WO2010032609A1 - オレフィンの製造方法およびその製造装置 - Google Patents
オレフィンの製造方法およびその製造装置 Download PDFInfo
- Publication number
- WO2010032609A1 WO2010032609A1 PCT/JP2009/065270 JP2009065270W WO2010032609A1 WO 2010032609 A1 WO2010032609 A1 WO 2010032609A1 JP 2009065270 W JP2009065270 W JP 2009065270W WO 2010032609 A1 WO2010032609 A1 WO 2010032609A1
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- Prior art keywords
- gas
- ethane
- fraction
- catalyst
- reactor
- Prior art date
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/20—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert heated gases or vapours
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
- C07C6/10—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond in hydrocarbons containing no six-membered aromatic rings
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- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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Definitions
- the present invention relates to an olefin production method and apparatus for producing an olefin having 3 or more carbon atoms by pyrolysis of ethane and catalytic conversion with a zeolite catalyst.
- Patent Document 1 discloses a method for producing propylene from ethylene obtained by thermally decomposing ethane in the presence of water vapor using a metathesis reaction.
- Patent Document 1 requires a compression step. Furthermore, this method requires a complicated and multi-stage purification process in order to remove low-boiling substances, high-boiling substances, acetylene, and water contained in the product gas generated by the thermal decomposition together with ethylene. Therefore, a method for producing an olefin having 3 or more carbon atoms more simply is desired.
- An object of the present invention is to provide a method for producing an olefin having 3 or more carbon atoms from ethane, which is simpler and more stable, and an apparatus for producing the same.
- the present inventors have obtained ethane as a medium-pore-diameter zeolite-containing catalyst without purifying a gas obtained by thermally decomposing ethane in the presence of water vapor.
- the inventors have found that an olefin having 3 or more carbon atoms can be stably produced by bringing them into contact with each other, thereby completing the present invention.
- the present invention provides the following method for producing an olefin having 3 or more carbon atoms.
- this invention provides the manufacturing apparatus of the following C3 or more olefins.
- a production apparatus for producing an olefin having 3 or more carbon atoms from ethane Connected to a first reactor for pyrolyzing ethane in the presence of water vapor to obtain ethane cracked gas, and receiving and cooling the ethane cracked gas flowing out from the first reactor to obtain a cooled fraction
- a second reactor connected to the cooler and filled with a catalyst containing an intermediate pore size zeolite for receiving the cooled fraction flowing out of the cooler and bringing it into contact with the catalyst.
- Olefin production equipment Connected to a first reactor for pyrolyzing ethane in the presence of water vapor to obtain ethane cracked gas, and receiving and cooling the ethane cracked gas flowing out from the first reactor to obtain a cooled fraction
- a second reactor connected to the cooler and filled with a catalyst containing an intermediate pore size zeolite for
- An apparatus for producing an olefin having 3 or more carbon atoms from ethane connected to a first reactor for thermally decomposing ethane in the presence of water vapor to obtain ethane decomposition gas, A chiller for receiving and cooling the ethane decomposition gas flowing out from one reactor to obtain a cooled fraction; and a cooling heavy fraction connected to the cooler and flowing out from the cooler, A gas-liquid separator for separating the gas into a liquid and a cooling gas; and the cooling gas connected to the gas-liquid separator and filled with a catalyst containing an intermediate pore size zeolite and flowing out of the gas-liquid separator A second reactor for accepting and contacting the catalyst with the catalyst.
- the production method and production apparatus of the present invention it is possible to provide a method for producing an olefin having 3 or more carbon atoms from ethane in a simple and stable manner, and a production apparatus therefor.
- the present embodiment modes for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail with reference to the drawings as necessary.
- the following embodiment is an exemplification for explaining the present invention, and is not intended to limit the present invention only to this embodiment.
- the present invention can be implemented in various forms without departing from the gist thereof.
- the same elements are denoted by the same reference numerals, and redundant description is omitted.
- the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified.
- the dimensional ratios in the drawings are not limited to the illustrated ratios.
- FIG. 1 is a schematic view of a production apparatus that can be used in the olefin production method of the present embodiment.
- the olefin production apparatus shown in FIG. 1 includes a first reactor (pyrolysis reactor 1), a cooler 2, a second reactor (catalyst reactor 3), and a separation device 4.
- Ethane and water vapor are supplied to the pyrolysis reactor 1 through a pipe 11.
- the pyrolysis reactor 1 containing ethane and water vapor is provided with a convection section (not shown), and the ethane and water vapor are preheated to about 600 ° C. there.
- a preheater may be installed outside the pyrolysis reactor 1 as necessary. The ethane preheated together with the steam is further heated and pyrolyzed in the pyrolysis reactor 1 to generate ethane cracking gas containing ethylene (ethane pyrolysis step).
- the ethane raw material supplied to the pyrolysis reactor 1 may contain a small amount of methane, propane, etc. in addition to ethane.
- the ethane raw material may be separated from natural gas, fractionated from petroleum gas, or by-produced by thermal decomposition of naphtha or heavy oil. Alternatively, the ethane raw material may be ethane generated in the production process of other products.
- the reaction temperature (pyrolysis temperature) in the ethane pyrolysis step is preferably in the range of 780 to 880 ° C.
- the reaction pressure is preferably in the range of 0.05 to 1 MPa, more preferably in the range of 0.1 to 0.5 MPa.
- the mass ratio of water vapor to ethane is preferably 0.1 to 2.0 in terms of water vapor / ethane, and more preferably 0.2 to 1.0.
- the residence time of steam and ethane in the thermal decomposition reactor 1 is preferably 5 seconds or less, and more preferably 2 seconds or less. From the viewpoint of suppressing coking, it is preferable that steam and ethane are supplied to the pyrolysis reactor 1 together.
- the outlet pressure can be measured at the measurement point of the reaction pressure, but since there is substantially no pressure difference between the inlet and the outlet, the reaction pressure can be measured at either the inlet or the outlet.
- the ethane decomposition gas may contain, for example, unreacted ethane, water, hydrogen, carbon monoxide, carbon dioxide, alkanes other than ethane, olefins other than ethylene, and aromatic hydrocarbons in addition to ethylene.
- alkanes include methane, propane, butane, pentane and hexane.
- olefins include propylene, butene, pentene, and hexene.
- the aromatic hydrocarbon include benzene, toluene, xylene, ethylbenzene, and styrene.
- the ethane cracking gas may contain cycloalkanes such as cyclopentane, methylcyclopentane and cyclohexane, and cycloolefins such as cyclopentene, methylcyclopentene and cyclohexene.
- the ethane decomposition gas usually contains acetylene compounds such as acetylene and methylacetylene, and diolefin (diene) compounds such as propadiene, butadiene, pentadiene, and cyclopentadiene.
- the pyrolysis reactor 1 is connected to the cooler 2 via a pipe 12.
- a normal heat exchanger is preferably used.
- water vapor is employed as the refrigerant, and the amount of heat of the ethane pyrolysis gas can be recovered as high-pressure water vapor, which can be used as a power source for the separation process described later.
- the cooler 2 shown in FIG. 1 is 1 unit
- the ethane decomposition gas containing ethylene flowing out from the thermal decomposition reactor 1 is supplied to the cooler 2 via the pipe 12.
- the ethane decomposition gas is cooled to 600 ° C. or lower to obtain a cooled fraction (cooling step).
- the reaction of olefins in the ethane cracking gas can be prevented.
- a preferable cooling temperature is in the range of 300 to 600 ° C.
- ethylene (described later) is converted to an olefin having 3 or more carbon atoms without reheating with a pyrolysis gas or a heater, or intermediate heating in a catalytic reactor.
- the reaction temperature for the conversion of can be adjusted to a suitable range. This is because the conversion reaction is an exothermic reaction, and if the temperature of the fraction to be subjected to the reaction is within this range, it is maintained at an appropriate temperature by the reaction heat without requiring heating.
- the cooling temperature is preferably 300 to 550 ° C., more preferably 300 to 500 ° C., and particularly preferably 300 to 450 ° C.
- the cooler 2 is connected to the catalytic reactor 3 via a pipe 13.
- the catalyst reactor 3 is filled with a catalyst containing an intermediate pore size zeolite (hereinafter simply referred to as “zeolite-containing catalyst”).
- zeolite-containing catalyst a catalyst containing an intermediate pore size zeolite
- the ethane decomposition gas cooled by the cooler 2 is supplied to the catalyst reactor 3 via the pipe 13 and is brought into contact with the zeolite-containing catalyst in the catalyst reactor 3.
- ethylene contained in the ethane cracking gas is converted into olefins having 3 or more carbon atoms, and a contact gas containing these olefins is obtained (contact conversion step).
- the ethane decomposition gas is cooled by the cooler 2 and flows out from the cooler 2 as a cooling fraction, and is supplied to the catalytic reactor 3 as it is without being subjected to a purification treatment, so that the catalytic conversion reaction is performed. To be served.
- a part of cooling fraction liquefies, as long as the whole quantity is supplied to catalytic conversion reaction, it is included by this embodiment. Even if the liquefied fraction is supplied to the catalytic reactor 3, there is substantially no obstacle.
- acetylene compounds and diene compounds contained in the ethane decomposition gas are also supplied to the catalyst reactor 3. These compounds are rich in polymerizability, and the polymerized product caulks the zeolite-containing catalyst to block its active site, which causes catalyst deterioration. From the viewpoint of stabilizing the catalytic conversion reaction of ethylene by preventing deterioration of the catalyst due to coking, acetylene compounds and diene compounds may be reduced to the minimum by treatment such as distillation separation and partial hydrogenation prior to the reaction. It has been considered preferable.
- the conversion reaction from ethylene to an olefin having 3 or more carbon atoms is an exothermic reaction, and the amount of heat generation increases as the amount of ethylene conversion increases. Therefore, in order to precisely control the conversion reaction temperature, the reaction heat is effective. It is also required to cope with the removal (heat removal). Therefore, the catalytic reactor 3 is required to have a performance that can cope with these problems.
- the type of the catalyst reactor 3 is not particularly limited, and any reactor type such as a fixed bed type reactor, a fluidized bed type reactor, or a moving bed type reactor can be used.
- the catalyst reactor 3 is a fixed bed reactor, a swing type catalyst reactor capable of switching between a catalytic conversion reaction and a catalyst regeneration step described later is preferable from the viewpoint of the above-described catalyst coking countermeasures. From the viewpoint of removing reaction heat, a multi-tube type catalytic reactor is preferable.
- the outlet gas composition of the catalytic reactor 3 varies. Therefore, in order to keep the composition within a certain range, the temperature of the ethane decomposition gas at the inlet of the catalytic reactor 3 is increased with time, or the intermediate heating temperature in the catalytic reactor 3 is increased, that is, the reactor is heated by external heating. The internal temperature may be raised.
- Examples of a method for increasing the temperature of the ethane decomposition gas at the inlet of the catalyst reactor 3 include a method for increasing the cooling temperature of the cooler 2 and a method for reheating with a preheater provided upstream of the catalyst reactor 3.
- a fluid bed type, riser type or spouted bed type catalyst reactor is preferably used. More preferably, from the viewpoint of efficiency when the catalyst is regenerated, a catalyst circulation type reactor having a catalyst regeneration device in a fluidized bed reactor is used.
- the catalyst circulation type reactor has a pipe that connects them so that the catalyst can be circulated between the fluidized bed reactor and the catalyst regeneration device.
- a catalytic conversion reaction of ethylene proceeds using a zeolite-containing catalyst. A part of the zeolite-containing catalyst subjected to the catalytic conversion reaction is withdrawn from the fluidized bed reactor continuously or intermittently, and is supplied to the catalyst regeneration device via a pipe.
- the catalyst regeneration device At least a part of the carbonaceous compound (coke) attached to the zeolite-containing catalyst is combusted by a catalyst regeneration method described later.
- the coke adhering to the catalyst is removed by combustion, whereby the catalyst performance is recovered.
- the zeolite-containing catalyst is re-supplied to the fluidized bed reactor via the pipe.
- a heat removal facility such as a cooling coil is preferably used for removing reaction heat generated by the catalytic conversion reaction.
- the regeneration method of the catalyst is as follows.
- a zeolite-containing catalyst is used for a long-term reaction, a carbonaceous compound may be formed on the catalyst, and the catalytic activity may be reduced.
- a fixed bed reactor by temporarily stopping the supply of the raw material (ethane decomposition gas) to the reactor, supplying a gas containing oxygen, and burning the coke accumulated in the zeolite-containing catalyst, The zeolite-containing catalyst can be regenerated.
- a part of the zeolite-containing catalyst is continuously or intermittently extracted from the reactor, calcined with a gas containing oxygen, and the attached coke is burned.
- the zeolite-containing catalyst can be regenerated.
- the regenerated zeolite-containing catalyst can be returned to the reactor.
- air or a mixed gas composed of air and an inert gas at a high temperature, preferably 400 to 700 ° C., the coke burns and the catalyst is regenerated.
- the zeolite in the zeolite-containing catalyst charged in the catalyst reactor 3 is a so-called “medium pore diameter zeolite” having a pore diameter of 5 to 6.5 mm.
- the term “medium pore diameter zeolite” means that the pore diameter ranges from a small pore diameter zeolite represented by A-type zeolite and a large pore diameter represented by mordenite, X-type and Y-type zeolite. It means a zeolite in the middle of the pore diameter of the zeolite, and means a zeolite having a so-called oxygen 10-membered ring in its crystal structure.
- the silica / alumina ratio (molar ratio; the same shall apply hereinafter) of zeolite is preferably 20 or more from the viewpoint of stability as a catalyst.
- the upper limit of the silica / alumina ratio is not particularly limited, but from the viewpoint of catalytic activity, generally, the silica / alumina ratio is more preferably in the range of 20 to 1000, and in the range of 20 to 500. And more preferably 20 to 300.
- the silica / alumina ratio of the zeolite can be determined by a known method, for example, by completely dissolving the zeolite in an alkaline aqueous solution and analyzing the resulting solution by plasma emission spectroscopy.
- Zeolite is not particularly limited as long as it falls within the category of “medium pore diameter zeolite”.
- Examples of the medium pore diameter zeolite include ZSM-5 and so-called pentasil-type zeolite having a structure similar to ZSM-5. That is, examples of the intermediate pore diameter zeolite include ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-18, ZSM-23, ZSM-35, and ZSM-39.
- a zeolite represented by an MFI structure in a skeleton structure type according to the IUPAC recommendation can be mentioned, and specifically, ZSM-5 can be mentioned.
- the “silica / alumina ratio” of metalloaluminosilicate or metallosilicate is calculated after converting the amount of aluminum atoms substituted by the above elements into the number of moles of Al 2 O 3 (alumina).
- the method for forming the zeolite-containing catalyst is not particularly limited and may be a general method. Specific examples include a method of spray drying a catalyst precursor, a method of compression molding, and a method of extrusion molding.
- a binder or a diluent for molding matrix
- the binder and the diluent for molding are not particularly limited, but porous refractory inorganic oxides such as alumina, silica, silica / alumina, zirconia, titania, diatomaceous earth, and clay can be used alone or in combination. .
- the mass ratio of the medium pore diameter zeolite to the binder and the molding diluent is medium pore diameter zeolite / (binder and molding diluent), preferably in the range of 10/90 to 90/10, more preferably 20 The range is from / 80 to 80/20.
- the slurry containing the intermediate pore size zeolite before spray drying is selected from the group consisting of nitrate, acetate and carbonate for the purpose of improving the shape and mechanical strength.
- One or more water-soluble compounds may be added.
- Preferable water-soluble compounds include ammonium salts that have high water solubility and can be decomposed and removed from the catalyst by calcination.
- the zeolite-containing catalyst may be subjected to heat treatment, preferably in the presence of water vapor, prior to contact with the ethane decomposition gas that is a cooling fraction.
- the temperature of the heat treatment is preferably 500 ° C. or higher, more preferably 500 to 900 ° C., regardless of the presence or absence of water vapor.
- the heat treatment is preferably performed under the condition that the partial pressure of water vapor is 0.01 atm or more.
- the acid amount (hereinafter referred to as TPD acid amount) determined from the high temperature desorption amount in the temperature-programmed desorption (TPD) spectrum of ammonia. May be used).
- TPD acid amount determined from the high temperature desorption amount in the temperature-programmed desorption (TPD) spectrum of ammonia. May be used).
- the conversion reaction proceeds when the zeolite-containing catalyst has a TPD acid amount exceeding zero.
- the amount of TPD acid is preferably 20 ⁇ mol / g-zeolite or more, more preferably 20 to 500 ⁇ mol / g-zeolite, and particularly preferably 20 to 300 ⁇ mol / g-zeolite.
- the upper limit of the amount of TPD acid is set from the viewpoint of olefin yield.
- the amount of TPD acid is measured by the following method. First, a sample catalyst is placed in a measurement cell of a temperature programmed desorption spectrum measuring apparatus, the inside of the measurement cell is replaced with helium gas, and the temperature is maintained at 100 ° C. Next, after the pressure in the measurement cell is reduced once, ammonia gas is supplied to set the pressure in the measurement cell to 100 Torr, and this state is maintained for 30 minutes to adsorb ammonia to the catalyst. The inside of the measurement cell is again depressurized to remove ammonia not adsorbed on the catalyst, and the inside of the cell is returned to atmospheric pressure with helium.
- the measurement cell was connected to a quadrupole mass spectrometer, the pressure in the cell was set to 200 Torr, and the temperature in the cell was increased to 600 ° C. at a temperature increase rate of 8.33 ° C./min.
- the temperature rising desorption spectrum is obtained by detecting the desorbed ammonia.
- the pressure in the cell during desorption is adjusted to be maintained at about 200 Torr.
- the obtained temperature-programmed desorption spectrum is divided by waveform separation based on Gaussian distribution, and the ammonia desorption amount is obtained from the sum of the areas of waveforms (peaks) having a peak top at a desorption temperature of 240 ° C. or higher.
- the value divided by the mass of the zeolite contained therein (unit: ⁇ mol / g-zeolite) is the TPD acid amount.
- 240 ° C.” is an index used only for determining the position of the peak top, and does not mean that only the area of the 240 ° C. or higher portion is obtained. As long as the peak top is a waveform of 240 ° C.
- the “area of the waveform” is the total area including the portion below 240 ° C.
- the sum of the areas of the respective waveforms is used.
- the zeolite-containing catalyst may contain at least one metal element selected from the group consisting of metals belonging to Group IB of the Periodic Table (hereinafter simply referred to as “Group IB metal”).
- Group IB metal metals belonging to Group IB of the Periodic Table
- “containing a metal element” means that the intermediate pore size zeolite in the zeolite-containing catalyst contains the metal element in a corresponding cation state, or that the metal element is contained in the zeolite-containing catalyst in the form of metal or oxidation. It means that it is carried in the state of an object.
- the “periodic table” in this specification refers to the cycle described in CRC Handbook of Chemistry and Physics, 75th edition, David R. Lide et al., CRC Press Inc. (1994-1995), pages 1-15. Means the table.
- the zeolite-containing catalyst contains a group IB metal element, that is, at least one metal element selected from the group consisting of copper, silver and gold. More preferred group IB metals include copper and silver, and more preferably silver. Examples of the method for causing the zeolite-containing catalyst to contain at least one metal element selected from the group consisting of a group IB metal element include a method for containing a group IB metal element in the medium pore diameter zeolite.
- the ion exchange treatment may be a liquid phase method or a solid phase method.
- the ion exchange treatment of the solid phase method is a method in which a solution containing a group IB metal is impregnated in a medium pore diameter zeolite (not containing a group IB metal) or a zeolite-containing catalyst.
- a salt of a Group IB metal for example, silver nitrate, silver acetate, silver sulfate, copper chloride, copper sulfate, copper nitrate, or gold chloride can be used. Of these, silver nitrate and copper nitrate are preferably used, and silver nitrate is more preferably used.
- the content of the group IB metal in the intermediate pore size zeolite is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the total amount of the intermediate pore size zeolite.
- the content of the group IB metal can be determined by X-ray fluorescence analysis or the like.
- ion exchange site of the intermediate pore size zeolite contained in the zeolite-containing catalyst is exchanged with a group IB metal cation and / or proton.
- ion exchange sites other than those exchanged with group IB metal cations and / or protons may be exchanged with alkali metal cations, alkaline earth metal cations, and other metal cations.
- the reaction temperature is preferably 400 to 650 ° C., more preferably 450 to 600 ° C.
- the partial pressure of the ethane decomposition gas is desirably low, and is usually 0.01 to 1 MPa, more preferably 0.05 to 0.5 MPa.
- Weight hourly space velocity WHSV of ethane decomposition gas to the mass of the zeolite-containing catalyst 0.1 ⁇ 50hr -1, preferably in the range of 0.2 ⁇ 20 hr -1.
- the catalytic conversion reaction is carried out under conditions in which paraffin does not substantially react, the conversion reaction of ethylene in the ethane cracking gas is selectively promoted, and the conversion reaction of paraffin is suppressed.
- by-products such as methane, ethane, propane, and butane due to the paraffin conversion reaction are suppressed, and separation and purification of olefins having 3 or more carbon atoms from the reaction mixture are easy.
- the reaction to produce olefins having 3 or more carbon atoms by catalytic conversion of olefins containing 2 or more carbons mainly composed of ethylene contained in ethane cracking gas is an equilibrium reaction, and in terms of equilibrium, the conversion rate of ethylene, which is a representative component Shows the maximum yield of olefins having 3 or more carbon atoms in the vicinity of 60 to 70% by mass. Therefore, in order to efficiently obtain an olefin having 3 or more carbon atoms, the ethylene conversion is preferably in the range of 45 to 85% by mass, more preferably 50 to 80% by mass.
- the conversion rate of ethylene is calculated by the following formula (2).
- Ethylene conversion rate (ethylene concentration in ethane cracking gas supplied to catalyst reactor 3 ⁇ ethylene concentration in contact gas flowing out from catalyst reactor 3) / ethylene in ethane cracking gas supplied to catalyst reactor 3 Concentration x 100 (2)
- the catalytic reactor 3 is connected to the separation device 4 via a pipe 14.
- the contact gas containing an olefin having 3 or more carbon atoms obtained in the catalyst reactor 3 is supplied to the separation device 4 via the pipe 14 and separated into each fraction by the separation device 4 (separation step).
- each fraction is separated by various methods such as fractional distillation and extraction, or a combination thereof.
- the separation device 4 is not particularly limited as long as it is a device suitable for those methods, and may be a distillation column such as a plate column or a packed column, for example.
- gasoline fraction refers to a fraction having a boiling point in the range of 30 to 220 ° C.
- Acrylonitrile and polypropylene can be produced from propylene collected via the pipe 16 by the method described in Japanese Patent No. 3214984.
- FIG. 2 is a schematic view of a production apparatus that can be used in another olefin production method of the present embodiment.
- a gas-liquid separator 5 is connected between the cooler 2 and the catalytic reactor 3, and a heavy component recovery tank 6 is connected to the gas-liquid separator 5.
- Separation device 8 for separating the C4 fraction flowing out from the separation device 4 into isobutene and normal butene, and a separation device 7 for separating the gasoline fraction into aromatic hydrocarbons and C5 fraction.
- piping for supplying each fraction separated by the separation devices 4 and 7 to the thermal decomposition reactor 1 or the catalytic reactor 3 is provided. is there.
- the cooling fraction obtained by cooling the ethane decomposition gas in the cooler 2 is a liquid heavy fraction that is a condensate contained therein and a lighter cooling gas than that.
- the gas-liquid separator 5 is not particularly limited as long as it is a device capable of separating gas and liquid, and may be, for example, a flash drum or a cyclone gas-liquid separator.
- the liquid heavy fraction separated by the gas-liquid separator 5 is extracted into the heavy component recovery tank 6 through the pipe 19, and the gas component that does not liquefy, that is, the cooling gas, is supplied through the pipe 13 to the catalytic reactor. 3 is sent.
- the liquid heavy fraction does not flow into the catalytic reactor 3, it is not an embodiment in which the entire amount of the cooled fraction is supplied to the catalytic reactor 3. It is different from the manufacturing method. However, when paying attention to the cooling gas that has not been liquefied, since the entire amount is subjected to the catalytic conversion reaction as it is without undergoing a purification treatment, the production method in terms of having no gas purification step. And in common.
- the component composition contained in the liquid heavy fraction and the cooling gas depends on the temperature and pressure of the cooler 2.
- the liquid heavy fraction mainly contains components having a boiling point higher than that of aromatic hydrocarbons and water
- the cooling gas mainly contains ethylene and ethane.
- the temperature of the cooling process In order to remove a part of the cooling fraction as a liquid heavy fraction, it may be necessary to set the temperature of the cooling process to be low to some extent. As a result, the temperature of the cooling gas flowing out from the gas-liquid separator 5 Can be lower than the feed temperature suitable for the subsequent reaction. In this case, it may be necessary to reheat the catalyst reactor 3 before supplying it to the catalyst reactor 3, which is not preferable in terms of heat. However, since the removal of the heavy fraction has an effect of suppressing the coking deterioration of the zeolite-containing catalyst packed in the catalyst reactor 3, the removal of the liquid heavy fraction is preferable in this respect.
- the cooling temperature of the ethane decomposition gas in the cooler 2 at least a part of the water contained in the ethane decomposition gas can be condensed and removed.
- the cooling gas may need to be reheated as described above.
- the removal of the heavy liquid fraction is preferable in terms of producing an effect of suppressing permanent (dealuminum) deterioration of the zeolite-containing catalyst. .
- aromatic hydrocarbons recovered here can produce benzene at a high concentration by dealkylation reaction as in the later-described aromatic hydrocarbons recovered from the gasoline fraction via the pipe 29, and are disproportionated. It is also possible to produce toluene at a high concentration by the reaction.
- various fractions are recycled and reused as raw materials.
- at least a part of unreacted ethylene recovered from the separation device 4 through the pipe 15 is recycled through the pipe 21 and merged with the cooling fraction or the cooling gas in the pipe 13, and then the catalytic reactor 3.
- the gas-liquid separator 5 is installed in the middle of the pipe 13, and the position where the recycled ethylene is combined with the cooling fraction or the cooling gas may be upstream or downstream of the gas-liquid separator 5. None, but downstream is preferred.
- At least a part of the ethane fractionated by the separation device 4 is recycled through the pipe 20, merged with ethane that has not been recycled in the pipe 11, and then supplied to the pyrolysis reactor 1.
- the separation apparatus 4 fractionated into a fraction having 2 or less carbon atoms (hereinafter referred to as “C2-fraction”) and a fraction having 3 or more carbon atoms (hereinafter referred to as “C3 + fraction”).
- C2-fraction fraction having 2 or less carbon atoms
- C3 + fraction fraction having 3 or more carbon atoms
- the remaining fraction is recycled through the pipe 21 as ethane-containing gas.
- a part of the C4 fraction recovered from the separation device 4 via the pipe 17 is also recycled via the pipe 22, merged with the cooling fraction or the cooling gas in the pipe 13, and then supplied to the catalytic reactor 3.
- the gas-liquid separator 5 is installed in the middle of the pipe 13
- the joining position of the recycled C4 fraction and the cooling fraction or the cooling gas is not limited to the upstream or downstream of the gas-liquid separator 5.
- the downstream of the separator 5 is preferred.
- after connecting the downstream end of the piping 22 in the middle of the piping 21 and combining the recycled ethylene and the C4 fraction they may be combined with the cooling fraction or the cooling gas (not shown). .
- a part of the gasoline fraction recovered from the separation device 4 through the pipe 18 is also recycled through the pipe 23, merged with the cooling fraction or the cooling gas in the pipe 13, and then supplied to the catalytic reactor 3.
- the gas-liquid separator 5 is installed in the middle of the pipe 13, and the recycled gasoline fraction is merged with the cooling gas downstream of the gas-liquid separator 5, or is merged with the cooling fraction upstream ( Not shown).
- the separation device 7 in this case is not particularly limited as long as it is a device capable of separating the C5 fraction from other components, and may be, for example, a distillation tower or a gas-liquid separator.
- the recycled C5 fraction is merged with the cooling fraction or the cooling gas in the pipe 13.
- the gas-liquid separator 5 is installed in the middle of the pipe 13, it is preferable to combine the recycled C5 fraction and the cooling fraction or the cooling gas with the cooling gas downstream of the gas-liquid separator 5.
- the recycled C5 fraction may be merged with the cooled fraction upstream of the gas-liquid separator 5 (not shown).
- a gasoline fraction is supplied to the separation device 7 to extract aromatic hydrocarbons, and one of the remaining fractions (raffinate) from which only the aromatic hydrocarbons have flowed out through the pipe 29
- the part may be recycled via the pipe 26.
- the separation device 7 in this case is not particularly limited as long as it can extract aromatic hydrocarbons from a gasoline fraction, and may be, for example, a distillation column.
- the gas-liquid separator 5 is installed in the middle of the pipe 13, and the recycled raffinate is merged with the cooling gas downstream of the gas-liquid separator 5, or is merged with the cooling fraction upstream (not shown).
- the fractions recycled to the catalytic reactor 3 such as the ethylene, C4 fraction, and gasoline fraction are heated in advance to the temperature of the cooling gas that has passed through the cooler 2, or the cooling temperature in the cooler 2 is increased. It is desirable to suitably adjust the temperature of the fraction supplied to the catalyst reactor 3.
- the cooling gas and the recycle fraction may be merged and then reheated with a heater (not shown) and supplied to the catalyst reactor 3.
- the separation device 8 is not particularly limited as long as it can separate isobutene and normal butene, and examples thereof include distillation columns such as a plate column and a packed column.
- methyl methacrylate can be produced by the method described in Japanese Patent No. 4076227. Further, from normal butene, butanol can be produced by a method described in JP-A-2005-225781 or the like, or methyl ethyl ketone or butadiene can be produced by a method described in JP-B 3-2126. Is possible.
- FIG. 3 shows a schematic diagram of an olefin production apparatus (pyrolysis-catalytic conversion reaction apparatus) used in the following Examples.
- the “holding pressure recovery unit” and “recovery unit” in FIG. 3 are provided with a separation device, and the components separated by the separation device are converted into a pyrolysis reactor and a cooler. Pipes were installed so that they could be recycled into fixed bed and fluidized bed reactors.
- the measurement methods performed in the examples are as follows. (1) Measurement of silica / alumina ratio of zeolite 0.2 g of zeolite was added to 50 g of 5N NaOH aqueous solution. This was transferred to a stainless steel micro cylinder with a Teflon (registered trademark) inner tube, and the micro cylinder was sealed. The zeolite was completely dissolved by holding the micro bomb in an oil bath for 15 to 70 hours. The obtained zeolite solution was diluted with ion-exchanged water, the silicon and aluminum concentrations in the diluted solution were measured with a plasma emission spectrometer (ICP apparatus), and the silica / alumina ratio of the zeolite was calculated from the results.
- ICP apparatus plasma emission spectrometer
- the ICP apparatus and measurement conditions were as follows. Equipment: Rigaku Denki Co., Ltd., trade name “JOBIN YVON (JY138 ULTRACE)” Measurement conditions Silicon measurement wavelength: 251.60 nm Aluminum measurement wavelength: 396.152 nm Plasma power: 1.0 kW Nebulizer gas: 0.28 L / min Sheath gas: 0.3 to 0.8 L / min Coolant gas: 13 L / min
- the inside of the cell was depressurized to 0.01 Torr. Subsequently, ammonia gas was supplied into the cell, and the pressure was adjusted to 100 Torr. In this state, the measurement cell was held for 30 minutes, and ammonia was adsorbed on the catalyst. The inside of the cell was again decompressed to remove ammonia that was not adsorbed on the catalyst, and then helium was supplied to the measurement cell as a carrier gas to return the inside of the cell to atmospheric pressure. Thereafter, the pressure in the cell is set to be maintained at 200 Torr, and the temperature is increased to 600 ° C. at a temperature increase rate of 8.33 ° C./min. Ammonia desorbed from the catalyst was detected by a mass spectrometer, and a temperature programmed desorption spectrum was obtained.
- the obtained temperature-programmed desorption spectrum was divided by waveform separation based on Gaussian distribution using waveform analysis software “Wave Analysis” (trade name) manufactured by Nippon Bell Co., Ltd.
- the ammonia desorption amount was calculated based on a separately obtained calibration curve from the total area of waveforms having a peak top at a desorption temperature of 240 ° C. or higher, and converted to the mass of zeolite (unit: ⁇ mol / g-zeolite).
- Example 1 An H-type ZSM-5 zeolite having a silica / alumina ratio of 27 was kneaded with silica sol and extruded to obtain a columnar catalyst having a diameter of 2 mm and a length of 3 to 5 mm.
- the zeolite content in the obtained molded product was 50% by mass.
- the obtained molded product was dried in air at 120 ° C. for 6 hours and then calcined in air at 700 ° C. for 5 hours.
- This calcined columnar catalyst was stirred and ion exchanged in a 1N nitric acid aqueous solution, washed with water, and dried in the atmosphere at 120 ° C. for 5 hours to obtain a zeolite-containing catalyst.
- the amount of TPD acid of this zeolite-containing catalyst was 222 ⁇ mol / g-catalyst. That is, the amount of TPD acid in terms of zeolite mass was 444 ⁇ mol / g-zeolite.
- Example 2 H-type ZSM-5 zeolite having a silica / alumina ratio of 412 was kneaded with silica sol and extruded.
- the zeolite content in the obtained molded product was 50% by mass.
- the obtained molded product was dried at 120 ° C. in the air for 6 hours and then calcined in the air at 700 ° C. for 5 hours to obtain a columnar catalyst having a diameter of 2 mm and a length of 3 to 5 mm.
- the obtained columnar catalyst was stirred and ion exchanged in a 1N nitric acid aqueous solution, washed with water, and dried in the atmosphere at 120 ° C. for 5 hours to obtain a zeolite-containing catalyst.
- the amount of TPD acid of the zeolite-containing catalyst was 43 ⁇ mol / g-catalyst. That is, the amount of TPD acid in terms of the mass of zeolite was 86 ⁇ mol / g-zeolite.
- the thermal decomposition reaction was performed in the same manner as in Example 1. Subsequently, the ethane decomposition gas flowing out from the thermal decomposition reactor was cooled to 397 ° C. with a cooler to obtain a cooled fraction. 12.3 g / hour of the obtained cooling fraction was passed through a 15 mm inner diameter stainless steel fixed bed reactor filled with 8.56 g of the zeolite-containing catalyst and contacted at a reaction temperature of 550 ° C. and a reaction pressure of 0.14 MPaG. A conversion reaction was performed. Table 2 shows the yield of each component in the ethane decomposition gas and the contact gas 18 hours after the start of the reaction.
- Example 3 To 2000 g of silica sol (manufactured by Nalco, silica content 15% by mass), 40 g of nitric acid (manufactured by Wako Pure Chemicals, reagent containing 60% by mass of nitric acid) was added to adjust the pH to 1.1. 100 g of ammonium nitrate (manufactured by Wako Pure Chemicals, special grade reagent) was added thereto, and then 300 g of NH 4 type ZSM-5 zeolite having a silica / alumina ratio of 42 was added to prepare a catalyst raw material slurry. The obtained catalyst raw material slurry was stirred at 25 ° C.
- the spray drying conditions of the catalyst raw material slurry were a spray dryer inlet fluid temperature: 220 ° C. and an outlet fluid temperature: 130 ° C., and the spray drying method was a rotating disk method.
- the obtained dry powder was calcined in the air at 700 ° C. for 5 hours using a muffle furnace to obtain a powdered catalyst.
- the obtained powdery catalyst was ion-exchanged in a 1N-diluted nitric acid aqueous solution at 25 ° C. for 1 hour, washed with water, and dried in air at 120 ° C. for 5 hours to prepare an ion-exchange catalyst.
- This ion exchange catalyst is packed in a stainless steel reactor having an inner diameter of 60 mm ⁇ , and subjected to steam treatment for 24 hours under conditions of a temperature of 650 ° C., 0.1 MPaG, a steam flow rate of 12 g / hour, and a nitrogen flow rate of 22.4 NL / hour.
- the amount of TPD acid in the obtained zeolite-containing catalyst was 17 ⁇ mol / g-catalyst. That is, the amount of TPD acid in terms of mass of zeolite was 34 ⁇ mol / g-zeolite.
- a pyrolysis reaction was performed in the same manner as in Example 1 except that the outlet temperature of the pyrolysis reactor was 855 ° C.
- the ethane decomposition gas flowing out from the thermal decomposition reactor was cooled to 415 ° C. with a cooler to obtain a cooled fraction.
- the obtained cooling fraction water content 27.6% by mass
- 221 g / hour was passed through a stainless steel fluidized bed reactor having an inner diameter of 52.7 mm packed with 212 g of the zeolite-containing catalyst, and the reaction temperature was 550 ° C.
- the catalytic conversion reaction was started at a reaction pressure of 0.14 MPaG.
- Example 4 Except that the cooling fraction 221 g / hour flowing through the fluidized bed reactor was replaced with a mixed gas of 193 g / hour cooling fraction and 21 g / hour of ethylene, and this mixed gas was passed through the fluidized bed reactor at 373 ° C. In the same manner as in No. 3, a contact gas was obtained.
- Example 4 corresponds to the case where 70% of the unreacted ethylene remaining in the contact gas is recycled. Table 4 shows the yield of each component in the mixed gas and the contact gas in the steady state.
- Example 5 The same procedure as in Example 3 was performed until the start of the catalytic conversion reaction.
- the obtained contact gas is cooled to 10 ° C. using a heat exchanger (not shown) at the outlet of the fluidized bed reactor, and then supplied to a gas-liquid separator (not shown) to separate water. It was supplied to a distillation column (not shown) as a separation device. A mixed liquid of the C4 fraction and the gasoline fraction was extracted from the bottom of the column, and 50% of the mixture was recycled to the fluidized bed reactor.
- the supply amount of the cooled fraction after stabilization to the fluidized bed reactor is 190 g / hour
- the supply amount of the recycled C4 / gasoline fraction to the fluidized bed reactor is 25 g / hour
- These mixed gases were reheated before being supplied to the fluidized bed reactor, and the temperature at the inlet of the fluidized bed reactor was 423 ° C.
- Table 4 shows the yield of each component in the mixed gas and the steady state contact gas. From this result, the total yield of C3 to C5 olefins per ethane fed to the pyrolysis reactor is 24.6% by mass in Example 3 of 1 pass, while in Example 4 of recycling. It was 31.8% by mass and 26.2% by mass in Example 5, and it was found that the yield of olefins having 3 or more carbon atoms was increased by recycling.
- Example 6 H-type ZSM-5 zeolite having a silica / alumina ratio of 280 was kneaded with silica sol and extruded. The zeolite content in the obtained molded product was 50% by mass. The obtained molded product was dried at 120 ° C. in the air for 6 hours and then calcined in the air at 700 ° C. for 5 hours to obtain a columnar catalyst having a diameter of 2 mm and a length of 3 to 5 mm. The obtained columnar catalyst was stirred and ion exchanged in a 1N nitric acid aqueous solution, washed with water, and dried in the atmosphere at 120 ° C. for 5 hours to obtain a zeolite-containing catalyst.
- the pyrolysis reaction was performed in the same manner as in Example 1 except that the outlet temperature of the pyrolysis reactor was 810 ° C. Subsequently, the ethane decomposition gas flowing out from the thermal decomposition reactor was cooled to 372 ° C. with a cooler to obtain a cooled fraction. Of the obtained cooling fraction (water content 27.7 mass%), 46.7 g / hour was passed through a stainless steel fixed bed reactor having an inner diameter of 27 mm packed with 30.0 g of the zeolite-containing catalyst, and the reaction temperature was 500. The catalytic conversion reaction was started at 0 ° C. and a reaction pressure of 0.14 MPaG.
- Table 5 shows the yield of each component in the ethane decomposition gas and the contact gas after the reaction was continued for 24 hours. These yields are based on the assumption that ethane (excluding recycled ones) supplied to the pyrolysis reactor is 100% by mass, and that the entire cooling fraction after the pyrolysis reaction is supplied to the fixed bed reactor. And expressed as a percentage by mass. The ethane content in the catalytic reaction gas 24 hours after the start of the reaction was 53.1% by mass on a dry basis.
- the amount of ethane newly supplied to the olefin production apparatus could be reduced.
- Example 7 The zeolite-containing catalyst prepared in Example 1 was charged into a quartz glass reactor having an inner diameter of 20 mm ⁇ , temperature 650 ° C., normal pressure, water vapor flow rate 31.8 g / hour, nitrogen flow rate 2.76 NL / hour, air flow rate 6.72 NL.
- the zeolite-containing catalyst according to Example 7 was obtained by performing steam treatment for 24 hours under the conditions of / hour.
- the amount of TPD acid of the obtained zeolite-containing catalyst was 21 ⁇ mol / g catalyst. That is, the amount of TPD acid in terms of the mass of zeolite was 42 ⁇ mol / g-zeolite.
- a thermal decomposition reaction was carried out in the same manner as in Example 3. Subsequently, when the ethane decomposition gas flowing out from the pyrolysis reactor was cooled to 80 ° C. with a cooler, a condensate was generated. Therefore, a gas-liquid separator (not shown) provided in the middle of the outlet pipe of the cooler was used. The condensate (heavy fraction) was separated and recovered. As a result, a heavy fraction of 15% by mass of the ethane decomposition gas was recovered. 12.0 g / hour of the remaining cooling gas (water content: 15.6% by mass) obtained by separating the heavy fraction from the ethane cracking gas was reheated to 389 ° C.
- the present invention is useful as an industrial production method from the viewpoint of diversity of olefin production raw materials. Since the present invention can stably produce an olefin having 3 or more carbon atoms from ethane by a simple method, it is extremely advantageous for industrial implementation.
- Pipe for recovering heavy fraction from the cooled fraction 20 ... Pipe for recycling ethane 21 ... piping for recycling ethylene, 22 ... C4 Piping for recycling the fraction, 23 ... Piping for recycling the gasoline fraction, 24 ... Piping for collecting the C5 fraction, 25 ... Piping for recycling the C5 fraction, 26 ... Recycling the raffinate Piping, 27 ... pipe for collecting isobutene, 28 ... pipe for collecting normal butene, 29 ... pipe for collecting aromatic hydrocarbons.
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Abstract
Description
例えば特許文献1には、エタンを水蒸気の存在下で熱分解して得られたエチレンから、メタセシス反応を用いてプロピレンを製造する方法が開示されている。
[1]水蒸気の共存下でエタンを熱分解して得られるエタン分解ガスを600℃以下に冷却して冷却留分を得る工程と、前記冷却留分を中間細孔径ゼオライトを含有する触媒と接触させて炭素数3以上のオレフィンを含む接触ガスを得る工程と、を有するオレフィンの製造方法。
[2]水蒸気の共存下でエタンを熱分解して得られるエタン分解ガスを600℃以下に冷却して冷却留分を得る工程と、前記冷却留分を液状の重質留分と冷却ガスとに分離する工程と、前記冷却ガスを中間細孔径ゼオライトを含有する触媒と接触させて炭素数3以上のオレフィンを含む接触ガスを得る工程と、を有するオレフィンの製造方法。
[3]前記重質留分から芳香族炭化水素の一部又は全部を分離して回収する工程を更に有する、上記[2]の製造方法。
[4]前記接触ガスを得る工程において、前記冷却留分又は前記冷却ガスを流動床反応器内で前記触媒と接触させ、前記接触ガスを得る工程を経た前記触媒の一部を前記流動床式反応器から連続的又は断続的に抜き出し、酸素を含むガスに接触させて前記触媒に付着した炭素質化合物の少なくとも一部を燃焼する工程と、前記燃焼する工程を経た前記触媒を前記流動床式反応器に再供給する工程と、を更に有する、上記[1]~[3]のいずれか一つの製造方法。
[5]前記冷却留分を得る工程において、前記エタン分解ガスを300~600℃に冷却する、上記[1]~[4]のいずれか一つの製造方法。
[6]前記接触ガスからエタンを分離する工程と、前記エタンの少なくとも一部を前記エタンを熱分解する際の原料としてリサイクルする工程と、を更に有する、上記[1]~[5]のいずれか一つの製造方法。
[7]前記接触ガスを得る工程において、前記エタン分解ガスに含まれるエチレンから、プロピレン、C4留分及びガソリン留分からなる群より選択される少なくとも一種を生成させる、上記[1]~[6]のいずれか一つの製造方法。
[8]前記少なくとも一種の一部及び/又は前記接触ガスを得る工程を経た未反応のエチレンの少なくとも一部を前記接触ガスを得る工程の原料としてリサイクルする、上記[7]の製造方法。
[9]前記C4留分からイソブテン及び/又はノルマルブテンを分離して回収する工程を更に有する、上記[7]又は[8]の製造方法。
[10]前記ガソリン留分から芳香族炭化水素の一部又は全部を分離して回収する工程を更に有する、上記[7]~[9]のいずれか一つの製造方法。
[11]エタンから炭素数3以上のオレフィンを製造するための製造装置であって、
水蒸気の共存下でエタンを熱分解してエタン分解ガスを得るための第一の反応器に接続され、前記第一の反応器から流出した前記エタン分解ガスを受け入れ冷却して冷却留分を得るための冷却器と、
該冷却器に接続され、かつ、中間細孔径ゼオライトを含有する触媒が充填され、前記冷却器から流出した前記冷却留分を受け入れ前記触媒に接触させるための第二の反応器と、を具備するオレフィンの製造装置。
[12]エタンから炭素数3以上のオレフィンを製造するための装置であって、水蒸気の共存下でエタンを熱分解してエタン分解ガスを得るための第一の反応器に接続され、前記第一の反応器から流出した前記エタン分解ガスを受け入れ冷却して冷却留分を得るための冷却器と、前記冷却器に接続され、前記冷却器から流出した前記冷却留分を液状の重質留分と冷却ガスとに分離するための気液分離器と、前記気液分離器に接続され、かつ、中間細孔径ゼオライトを含有する触媒が充填され、前記気液分離器から流出した前記冷却ガスを受け入れ前記触媒に接触させるための第二の反応器と、を具備するオレフィンの製造装置。
エタン転化率=(熱分解反応器入口の供給流中のエタン濃度-熱分解反応器出口の排出流中のエタン濃度)/熱分解反応器入口の供給流中のエタン濃度×100 (1)
また、エタン分解ガスは、アセチレン、メチルアセチレンなどのアセチレン化合物類、及び、プロパジエン、ブタジエン、ペンタジエン、シクロペンタジエンなどのジオレフィン(ジエン)化合物類を通常含む。
触媒反応器3の形式は、特に制限されず、固定床式反応器、流動床式反応器、移動床式反応器などのいずれの反応器形式も利用できる。
まず、昇温脱離スペクトル測定装置の測定セルにサンプルの触媒を入れ、測定セル内をヘリウムガスで置換し、温度を100℃に保持する。次いで、測定セル内を一旦減圧した後、アンモニアガスを供給して測定セル内の圧力を100Torrとし、その状態で30分間保持し、触媒にアンモニアを吸着させる。測定セル内を再度、減圧して触媒に吸着されていないアンモニアを除去し、ヘリウムによりセル内を大気圧に戻す。その後、測定セルを四重極型質量分析計に接続し、セル内の圧力を200Torrに設定し、セル内を8.33℃/分の昇温速度で600℃まで昇温しながら、触媒から脱離してくるアンモニアを検出して昇温脱離スペクトルを得る。脱離の間のセル内の圧力は約200Torrに保たれるように調整する。
ゼオライト含有触媒に、IB族金属元素からなる群より選ばれる少なくとも1種の金属元素を含有させる方法としては、中間細孔径ゼオライトにIB族金属元素を含有させる方法が挙げられる。より具体的には、IB族金属を含有していない中間細孔径ゼオライト又はゼオライト含有触媒をイオン交換する方法が挙げられ、イオン交換処理は液相法でも固相法でもよい。固相法のイオン交換処理は、IB族金属を含む溶液を、(IB族金属を含有していない)中間細孔径ゼオライト又はゼオライト含有触媒に含浸する方法である。IB族金属を含む溶液の調製には、IB族金属の塩、例えば、硝酸銀、酢酸銀、硫酸銀、塩化銅、硫酸銅、硝酸銅、塩化金を用いることができる。これらの中で好ましくは、硝酸銀、硝酸銅が用いられ、より好ましくは、硝酸銀が用いられる。中間細孔径ゼオライト中のIB族金属の含有量は、中間細孔径ゼオライトの全量に対して0.1~10質量%が好ましく、より好ましくは0.2~5質量%である。IB族金属の含有量はX線蛍光分析法などにより求めることができる。
すなわち、反応温度は、好ましくは400~650℃、より好ましくは450~600℃である。エタン分解ガスの分圧は低いほうが望ましく、通常0.01~1MPa、より好ましくは0.05~0.5MPaである。ゼオライト含有触媒の質量に対するエタン分解ガスの重量時間空間速度WHSVは、0.1~50hr-1、好ましくは0.2~20hr-1の範囲である。
エチレン転化率=(触媒反応器3に供給されるエタン分解ガス中のエチレン濃度-触媒反応器3から流出する接触ガス中のエチレン濃度)/触媒反応器3に供給されるエタン分解ガス中のエチレン濃度×100 (2)
配管16を介して回収されたプロピレンから、特許第3214984号公報等に記載の方法によって、アクリロニトリルやポリプロピレンを製造することができる。
(1)ゼオライトのシリカ/アルミナ比の測定
ゼオライト0.2gを5NのNaOH水溶液50gに加えた。これをテフロン(登録商標)製内管付きのステンレス製マイクロボンベに移し、マイクロボンベを密閉した。オイルバス中でマイクロボンベを15~70時間保持することにより、ゼオライトを完全に溶解した。得られたゼオライトの溶液をイオン交換水で希釈し、希釈液中の珪素、アルミニウム濃度をプラズマ発光分光分析計(ICP装置)にて測定し、その結果からゼオライトのシリカ/アルミナ比を算出した。
ICP装置及び測定条件は下記のとおりであった。
装置:理学電気社製、商品名「JOBIN YVON(JY138 ULTRACE)」
測定条件
珪素測定波長 : 251.60nm
アルミニウム測定波長: 396.152nm
プラズマパワー : 1.0kw
ネブライザーガス : 0.28L/分
シースガス : 0.3~0.8L/分
クーラントガス : 13L/分
日本ベル株式会社製の全自動昇温脱離スペクトル装置「TPD-1-ATw」(商品名)を用い、付属のマニュアルに準じて下記の方法にて触媒のTPD酸量を測定した。
まず、専用ガラス製セルに触媒試料100mgを充填した。この際、触媒試料が成形体の場合には粉末状にして充填した。次いで、キャリアガスとしてヘリウムを50cc/分でセルに供給しながら、前処理として500℃まで昇温して1時間加熱処理を施した後、100℃に温度設定した。温度が100℃で安定した後、セル内を0.01Torrまで減圧した。続いて、セル内にアンモニアガスを供給し、圧力を100Torrに調整した。その状態で測定セルを30分間保持し、触媒にアンモニアを吸着させた。セル内を再度減圧して、触媒に吸着されていないアンモニアを除去した後、次いで、測定セルにキャリアガスとしてヘリウムを供給し、セル内を大気圧に戻した。しかる後、セル内の圧力が200Torrに保たれるように設定し、8.33℃/分の昇温速度で600℃まで昇温しながら、セルと接続されたアネルバ株式会社製の四重極型質量分析計で触媒から脱離してくるアンモニアを検出し、昇温脱離スペクトルを得た。
波形分離解析の結果、240℃以上の脱離温度でピークトップを有する波形の面積の総和から、別途求めた検量線に基づいてアンモニア脱離量を求め、ゼオライトの質量当たりに換算した(単位はμmol/g-ゼオライト)。
エタン分解ガス(冷却留分)を冷却器の出口から、あるいは接触ガスを固定床又は流動床反応器の出口から、図3中の「分析ユニット」に備えられる直接ガスクロマトグラフィー(検出器:TCD、FID)に導入して組成を分析した。なお、ガスクロマトグラフィーによる分析は以下の条件で行った。
(ガスクロマトグラフィー分析条件)
装置 : 島津製作所社製、商品名「GC-17A」
カラム: 米国SUPELCO社製カスタムキャピラリーカラム、商品名「SPB-1」、内径 0.25mm、長さ 60m、フィルム厚 3.0μm
サンプルガス量: 1mL(サンプリングラインは200~300℃に保温)
昇温プログラム: 40℃で12分間保持し、次いで5℃/分で200℃まで昇温した後、200℃で22分間保持する。
スプリット比: 200:1
キャリアガス(窒素)流量: 120mL/分
FID検出器: エアー供給圧50kPa(約500mL/分)、水素供給圧60kPa(約50mL/分)
測定方法: TCD検出器とFID検出器とを直列に連結して、水素及び炭素数1及び2の炭化水素をTCD検出器で検出し、炭素数3以上の炭化水素をFID検出器で検出した。分析開始10分後に、検出の出力をTCDからFIDに切り替えた。
シリカ/アルミナ比が27であるH型のZSM-5ゼオライトをシリカゾルと混練、押出成形し、直径2mm、長さ3~5mmの柱状触媒を得た。得られた成形物におけるゼオライトの含有量は50質量%であった。得られた成形物を大気中、120℃で6時間乾燥した後、大気中、700℃で5時間焼成した。この焼成処理した柱状触媒を1N-硝酸水溶液中で攪拌しイオン交換した後、水洗し、大気中、120℃で5時間乾燥し、ゼオライト含有触媒を得た。このゼオライト含有触媒のTPD酸量は、222μmol/g-触媒であった。すなわち、ゼオライトの質量換算でTPD酸量は444μmol/g-ゼオライトであった。
シリカ/アルミナ比が412であるH型のZSM-5ゼオライトをシリカゾルと混練し、押出成形した。得られた成形物におけるゼオライトの含有量は50質量%であった。得られた成形物を大気中、120℃で6時間乾燥した後、大気中、700℃で5時間焼成し、直径2mm、長さ3~5mmの柱状触媒を得た。得られた柱状触媒を1N-硝酸水溶液中で攪拌しイオン交換した後、水洗し、大気中、120℃で5時間乾燥し、ゼオライト含有触媒を得た。このゼオライト含有触媒のTPD酸量は、43μmol/g-触媒であった。すなわち、ゼオライトの質量換算でTPD酸量は86μmol/g-ゼオライトであった。
シリカゾル(Nalco社製、シリカ含有率15質量%)2000gに硝酸(和光純薬製、硝酸60質量%含有試薬)40gを加えpHを1.1に調整した。そこに硝酸アンモニウム(和光純薬製、特級試薬)100gを添加し、次いでシリカ/アルミナ比が42であるNH4型のZSM-5ゼオライト300gを添加して触媒原料スラリーを調製した。得られた触媒原料スラリーを25℃で3時間撹拌した後、噴霧乾燥機で噴霧乾燥して乾燥粉末を得た。触媒原料スラリーの噴霧乾燥条件は、噴霧乾燥機入口流体温度:220℃、出口流体温度:130℃であり、噴霧乾燥の方式は回転円盤方式であった。得られた乾燥粉末をマッフル炉を用いて700℃で5時間、空気下で焼成し粉末状触媒を得た。
得られた粉末状触媒を1N-希硝酸水溶液中、25℃で1時間イオン交換した後、水洗し、大気中、120℃で5時間乾燥し、イオン交換触媒を調製した。このイオン交換触媒を内径60mmφのステンレス製反応器に充填し、温度650℃、0.1MPaG、水蒸気流量12g/時間、窒素流量22.4NL/時間の条件で24時間水蒸気処理を行い、ゼオライト含有触媒を得た。得られたゼオライト含有触媒のTPD酸量は、17μmol/g-触媒であった。すなわち、ゼオライトの質量換算でTPD酸量は34μmol/g-ゼオライトであった。
エタン分解ガス及び定常状態における接触ガスにおける各成分の収率を表3に示す。
流動床反応器に流通する冷却留分221g/時間を冷却留分193g/時間とエチレン21g/時間との混合ガスに代え、この混合ガスを373℃で流動床反応器に流通した以外は実施例3と同様にして接触ガスを得た。この実施例4は、接触ガス中に残存する未反応エチレンの70%をリサイクルした場合に相当する。
上記混合ガス及び定常状態における接触ガスにおける各成分の収率を表4に示す。
接触転化反応の開始まで実施例3と同様にした。得られた接触ガスを流動床反応器の出口で熱交換器(図示せず)を用いて10℃まで冷却した後、気液分離器(図示せず)に供給し、水を分離してから分離装置である蒸留塔(図示せず)に供給した。塔底からC4留分とガソリン留分との混合液を抜き出し、その50%を流動床反応器にリサイクルした。接触転化反応の条件について、安定後の冷却留分の流動床反応器への供給量は190g/時間、リサイクルしたC4/ガソリン留分の流動床反応器への供給量は25g/時間であり、これらの混合ガスを流動床反応器に供給する前に再加熱し、流動床反応器入口での温度は423℃だった。
上記混合ガス及び定常状態の接触ガスにおける各成分の収率を表4に示す。
この結果から、熱分解反応器に供給されるエタン当たりのC3~C5オレフィンの合計収率は、1パスの実施例3で24.6質量%であるのに対して、リサイクルの実施例4で31.8質量%、実施例5で26.2質量%であり、リサイクルによって炭素数3以上のオレフィン収率が高まっていることがわかった。
シリカ/アルミナ比が280であるH型のZSM-5ゼオライトをシリカゾルと混練し、押出成形した。得られた成形物におけるゼオライトの含有量は50質量%であった。得られた成形物を大気中、120℃で6時間乾燥した後、大気中、700℃で5時間焼成し、直径2mm、長さ3~5mmの柱状触媒を得た。得られた柱状触媒を1N-硝酸水溶液中で攪拌しイオン交換した後、水洗し、大気中、120℃で5時間乾燥し、ゼオライト含有触媒を得た。
得られた冷却留分(含水率27.7質量%)のうち46.7g/時間を、上記ゼオライト含有触媒30.0gを充填した内径27mmのステンレス製固定床反応器に流通し、反応温度500℃、反応圧力0.14MPaGで接触転化反応を開始した。
反応を24時間継続した後のエタン分解ガス及び接触ガスにおける各成分の収率を表5に示す。なお、これらの収率は熱分解反応器に供給するエタン(リサイクルしたものを除く。)を100質量%とし、熱分解反応後の冷却留分の全量が固定床反応器に供給されたと仮定して、質量百分率で示される。
反応開始から24時間後の触媒反応ガス中のエタン含有量はドライベースで53.1質量%であった。炭素数3以上のオレフィンを含む接触ガスからエタンを分離して回収し、少なくとも一部を熱分解反応器へリサイクルすることで、オレフィンの製造装置に新たに供給するエタン量を削減できた。
実施例1で調製したゼオライト含有触媒を内径20mmφの石英ガラス製反応器に充填し、温度650℃、常圧、水蒸気流量31.8g/時間、窒素流量2.76NL/時間、空気流量6.72NL/時間の条件で24時間水蒸気処理を行い、実施例7に係るゼオライト含有触媒を得た。得られたゼオライト含有触媒のTPD酸量は、21μmol/g触媒であった。すなわち、ゼオライトの質量換算でTPD酸量は42μmol/g-ゼオライトであった。
エタン分解ガスから重質留分を分離した残りの冷却ガス(含水率:15.6質量%)のうち12.0g/時間を389℃まで加熱器(図示せず)により再加熱した後、上記ゼオライト含有触媒8.56gを充填した内径15mmのステンレス製固定床反応器に流通し、反応温度550℃、反応圧力0.12MPaGで接触転化反応を行った。冷却ガス及び反応開始13時間後の接触ガスにおける各成分の収率を表6に示す。なお、これらの収率は熱分解反応器に供給するエタンを100質量%とし、冷却ガスの全量が固定床反応器に供給されたと仮定して、質量百分率で示される。
Claims (12)
- 水蒸気の共存下でエタンを熱分解して得られるエタン分解ガスを600℃以下に冷却して冷却留分を得る工程と、前記冷却留分を中間細孔径ゼオライトを含有する触媒と接触させて炭素数3以上のオレフィンを含む接触ガスを得る工程と、を有するオレフィンの製造方法。
- 水蒸気の共存下でエタンを熱分解して得られるエタン分解ガスを600℃以下に冷却して冷却留分を得る工程と、前記冷却留分を液状の重質留分と冷却ガスとに分離する工程と、前記冷却ガスを中間細孔径ゼオライトを含有する触媒と接触させて炭素数3以上のオレフィンを含む接触ガスを得る工程と、を有するオレフィンの製造方法。
- 前記重質留分から芳香族炭化水素の一部又は全部を分離して回収する工程を更に有する、請求項2に記載の製造方法。
- 前記接触ガスを得る工程において、前記冷却留分又は前記冷却ガスを流動床反応器内で前記触媒と接触させ、
前記接触ガスを得る工程を経た前記触媒の一部を前記流動床式反応器から連続的又は断続的に抜き出し、酸素を含むガスに接触させて前記触媒に付着した炭素質化合物の少なくとも一部を燃焼する工程と、
前記燃焼する工程を経た前記触媒を前記流動床式反応器に再供給する工程と、
を更に有する、請求項1~3のいずれか一項に記載の製造方法。 - 前記冷却留分を得る工程において、前記エタン分解ガスを300~600℃に冷却する、請求項1~4のいずれか一項に記載の製造方法。
- 前記接触ガスからエタンを分離する工程と、前記エタンの少なくとも一部を前記エタンを熱分解する際の原料としてリサイクルする工程と、を更に有する、請求項1~5のいずれか一項に記載の製造方法。
- 前記接触ガスを得る工程において、前記エタン分解ガスに含まれるエチレンから、プロピレン、C4留分及びガソリン留分からなる群より選択される少なくとも一種を生成させる、請求項1~6のいずれか一項に記載の製造方法。
- 前記少なくとも一種の一部及び/又は前記接触ガスを得る工程を経た未反応のエチレンの少なくとも一部を前記接触ガスを得る工程の原料としてリサイクルする、請求項7に記載の製造方法。
- 前記C4留分からイソブテン及び/又はノルマルブテンを分離して回収する工程を更に有する、請求項7又は8に記載の製造方法。
- 前記ガソリン留分から芳香族炭化水素の一部又は全部を分離して回収する工程を更に有する、請求項7~9のいずれか一項に記載の製造方法。
- エタンから炭素数3以上のオレフィンを製造するための装置であって、
水蒸気の共存下でエタンを熱分解してエタン分解ガスを得るための第一の反応器に接続され、前記第一の反応器から流出した前記エタン分解ガスを受け入れ冷却して冷却留分を得るための冷却器と、
該冷却器に接続され、かつ、中間細孔径ゼオライトを含有する触媒が充填され、前記冷却器から流出した前記冷却留分を受け入れ前記触媒に接触させるための第二の反応器と、
を具備するオレフィンの製造装置。 - エタンから炭素数3以上のオレフィンを製造するための装置であって、
水蒸気の共存下でエタンを熱分解してエタン分解ガスを得るための第一の反応器に接続され、前記第一の反応器から流出した前記エタン分解ガスを受け入れ冷却して冷却留分を得るための冷却器と、
前記冷却器に接続され、前記冷却器から流出した前記冷却留分を液状の重質留分と冷却ガスとに分離するための気液分離器と、
前記気液分離器に接続され、かつ、中間細孔径ゼオライトを含有する触媒が充填され、前記気液分離器から流出した前記冷却ガスを受け入れ前記触媒に接触させるための第二の反応器と、
を具備するオレフィンの製造装置。
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