prepared through hydrothermal synthesis of a boron compound, a titanium compound, a silicon compound and a structure directing agent, into contact with an aqueous solution of a strong acid under reflux conditions to remove the structure directing agent, and then adjusting a molar ratio (Si/N ratio) of silicon to nitrogen to 21 or more (see, for example, JP-A-2005-262164 ) .
  • a layered compound also referred to as an as-synthesized sample
  • Si/N ratio molar ratio
  • a Ti-MWW precursor containing 13.5 to 14.2% by weight of a structure directing agent is obtained by subjecting a compound, which is obtained by mixing Ti-MWW, piperidine and water, to a hydrothermal treatment and then washed with water.
  • a molar ratio of silicon to nitrogen (Si/N ratio) of the Ti-MWW precursor was from 5 to 20, and preferably from 8.5 to 8.6, calculated from a molar ratio of silicon to titanium (Si/Ti ratio) and a molar ratio of silicon to boron (Si/B ratio) .
  • Si/N ratio since the content of nitrogen is higher as compared with the molar ratio (Si/N ratio) in a conventionally known Ti-MWW
  • the Ti-MWW precursor can be used as a preferable titanosilicate catalyst (Ti-MWW precursor) .
  • Ti-MWW can be obtained by crystallizing the Ti-MWW precursor obtained as mentioned above through firing.
  • the Ti-MWW precursor having a Si/N ratio of 5 to 20 (hereinafter sometimes referred to as the present
  • Ti (titanium) , Si (silicon) and B (boron) can be measured by alkaline resolution-nitric acid dissolution-ICP spectrometry, while N (nitrogen) can be measured by an oxygen circulation combustion TCD detection system (SUMIGRAPH Model NCH-22F (manufactured by Sumika Chemical Analysis Service, Ltd.) was used in Examples of the present description) .
  • the Ti- M W precursor is a generic term of a precursor which is converted into Ti-MWW as a crystalline titanosilicate having a MWW (according to the structure code of the
  • titanosilicate is a generic term of a titanosilicate in which a part of Si in the tectosilicate is isomorphously substituted with Ti (see descriptions of item of "Titanosilicate” of Dictionary of Catalyst
  • the present precursor can be obtained by a method in which a titanosilicate having an X-ray diffraction pattern with the value shown below is brought into contact with a structure directing agent capable of forming zeolite having a M W structure.
  • These X-ray diffraction patterns may be measured by a general X-ray diffractometer using copper K-alpha radiation.
  • Ti-MWW precursor for example, those described in JP-A-2005-262164
  • Ti-YNU- 1 for example, those described in Angewandte Chemie
  • crystalline titanosilicates Ti-MWW for example, those described in JP- A-2003-327425
  • crystalline titanosilicates Ti-MWW for example, those described in JP- A-2003-327425
  • IZA International Zeolite Association
  • Ti-MCM-68 for example, those described in JP-A-2008-50186
  • crystalline titanosilicate having a MSE structure according to the structure code of IZA and the like.
  • the present precursor may be usually synthesized by bringing a layered compound (see, for example, Chemistry Letters 774-775 (2000) , described as an as-synthesized sample in the same document) , which is obtained by mixing a silicon compound, a boron compound, a titanium compound, water and a structure directing agent, and then subjecting the mixture to a heat treatment, into contact with 2M nitric acid to remove the structure directing agent.
  • the above-mentioned layered compound called as the as- synthesized sample is converted into a zeolite having a MWW structure when this layered compound is fired as it is.
  • the zeolite is not a titanosilicate catalyst since an ultraviolet-visible absorption spectrum does not
  • the present precursor can also be produced by
  • a layered borosilicate which is obtained by heating a mixture containing a structure directing agent, a boron compound, a silicon compound and water, into contact with acid or the like to remove the structure directing agent, firing the product to obtain B- MW , removing boron from the thus obtained B-MWW using an acid or the like, adding a structure directing agent, a titanium compound and water to obtain a mixture, heating the mixture to obtain a layered compound, and then bringing the layered compound into contact with 6M nitric acid to remove the structure directing agent (for example, Chemical Communication 1026-1027, (2002)).
  • the present precursor can also be produced by bringing a layered borosilicate, which is
  • the Ti-MWW precursor which is obtained from the layered compound obtained by various methods as mentioned above, has an Si/N ratio of 21 or more, and the Ti-MWW precursor is converted into Ti-MWW, in which an
  • ultraviolet-visible absorption spectrum exhibits a peak at
  • Examples of the structure directing agent i.e., a structure directing agent capable of forming a zeolite having a MWW structure
  • examples of the structure directing agent include piperidine,
  • hexamethyleneimine an -V, N,AJ-trimethyl-l-adamantaneammonium salt (for example, W, N,W-trimethyl-l-adamantaneammonium hydroxide, ⁇ , ⁇ ,- N-trimethyl-l-adamantaneammonium iodide, etc.), an octyltrimethyl ammonium salt (for example, octyltrimethylammonium hydroxide, octyltrimethylammonium bromide, etc.) (see, for example, Chemistry Letters 916-917 (2007)) and the like.
  • piperidine, hexamethyleneimine and the like are exemplified. These compounds may be used alone, or two or more kinds may be used in the form of a mixture at any mixing ratio.
  • the amount of the structure directing agent to be used to form a zeolite having a MWW structure is from 0.001 time to 100 times, and preferably from 0.1 time to 10 times, in terms of a ratio of the weight of the structure directing agent to the weight of the titanosilicate.
  • Contact between the structure directing agent and the titanosilicate may be usually performed by heating under pressure in a closed container such as an autoclave, and also can be performed by a method of mixing in a flask made of glass while stirring under atmospheric pressure, or mixing without stirring.
  • the temperature in case of contacting is, for example, from 0°C to 250°C, and
  • the pressure in case of contacting is, for example, from 0 MPa to 10 MPa in terms of a gauge pressure.
  • the present precursor obtained after contacting is usually separated by filtration.
  • the present precursor having a Si/N ratio within a range from 5 to 20 is obtained by optionally washing with water or the like. Washing may be performed by appropriately adjusting the amount of a wash, the pH of a washing filtrate and the like while optionally monitoring.
  • the present precursor thus produced can be used as a catalyst in an oxidation reaction or the like.
  • the Si/N ratio of the present precursor is, for example, within a range from 10 to 20, and preferably from 10 to 16.
  • the present precursor may be silylated using a silylating agent, for example, 1, 1, 1, 3, 3, 3-hexamethyldisilazane or the like.
  • the specific surface area value ( SH 2 O ) measured by a steam adsorption method to a specific surface area value ( SN 2 ) measured by a nitrogen adsorption method in the present precursor is, for example, within a range from 0.7 to 1.5, and preferably from 0.8 to 1.3.
  • the specific surface area value ( SN 2 ) measured by nitrogen adsorption may be determined by degassing a sample at 150°C, measuring, for example, through a nitrogen adsorption method using "BELSORP-mini" (manufactured by BEL Japan, Inc.),. followed by calculation through a BET method.
  • adsorption may be determined by degassing a sample at 150°C, measuring, for example, through a steam adsorption method at an adsorption temperature of 298 K using "BELSORP-aqua3"
  • raw material (a) as one of raw materials to be used to react (i.e., epoxidation reaction) main raw materials in an acetonitrile-containing solvent in the presence of a catalyst in the obtaining method of the present invention
  • hydrogen peroxide used as the "raw material (a)” may be a commercially available product (i.e., hydrogen peroxide solution) and may be generated from
  • the concentration of hydrogen peroxide in the hydrogen peroxide solution is within a range from 0.0001% by weight to 100% by weight, and more preferably from
  • the amount of the hydrogen peroxide varies depending on the kind, reaction conditions and the like and, for example, a ratio (molar ratio) of the amount of hydrogen peroxide to the amount of propylene as the raw material (b) existing in the reaction system is within a range from
  • the "hydrogen peroxide" among the “raw material (a)” as one of raw materials to be used to react i.e., epoxidation
  • main raw materials in an acetonitrile-containing solvent in the presence of a catalyst may be fed in a state of being dissolved in the below-mentioned solvents such as water and acetonitrile .
  • solvents such as water and acetonitrile .
  • Examples of the solvent other than acetonitrile used to dissolve the hydrogen peroxide include an alcohol solvent, a ketone solvent, a nitrile solvent, an ether solvent, an aliphatic hydrocarbon, an aromatic hydrocarbon, a halogenated hydrocarbon, an ester solvent, a mixture thereof and the like.
  • the alcohol solvent examples include aliphatic alcohols having 1 to 8 carbon atoms, such as methanol, ethanol, isopropanol and t-butanol; glycols having 2 to 8 carbon atoms, such as ethylene glycol and propylene glycol; and the like. Monohydric alcohols having 1 to 4 carbon atoms are preferable, and t-butanol is more preferable.
  • aliphatic hydrocarbon examples include
  • aliphatic hydrocarbons having 5 to 10 carbon atoms, such as hexane and heptane, and the like.
  • aromatic hydrocarbon examples include aromatic hydrocarbon having 6 to 15 carbon atoms, such as benzene, toluene and xylene, and the like.
  • nitrile solvent examples include alkylnitriles having 2 to 4 carbon atoms, such as propionitrile,
  • Examples of the acetonitrile used to dissolve hydrogen peroxide include purified acetonitrile, crude acetonitrile by-produced in the production process of acrylonitrile and the like.
  • Examples of impurities other than acetonitrile contained in the crude acetonitrile include water, acetone, acrylonitrile, oxazole, allyl alcohol, propionitrile, hydrocyanic acid, ammonia, copper, iron and the like.
  • the content of copper and iron is preferably a trace amount of 1% by weight or less.
  • Purity of the acetonitrile is, for example, 95% by weight or more, preferably 99% by weight or more, and more preferably 99.9% by weight or more.
  • Examples of the noble metal catalyst such as palladium used to generate "hydrogen peroxide” from “oxygen and hydrogen” in the present invention include catalysts containing noble metals such as palladium, platinum, ruthenium, rhodium, iridium, osmium and gold; or alloy or mixtures of these noble metals.
  • Examples of preferable noble metal include palladium, platinum, gold and the like. Examples of more preferable noble metal include palladium and the like.
  • the above-mentioned palladium or the below-mentioned palladium compound may be used, for example, in the form of colloids (see, for example, JP-A-2002-294301, Example 1) .
  • the content of the noble metal in the noble metal catalyst is, for example, within a range from 0.01% by weight to 20% by weight, and preferably from 0.1% by weight to 5% by weight.
  • the noble metal catalyst is a noble metal
  • the compound and the noble metal is palladium
  • noble metal other than palladium examples include platinum, gold and the like.
  • the palladium compound examples include tetravalent palladium compounds such as sodium hexachloropalladate (IV) tetrahydrate and potassium hexachloropalladate (IV);
  • the noble metal catalyst such as a palladium used to generate "hydrogen peroxide” from “oxygen and hydrogen” in the present invention may be a noble metal catalyst in a state of being supported on a carrier.
  • the "carrier” include carbon; oxides such as silica, alumina, titania, zirconia and niobia; hydrates such as niobic acid, zirconic acid, tungstic acid and titanic acid; mixtures thereof; noble metal catalysts such as a
  • Examples of the method for preparing a noble metal catalyst in a state of being supported on a carrier among noble metal catalysts such as a palladium used to generate "hydrogen peroxide" from “oxygen and hydrogen” in the present invention include a conventional method such as an impregnation method.
  • the noble metal catalyst obtained by a conventional method such as an impregnation method may be subjected to a reduction treatment using a reducing gas.
  • Examples of the method of the reduction treatment include a method in which a reduction treatment is performed by injecting a reducing gas into a packed tube filled with a solid noble metal catalyst.
  • examples of the method of the reduction treatment include a method in which a reduction treatment is performed by injecting a reducing gas into a packed tube filled with a solid noble metal catalyst.
  • reducing gas include hydrogen, carbon monoxide, methane, ethane, propane, butane, ethylene, propylene, butene, butadiene, or a mixed gas of two or more kinds selected from these gases. Among them, hydrogen is preferable.
  • Examples of the reducing gas include nitrogen, helium, : argon, steam, or a mixed gas thereof.
  • a partial pressure ratio of oxygen to hydrogen (oxygen: hydrogen) in a mixed gas of oxygen and hydrogen to be fed in a reactor is, for example, within a range from 1:50 to 50:1, and preferably from 1:10 to 10:1. It is preferred that the partial pressure of oxygen is more than 1:50 in terms of oxygen : hydrogen since the formation rate of propylene oxide may increase.
  • the partial pressure of oxygen is less than 50:1 in terms of oxygen : hydrogen since the formation of byproducts in which a carbon-carbon double bond of propylene is reduced with a hydrogen atom is reduced, and thus selectivity to propylene oxide may be improved.
  • diatoma examples include nitrogen, argon, carbon dioxide, methane, ethane, propane and the like.
  • nitrogen and propane are preferable, and nitrogen is more preferable.
  • a mixing ratio thereof will be described by way of the case where the diluent gas is a nitrogen gas, as an example. It is preferred the case where the total concentration of hydrogen and propylene is 4.9% by volume or less, the concentration of oxygen is 9% by volume or less and the balance is a nitrogen gas, or the case where the total concentration of hydrogen and
  • propylene is 50% by volume or more, the concentration of oxygen is 50% by volume or less and the balance is a nitrogen gas.
  • An oxygen gas, and air containing oxygen may be used as oxygen.
  • the oxygen gas include an oxygen gas produced by an inexpensive pressure swing method, a high purity oxygen gas produced by cryogenic separation and the like.
  • the feed amount of oxygen is, for example, within a range from 0.005 to 10 mol, and preferably from 0.05 to 5 mol, based on 1 mol of propylene to be fed.
  • Examples of hydrogen include those obtained by steam- reforming hydrogen and the like. Purity of hydrogen is 80% by volume or more, and preferably 90% by volume or more.
  • the feed amount of hydrogen is, for example, within a range from 0.05 to 10 mol, and preferably from 0.05 to 5 mol, based on 1 mol of propylene to be fed.
  • a quinoid compound-containing solution is usually obtained from a discharging tube of bottom liquid of a first distillation column connected to the bottom section of the below- mentioned first distillation column.
  • a quinoid compound crystal may be obtained.
  • the obtained quinoid compound crystal is usually separated by filtration.
  • the filtration system include a pressurization system, a centre system and the like.
  • the quinoid compound crystal may be washed with a mixed
  • the filtration temperature may be, for example, the same temperature as the crystallization temperature.
  • the thus obtained quinoid compound i.e., a recovered quinoid compound
  • the quinoid compound is preferably recycled, for example, after dissolving in a mixed solution of
  • Examples of the quinoid compound include a compound represented by the formula (1):
  • R 1 , R 2 , R 3 and R 4 each independently represents hydrogen atom, or R 1 and R 2 , or R 3 and R 4 may be taken together with a carbon atom to which R 1 , R 2 , R 3 and R 4 are attached to form a benzene ring which may have a
  • X and Y each independently represents an oxygen atom or a NH group.
  • Examples of the compound represented by the formula (1) include:
  • Examples of the compound represented by the formula (1) include an anthraquinone compound represented by the formula (2) :
  • R 5 , R 6 , R 7 and R 8 each independently represents a hydrogen atom, a hydroxyl group or an alkyl group (for example, alkyl groups having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group) ) .
  • Examples of X and Y in the compound represented by the formula (1) preferably include an oxygen atom.
  • Examples of the compound represented by the formula (1) include quinone compounds such as benzoquinone and naphthoquinone; anthraquinones ; 2-alkylanthraquinone compounds such as 2-ethylanthraquinone, 2-t- butylanthraquinone, 2-amylanthraquinone, 2- methylanthraquinone, 2-butylanthraquinone, 2-t- amylanthraquinone, 2-isopropylanthraquinone, 2-s- butylanthraquinone and 2-s-amylanthraquinone;
  • quinone compounds such as benzoquinone and naphthoquinone
  • anthraquinones 2-alkylanthraquinone compounds such as 2-ethylanthraquinone, 2-t- butylanthraquinone, 2-amylanthraquinone, 2- methylanthraquinone, 2-butylan
  • polyalkylanthraquinone compounds such as 1,3- diethylanthraquinone, 2, 3-dimethylanthraquinone, 1,4- dimethylanthraquinone and 2, 7-dimethylanthraquinone;
  • polyhydroxyanthraquinone compounds such as 2,6- dihydroxyanthraquinone
  • p-quinoid compounds such as
  • examples thereof include anthraquinone, a 2- alkylanthraquinone compound (X and Y in the formula (2) represent an oxygen atom, R 5 represents an alkyl group, R 6 represents hydrogen, and R 7 and R 8 represent a hydrogen atom) and the like.
  • the use amount of such a quinoid compound is within a range from 0.001 mmol to 500 mmol, and preferably from 0.01 mmol to 50 mmol, based on 1 kg of the solvent.
  • the quinoid compound can also be prepared by oxidizing a dihydro form of the quinoid compound using oxygen in the reaction system.
  • oxidation with oxygen may be performed in the reaction system by adding a quinoid compound such as 9, 10-anthracenediol or a compound obtained by hydrogenating hydroquinone or the like in a liquid phase to generate a quinoid compound, and the obtained quinoid compound may be used.
  • Examples of the "dihydro form of the quinoid compound” include a compound represented by the formula (3) :
  • R 1 , R 2 , R 3 , R 4 , X and Y have the same meanings as defined above, as a dihydro form of a compound represented by the formula (1), and a compound represented by the formula (4 ) :
  • preferred compound is a dihydro form corresponding to the above- . mentioned preferred quinoid compound.
  • X and Y in the compound represented by the formula (3) and the compound represented by the formula (4) are preferably, for example, oxygen atoms.
  • raw material (b) as one of raw materials to be used to react (i.e., epoxidation reaction) main raw materials in an acetonitrile-containing solvent in the presence of a catalyst, is propylene.
  • propylene examples include those produced by pyrolysis, heavy oil catalytic cracking or methanol
  • the propylene may be purified propylene, or crude propylene obtained without subjecting to the purification step.
  • Preferred propylene is, for example, propylene having a purity of 90% by volume or more, and preferably
  • Examples of impurities contained in propylene include propane, cyclopropane, methylacetylene, propadiene,
  • butadiene butanes, butenes, ethylene, ethane, methane, hydrogen and the like.
  • Examples of the form of the propylene include gas, liquid and the like.
  • examples of "liquid” include
  • liquid of propylene alone (i) a mixed solution in which propylene is, for example, dissolved in an organic solvent or a mixed solvent of an organic solvent and water.
  • gases include (i) gas of propylene alone, (ii) a mixed gas of gaseous propylene and the other gas
  • component such as a nitrogen gas or a hydrogen gas.
  • the amount of the propylene varies depending on the kind, reaction conditions and the like, and is 0.01 part by weight or more, and more preferably 0.1 part by weight or more, based on 100 parts by weight of the amount of a mixture of an acetonitrile-containing solvent existing in the reaction system, a catalyst and main raw materials.
  • the amount of a titanosilicate catalyst among the catalyst varies depending on the kind, reaction conditions and the like, and is, for example, within a range from 0.01 part by weight to 20 parts by weight, preferably from 0.1 part by weight to 10 parts by weigh, and more preferably from 0.5 part by weight to 8 parts by weight, based on 100 parts by weight of a mixture of an acetonitrile-containing solvent existing in the reaction system, a catalyst and main raw materials.
  • acetonitrile-containing solvent means a solvent containing acetonitrile, and the acetonitrile-containing solvent may contain solvents other than acetonitrile.
  • solvents other than acetonitrile include organic solvents other than acetonitrile, water and the like.
  • acetonitrile-containing solvent is, for example, preferably within a range of 50% or more, and more preferably from 60% to 100%.
  • the reaction temperature at which main raw materials are reacted i.e., epoxidation reaction
  • the reaction pressure gauge pressure
  • the reaction pressure is, for example, 0.1 MPa or more, preferably 1 Pa or more, more preferably 10 MPa or more, and still more preferably 20 MPa or more, under pressure.
  • an ammonium salt, an alkyl ammonium salt and an alkylaryl ammonium salt may be allowed to exist in the reaction system.
  • the "buffer agent” means a compound which exerts a buffer action on the concentration of hydrogen ions of the solution, such as a salt.
  • the amount of the buffer agent is, for example, a value of solubility or less of the buffer agent in a
  • mixture of an acetonitrile-containing solvent, a catalyst and main raw materials, which exists in the reaction system and is preferably within a range from 0.001 mmol to 100 mmol, based on 1 kg of the mixture.
  • buffer agent examples include buffer agents composed of (1) an anion selected from the group consisting of a sulfate ion, a hydrogen sulfate ion, a carbonate ion, a hydrogen carbonate ion, a phosphate ion, a hydrogen phosphate ion, a dihydrogen phosphate ion, a hydrogen pyrophosphate ion, a pyrophosphate ion, a halogen ion, a nitrate ion, a hydroxide ion and Ci-Cio carboxylate ion, and (2) a cation selected from the group consisting of ammonium, C1-C20 alkylammonium, C7-C20 alkylarylammonium, alkali metals and alkali earth metals
  • C1-C10 carboxylate ion examples include a formate ion, an acetate ion, a propionate ion, a butyrate ion, a valerate ion, a caproate ion, a caprylate ion, a capric acid ion and a benzoic acid ion.
  • alkylammonium examples include
  • cation selected from the group consisting of alkali metal and alkaline-earth metal include a lithium cation, a sodium cation, a potassium cation, a rubidium cation, a cesium cation, a magnesium cation, a calcium cation, a strontium cation, a barium cation and the like.
  • preferred buffer agent include ammonium salts of inorganic acids, such as ammonium sulfate, ammonium hydrogen sulfate, ammonium carbonate, ammonium hydrogen carbonate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, ammonium hydrogen pyrophosphate, ammonium pyrophosphate, ammonium chloride and ammonium nitrate; and ammonium salts of Ci to Cio carboxylic acids, such as ammonium benzoate and ammonium acetate.
  • preferred ammonium salt include ammonium benzoate, ammonium dihydrogen phosphate,
  • main raw materials are reacted (i.e., epoxidation reaction) in an acetonitrile-containing solvent in the presence of a catalyst, it is preferred that the reaction is continuously performed.
  • main raw materials are reacted (i.e., epoxidation reaction) in an acetonitrile-containing solvent in the presence of a catalyst.
  • hydrogen and oxygen, and propylene to be continuously fed in the epoxidation reaction tank may be continuously fed as a mixed gas which is optionally mixed with a diluent gas.
  • Propylene may be fed as a liquid.
  • the epoxidation reaction tank is preferably equipped with mixing means such as a stirring blade.
  • mixing means such as a stirring blade.
  • hydrogen peroxide may be efficiently mixed with the catalyst.
  • epoxidation reaction tank include an epoxidation reaction tank denoted by (3) in Fig. 1 (hereinafter sometimes referred to as an epoxidation reaction tank (3)).
  • the epoxidation reaction tank (3) includes a paddle blade therein, and also includes a feeding tube of raw materials of an epoxidation reaction, denoted by the reference numeral (9) in Fig. 1, for continuously receiving a mixed gas containing oxygen, hydrogen and olefin to the epoxidation reaction tank (3) (hereinafter sometimes referred to as a feeding tube of raw materials of an epoxidation reaction (9)), and an epoxidation reaction mass discharging/feeding tube, denoted by the reference numeral (12) in Fig. 1, for continuously feeding a reaction mass to the below-mentioned gas-liquid separation tank from the epoxidation reaction tank (3) (hereinafter sometimes referred to as an epoxidation reaction mass
  • reaction mass is continuously fed to the epoxidation reaction mass discharging/feeding tube (12) from the epoxidation reaction tank (3) .
  • a plurality of the epoxidation reaction tanks may exist.
  • the epoxidation reaction tank (1) includes a paddle blade therein, and also includes a feeding tube of raw materials of an epoxidation reaction (9) for continuously receiving a mixed gas containing oxygen, hydrogen and olefin to the epoxidation reaction tank (1), and an
  • epoxidation reaction mass discharging/feeding tube denoted by the reference numeral (10) in Fig. 1, for continuously feeding a reaction mass to the epoxidation reaction tank (2) from the epoxidation reaction tank (1) (hereinafter sometimes referred to as an epoxidation reaction mass discharging/feeding tube (10)) connected thereto.
  • the epoxidation reaction is performed in the epoxidation reaction tank (1) and the obtained reaction mass is
  • the epoxidation reaction tank (2) includes a paddle blade therein, and also include a feeding tube of raw materials of an epoxidation reaction (9) for continuously receiving a mixed gas containing oxygen, hydrogen and olefin to the epoxidation reaction tank (2), and an epoxidation reaction mass discharging/feeding tube, denoted by the reference numeral (11) in Fig. 1, for continuously feeding a reaction mass to the epoxidation reaction tank (3) from the
  • epoxidation reaction tank (2) (hereinafter sometimes referred to as epoxidation reaction mass
  • the catalyst In case of extracting the reaction mass from the epoxidation reaction tank, the catalyst preferably remains in the epoxidation reaction tank. Examples of the
  • extraction method include (i) a method in which only a supernatant of the reaction mass is extracted so that the catalyst is not introduced from the epoxidation reaction tank, (ii) a method in which the catalyst is separated and removed by providing a filter in a passage of an
  • the catalyst when the reaction mass is fed to the second epoxidation reaction tank from the first epoxidation reaction tank, the catalyst may be removed from the reaction mass and the reaction mass may be fed to epoxidation reaction tank of the subsequent step, in the same manner as described above.
  • Examples of the epoxidation reaction tank include a flow fixed bed reactor, a flow slurry complete mixing device and the like.
  • the flow slurry complete mixing device it is possible to further feed again the catalyst, obtained by filtering the reaction mass through a filter provided inside or outside the device, into the device.
  • a filter provided inside or outside the device
  • examples thereof include (i) a method in which a part of catalyst existing in the device is extracted continuously or intermittently and the extracted catalyst is subjected to a catalyst regeneration treatment, and then the catalyst subjected to a regeneration treatment is fed again into the device, (ii) a method in which a part of catalyst existing in the device is extracted continuously or intermittently and a new catalyst is additionally fed into the device in the amount corresponding to the discharged catalyst and the like.
  • catalyst with reduced productivity of propylene oxide is subjected to a catalyst regeneration treatment so as to regenerate the catalyst. It is also possible to perform the treatment while alternately repeating the epoxidation reaction and regeneration of the catalyst.
  • catalyst regeneration treatment includes those molded using a mold release agent.
  • propylene oxide can be recovered from a reaction mass obtained through an epoxidation reaction by performing a separation operation such as distillation.
  • reaction tanks denoted by the reference numerals (1) to (3) in Fig. 2 and a reaction mass is continuously fed to the epoxidation reaction mass discharging/feeding tube (12) from the epoxidation reaction tank (3) . Then, the reaction mass is fed to a gas-liquid separation tank continuously (4) as a liquid gas, and then propylene oxide existing in the reaction mass, obtained by separating into a reaction mass as a liquid part and a gas as a gas part under a pressure which is the same as or lower than that used in the epoxidation reaction, is recovered.
  • the reaction mass as a liquid part includes, in addition to acetonitrile, propylene oxide and water, byproducts such as amides, oxazolines and aldehydes by- produced in the epoxidation reaction.
  • amides derived from acetonitrile include acetamide, N- (2-hydroxy-propan-l-yl) acetamide, N- (l-hydroxypropan-2-yl) acetamide) and the like.
  • oxazolines include 2,4- dimethyloxazoline, 2 , 5-dimethyloxazoline and the like.
  • aldehydes include formaldehyde, acetaldehyde, propionaldehyde and the like.
  • an epoxidation reaction mass discharging/feeding tube (12) for continuously receiving a reaction mass from the epoxidation reaction tank (3) , an epoxidation reaction mass discharging/feeding tube, denoted by the reference numeral (13) in Fig. 1, for continuously feeding a reaction mass as a liquid part, from which a gas part (i.e., gas component) is separated, to an oximation reaction tank (5) (hereinafter sometimes referred to as epoxidation reaction mass discharging/feeding tube (13)), and a reaction mass discharging tube after gas separation, denoted by the reference numeral (14) in Fig.
  • reaction mass discharging tube (14) for discharging a gas from which a liquid part (i.e., gas component) is separated (hereinafter sometimes referred to as a reaction mass discharging tube (14) after gas separation) are connected. Then, reaction mass as a liquid part, from which a gas part (i.e., gas component) is separated, is continuously fed to the oximation reaction tank (5) .
  • discharging/feeding tube (12) for continuously receiving a reaction mass from the epoxidation reaction tank (3), an epoxidation reaction mass discharging/feeding tube (13) for continuously feeding a reaction mass as a liquid part, from which a gas part (i.e., gas component) is separated, to the first distillation column (crude propylene oxide separation column) (6), and a reaction mass discharging tube (14) after gas separation, for discharging a gas part (i.e., gas component) from which a liquid part is separated, are connected. Then, a reaction mass as a liquid part, from which a gas part (i.e., gas component) is separated, is continuously fed to the first distillation column (crude propylene oxide separation column) (6) .
  • the theoretical plate number is within a range from 1 to 200.
  • the temperature is within a range from 0°C to 300°C
  • the pressure is within a range from 0.005 MPa to 10 MPa
  • the reflux ratio is within a range from 0.001 to 10.
  • a crude propylene oxide is obtained as a top liquid of the column, which contains propylene oxide, from a discharging tube of top liquid of a first distillation column (hereinafter sometimes referred to as a discharging tube of a top liquid of a first distillation column (18)), denoted by the reference numeral (18) in Fig. 2, connected to the top section of the column.
  • the obtained crude propylene oxide may be further purified by a known method or a method analogous thereto.
  • a solution containing acetonitrile, water, amides, oxazolines, and aldehydes is obtained from a discharging tube of bottom liquid of a first distillation column (hereinafter sometimes referred to as discharging tube of bottom liquid of a first distillation column (17)), denoted by the reference numeral (17) in Fig. 2, connected to the bottom section of the column.
  • discharging tube of bottom liquid of a first distillation column (17) denoted by the reference numeral (17) in Fig. 2
  • the bottom liquid of the column is obtained as a quinoid compound- containing solution.
  • the reaction mass from the epoxidation reaction tank (3) is continuously separated into a gas part (i.e., gas component) composed mainly of hydrogen/oxygen/nitrogen, a recovered propylene, a crude propylene oxide, a recovered solvent and a gas part (i.e., gas component) composed mainly of hydrogen/oxygen/nitrogen, a recovered propylene, a crude propylene oxide, a recovered solvent and a gas part (i.e., gas component) composed mainly of hydrogen/oxygen/nitrogen, a recovered propylene, a crude propylene oxide, a recovered solvent and a
  • gas part i.e., gas component
  • first distillation column sometimes referred to as a first distillation column
  • second distillation column acetonitrile solvent separation column (7)
  • propane separation column a propylene oxide purification column
  • solvent purification column a solvent purification column
  • recovered solvent and recovered quinone compound are recycled after subjecting to the epoxidation reaction again
  • the recovered propylene contains, for example, impurities such as propane, cyclopropane, methylacetylene, propadiene, butadiene, butanes, butenes, ethylene, ethane, methane and hydrogen, it may be optionally recycled after separation and purification.
  • an amino group and/or a hydroxyl group may be substituted or not.
  • hydroxylamine (NH 2 OH), N- isopropylhydroxylamine, N, N-diethylhydroxylamine, N,0- dimethylhydroxylamine , O-benzylhydroxylamine, 0- methylhydroxylamine, N-methylhydroxylamine, N,0- dimethylhydroxylamine, O-ethylhydroxylamine, N- ethylhydroxylamine, 0, -diethylhydroxylamine, N- phenylhydroxylamine, O-pentylhydroxylamine, 0-(2- methylpropyl) hydroxylamine, 0- (3-methylbutyl) hydroxylamine , O-hexylhydroxylamine, O-decylhydroxylamine and 0- benzylhydroxylamine .
  • hydroxylamine (NH2OH) is preferably exemplified.
  • the hydroxylamine compound may be handled as a salt. Specifically,
  • hydroxylamine sulfate or hydroxylamine hydrochloride can be preferably exemplified.
  • the use amount of the hydroxylamine compound is, for example, within a range from 0.1 mol to 100 mol, and more preferably from 1 mol to 10 mol, based on 1 mol of
  • acetaldehyde contained in the reaction mass is entirely or partially converted into acetaldoxime by mixing in the obtained reaction mass (i.e., oximation reaction) is, for example, within a range from 0°C to 200°C, and preferably from 20°C to 150°C.
  • the reaction pressure gauge pressure
  • the reaction may be the same pressure as that used in the epoxidation reaction, or reduced after the epoxidation reaction and may be normal pressure or reduced pressure.
  • the reaction may be performed under the same pressure as in the prestep of the oxime reaction.
  • the time (specifically, retention time of a reaction mass in a reaction tank for oxime reaction) used for the reaction in which acetaldehyde contained in the reaction mass is entirely or partially converted into acetaldoxime by mixing in the obtained reaction mass (i.e., oximation reaction) is, for example, 0.01 hour or more, and preferably within a range from 0.1 hour to 10 hours.
  • the obtaining method of the present invention further includes, in addition to the epoxidation reaction, an oximation reaction in which a hydroxylamine compound is mixed in the reaction mass obtained by the reaction and then acetaldehyde contained in the reaction mass as byproducts is entirely or partially converted into
  • the oximation reaction may be carried out in any process between a gas-liquid separation tank (4) after the epoxidation reaction and the second distillation column (acetonitrile solvent separation column) (7).
  • the oximation reaction is carried out as the process existing between the gas-liquid separation tank (4) after the epoxidation reaction and the first distillation column (crude propylene oxide separation column) (6) (see, for example, Fig. 1) .
  • the oximation reaction is carried out as the process existing between the first distillation column (crude propylene oxide separation column) (6) and the second distillation column (acetonitrile solvent separation column) (7) (see, for example, Fig. 2).
  • the oximation reaction may be carried out plural times by using these processes in combination.
  • the first obtaining method of the present invention is composed of the separation/removal step and the recovery step.
  • the separation/removal step includes both of the process based on the epoxidation reaction and the process based on the oximation reaction.
  • hydroxylamine compound in the reaction mass which is obtained by feeding, as a liquid gas, a reaction mass obtained by reacting the main raw materials into a gas- liquid separator, and separating into a reaction mass as a liquid part and a gas as a gas part under a pressure which is the same as or lower than that obtained in the
  • the separation/removal step is the step of distilling a reaction mass before removing acetaldoxime
  • the distillation step includes the step of separating or removing by recovering a top liquid of the column, which contains propylene oxide, from a top section of a distillation column and also recovering a bottom liquid of the column, which contains acetaldoxime and acetonitrile, from a bottom section of a distillation column.
  • an oximation reaction tank denoted by the reference numeral (5) in Fig. 1 (hereinafter sometimes referred to as an oximation reaction tank (5)) as one of embodiments of the specific apparatus for oximation
  • reaction includes a paddle blade therein, and also includes an epoxidation reaction mass discharging/feeding tube (13) for continuously receiving a reaction mass from a gas- liquid separation tank (4), a hydroxylamine compound- containing solution feeding tube, denoted by the reference numeral (15) in Fig. 1, for continuously receiving a hydroxylamine compound-containing solution (hereinafter sometimes referred to as a hydroxylamine compound- containing solution feeding tube (15)), and a reaction mass discharging/feeding tube to first distillation column after oximation reaction denoted by the reference numeral (16) in Fig.
  • reaction mass discharging/feeding tube to a first distillation column after an oximation reaction (16) connected thereto. Then, a reaction mass containing propylene oxide in which the content of acetaldehyde is reduced is obtained from the reaction mass discharging/feeding tube to a first
  • first distillation column (6) In the first distillation column denoted by the reference numeral (6) in Fig. 1 (hereinafter sometimes referred to as a first distillation column (6)) as one of embodiments of the specific first distillation column, by feeding a reaction mass containing propylene oxide in which the content of acetaldehyde is reduced from the reaction mass discharging/feeding tube to a first distillation column after an oximation reaction (16), a crude propylene oxide is obtained as a top liquid of the column, which contains propylene oxide, from a discharging tube of a top liquid of a first distillation column (18) connected to the top section of the column.
  • the obtained crude propylene oxide may be further purified by a known method or a method analogous thereto.
  • a solution containing acetonitrile, water, amides, oxazolines, and acetaldoxime formed by modification of acetaldehyde is obtained from a discharging tube of a bottom liquid of a first distillation column (17) connected to the bottom section of the column.
  • a bottom liquid of the column is obtained as a quinoid compound-containing solution.
  • a second distillation column denoted by the reference numeral (7) in Fig. 1 (hereinafter sometimes referred to as a second distillation column (7) ) as one of embodiments of the specific second distillation column, by feeding a solution containing acetonitrile, water, amides, oxazolines, and acetaldoxime formed by modification of acetaldehyde from a discharging tube of a bottom liquid of a first distillation column (17), acetonitrile is obtained from a discharging tube of a top liquid of a second
  • distillation column denoted by the reference numeral (20) in Fig. 1 connected to the top section of the column
  • a discharging tube of a top liquid of a second distillation column (20) (hereinafter sometimes referred to as a discharging tube of a top liquid of a second distillation column (20)).
  • a solution containing water, amides, oxazolines, and acetaldoxime formed by modification of acetaldehyde is obtained from a discharging tube of a bottom liquid of a second distillation column denoted by the reference numeral (19) in Fig. 1 connected to the bottom section of the column (hereinafter sometimes
  • a discharging tube of a bottom liquid of a second distillation column (19) referred to as a discharging tube of a bottom liquid of a second distillation column (19)
  • the theoretical plate number is within a range from 1 to 100.
  • the temperature is within a range from 0°C to 300°C
  • the pressure is within a range from 0.005 MPa to 10 MPa
  • the reflux ratio is within a range from 0.001 to 10.
  • Acetonitrile (the composition of acetonitrile depends on distillation column pressure conditions and is usually within a range from 50/50 to 100/0 (acetonitrile/water :
  • weight ratio) ) obtained from the discharging tube of a top liquid of a second distillation column (20) connected to the top section of the column may be directly recycled to the epoxidation reaction, or may be further purified by a known method or a method analogous thereto.
  • the second obtaining method of the present invention is composed of the recovery step and the separation/removal step.
  • the separation/removal step does not include the process based on the epoxidation reaction, and only includes the process based on the oximation reaction.
  • the recovery step the step of recovering propylene oxide existing in the reaction mass which is obtained by feeding, as a liquid gas, a reaction mass obtained by reacting the main raw materials into a gas-liquid separator, and then separating into a reaction mass as a liquid part and a gas as a gas part under a pressure which is the same as or lower than that obtained in the reaction.
  • the separation/removal step is the step of distilling a reaction mass before removing acetaldoxime
  • the distillation step includes the step of separating or removing by recovering a top liquid of the column, which contains acetonitrile , from a top section of a distillation column and also recovering a bottom liquid of the column, which contains acetaldoxime, from a bottom section of a distillation column.
  • an oximation reaction tank denoted by the reference numeral (5) in Fig. 2 (hereinafter sometimes referred to as an oximation reaction tank (5) ) as one of embodiments of the specific apparatus for oximation
  • reaction includes a paddle blade therein, and also includes a discharging tube of bottom liquid of a first distillation column (17) for continuously receiving a reaction mass from a first distillation column (crude propylene oxide
  • reaction mass discharging/feeding tube to second a hydroxylamine compound-containing solution feeding tube (15) for continuously receiving a hydroxylamine compound-containing solution and a reaction mass discharging/feeding tube to a second distillation column after an oximation reaction denoted by the reference numeral (16) in Fig. 2 (hereinafter sometimes referred to as reaction mass discharging/feeding tube to second
  • reaction mass containing acetonitrile in which the content of acetaldehyde is reduced is obtained from a reaction mass
  • acetonitrile is obtained from a discharging tube of a top liquid of a second distillation column (20) connected to the top section of the column.
  • the theoretical plate number is within a range from 1 to 100.
  • the temperature is within a range from 0°C to 300°C
  • the pressure is within a range from 0.005 MPa to 10 MPa
  • the reflux ratio is within a range from 0.001 to 10.
  • Acetonitrile (the composition of acetonitrile depends on distillation column pressure conditions and is usually within a range from 50/50 to 100/0 (acetonitrile/water :
  • weight ratio) ) obtained from the discharging tube of a top liquid of a second distillation column (20) connected to the top section of the column may be directly recycled to the epoxidation reaction, or may be further purified by a known method or a method analogous thereto.
  • the Ti-MWW precursor used in Example 1 was prepared in the following manner.
  • the obtained filter cake was dried at 50°C to obtain a white powder in a state of still containing water.
  • 750 mL of 2N nitric acid was added and then the obtained mixture was heated under reflux for 20 hours. The heated mixture was filtered and then the separated filter cake was washed with water until the filtrate becomes nearly neutral.
  • the obtained filter cake was sufficiently dried at 50°C to obtain 11 g of a white powder.
  • the obtained white powder was subjected to the measurement of an X-ray diffraction pattern by an X-ray diffractometer using copper K-alpha radiation. As a result, it was confirmed that the white powder is a Ti- WW precursor.
  • titanium determined by ICP spectrometry was 1.6% by weight.
  • the Ti-MWW precursor thus obtained was further fired at 530°C for 6 hours.
  • the obtained fired product (27 g) was dissolved in an autoclave at room temperature under an air atmosphere while stirring with a mixture of 23 g of piperidine and 45 g of pure water to. prepare a gel, and then the gel was aged for 1.5 hours.
  • the obtained white powder was subjected to the measurement of an X-ray diffraction pattern by an X-ray diffractometer using copper K-alpha radiation. As a result, it was confirmed that the white powder has a MWW precursor
  • a precursor treated in advance with hydrogen peroxide was used as a Ti-MWW precursor to be used in an epoxidation reaction in the subsequent step. Namely, a treated substance, obtained by treating 2.28 g of a Ti-MWW
  • water/acetonitrile 20/80 (weight ratio) containing 0.1% by weight of hydrogen peroxide, at room temperature for 1 hour, was filtered and then the separated filter cake was recovered and the filter cake was used in the epoxidation reaction- in the subsequent step.
  • a reaction mass obtained by removing both a Ti-MWW precursor and a palladium-supported activated carbon catalyst through filtration using a sintered filter is subjected to gas- liquid separation under a normal pressure using a gas- liquid separation tank, whereby, a liquid component and a gas component were continuously extracted from the gas- liquid separation tank while separating.
  • propylene oxide in the extracted liquid component increased to 9.8% by weight, and the concentration of propylene glycol increased to 0.1% by weight. Furthermore, the concentration of acetaldehyde (ACH) in the above component was 4 ppm by weight.
  • ACH acetaldehyde
  • anthraquinone (a compound corresponding to a quinone compound) in the concentration of 15 ppm by weight and diammonium hydrogen phosphate ((NH 4 ) 2 HP0 4 , a compound corresponding to a buffer agent) in the
  • hydroxyamine/acetaldehyde becomes the value described in Table 1, was stirred at 70°C.
  • Table 2 the results of a test (Comparative Example) carried out in the same manner, except that hydroxyamine hydrochloride
  • acetaldehyde ACH in the concentration of 28 ppm by weight, propylene glycol in the concentration of 0.38% by weight, anthraquinone (a compound corresponding to a quinone compound) in the concentration of 15 ppm by weight and diammonium hydrogen phosphate ( (NH 4 ) 2 HP0 4 , a compound corresponding to a buffer agent) in the
  • acetaldehyde in the concentration of 28 ppm by weight, propylene oxide in the concentration of 10.5 by weight, anthraquinone (a compound corresponding to a quinone compound) in the concentration of 15 ppm by weight and diammonium hydrogen phosphate ((NH 4 ) 2 HP0 4 , a compound corresponding to a buffer agent) in the concentration of 40 ppm by weight was prepared.
  • hydroxyamine/acetaldehyde becomes the value described in Table 3, was stirred at 70°C.
  • Table 4 the results of a test (Comparative Example) carried out in the same manner, except that hydroxyamine sulfate

Abstract

La présente invention a pour but de proposer un procédé d'obtention d'oxyde de propylène, dans lequel la teneur d'acétaldéhyde est réduite en permettant l'élimination d'acétaldéhyde. De manière plus spécifique, la présente invention concerne un procédé d'obtention d'oxyde de propylène, qui comprend les étapes consistant à mélanger un composé hydroxylamine dans une masse réactionnelle qui est obtenue par réaction à la fois de matières brutes de (a) peroxyde hydrogène, ou hydrogène et oxygène, et (b) propylène dans un solvant contenant de l'acétonitrile en présence d'un catalyseur, permettant ainsi de convertir entièrement ou partiellement l'acétaldéhyde contenu dans la masse réactionnelle en acétaldoxime, puis à séparer ou à retirer l'acétaldoxime de la masse réactionnelle ; et à récupérer la masse réactionnelle obtenue par l'étape précédente ou l'oxyde de propylène existant dans la masse réactionnelle.
PCT/JP2012/059946 2011-04-08 2012-04-05 Procédé d'obtention d'oxyde de propylène WO2012137979A1 (fr)

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