WO2009113613A1 - 炭化水素化合物の合成反応システム、及び粉化粒子の除去方法 - Google Patents
炭化水素化合物の合成反応システム、及び粉化粒子の除去方法 Download PDFInfo
- Publication number
- WO2009113613A1 WO2009113613A1 PCT/JP2009/054759 JP2009054759W WO2009113613A1 WO 2009113613 A1 WO2009113613 A1 WO 2009113613A1 JP 2009054759 W JP2009054759 W JP 2009054759W WO 2009113613 A1 WO2009113613 A1 WO 2009113613A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- filter
- hydrocarbon compound
- gas
- liquid
- synthesis reaction
- Prior art date
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/10—Filter screens essentially made of metal
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
-
- 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
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
-
- 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
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/34—Apparatus, reactors
- C10G2/342—Apparatus, reactors with moving solid catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/06—Filter cloth, e.g. knitted, woven non-woven; self-supported material
- B01D2239/065—More than one layer present in the filtering material
- B01D2239/0668—The layers being joined by heat or melt-bonding
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00004—Scale aspects
- B01J2219/00006—Large-scale industrial plants
Definitions
- the present invention relates to a hydrocarbon compound synthesis reaction in which a synthesis gas mainly composed of carbon monoxide gas and hydrogen gas is blown into a slurry in which solid catalyst particles are suspended in liquid hydrocarbon to synthesize a hydrocarbon compound.
- the present invention relates to a system and a method for removing pulverized particles that removes catalyst particles (pulverized particles) contained in a hydrocarbon compound in a pulverized state.
- FT synthesis reaction a hydrocarbon compound synthesized by a Fischer-Tropsch synthesis reaction
- a synthesis gas mainly composed of carbon monoxide gas (CO) and hydrogen gas (H 2 )
- a synthesis gas is blown into a slurry in which solid catalyst particles are suspended in a liquid hydrocarbon to perform an FT synthesis reaction.
- the hydrocarbon compound synthesized by the FT synthesis reaction is used as a raw material for liquid fuel products such as naphtha (crude gasoline), kerosene, and light oil.
- the bubble column type slurry bed FT reaction system includes, for example, a reactor main body that contains slurry, a gas supply unit that blows synthesis gas into the bottom of the reactor main body, and a hydrocarbon synthesized in the reactor main body.
- a so-called external circulation type equipped with an external circulation section for allowing a slurry containing a compound to flow out of the reactor main body and for allowing the slurry to flow again into the reactor main body through a separator for separating the hydrocarbon compound from the slurry.
- the particle size of the catalyst particles contained in the slurry is gradually reduced due to friction with the same catalyst particles, friction with the inner wall of the reactor body, thermal damage due to the FT synthesis reaction, etc. Powdered little by little.
- the pulverized catalyst particles (hereinafter referred to as pulverized particles) are clearly smaller than the normal catalyst particles that are not pulverized, together with the separated hydrocarbon compound without being captured in the separator,
- the liquid fuel product may flow into a process (upgrading process).
- upgrading process When the powdered particles flow into the manufacturing process of the liquid fuel product, there is a risk of deteriorating the catalyst used in the process or reducing the quality of the liquid fuel product.
- the present invention has been made in view of such problems, and in a synthesis reaction system for performing an FT synthesis reaction, the powdered particles are prevented from flowing into the production process of the liquid fuel product, It aims at providing the removal method of the suitable powdered particle which prevents a quality fall.
- the synthesis reaction system of the present invention includes a reactor for synthesizing a hydrocarbon compound by a chemical reaction between a synthesis gas mainly composed of hydrogen and carbon monoxide and a slurry in which solid catalyst particles are suspended in a liquid.
- a separator for separating the hydrocarbon compound from the slurry; and a filter for filtering the hydrocarbon compound taken out from the separator and capturing powdered catalyst particles.
- the pulverized particles are removed from the hydrocarbon compound by capturing the pulverized particles in the filter. Therefore, it is possible to suppress mixing of pulverized particles into the hydrocarbon compound used in the manufacturing process of the liquid fuel product, and it is possible to prevent the quality of the liquid fuel product from being deteriorated. Further, since the catalyst used in the manufacturing process of the liquid fuel product does not deteriorate based on the pulverized particles, the maintenance of the apparatus for manufacturing the liquid fuel product can be easily performed, and the apparatus is long. It can be operated continuously for a stable time.
- the amount of catalyst particles and pulverized particles contained in the hydrocarbon compound separated in the separator is affected by the flow rate of the slurry circulating between the reactor and the separator. Therefore, in the filter, the hydrocarbon compound can be filtered without being affected by the slurry flow rate described above.
- a plurality of the filters are provided, and the separators and the respective filters are individually connected by supply lines for supplying the hydrocarbon compounds from the separators to the respective filters. May be.
- the hydrocarbon compound taken out from the separator can be divided and supplied to a plurality of filter units, so that the hydrocarbon compound taken out from the separator contains a large amount of powdered particles. Even if it is, it can be sufficiently removed.
- each supply line is opened and closed by the valve so that one filter filters the hydrocarbon compound and another filter does not filter the hydrocarbon compound. While filtering the hydrocarbon compound in one filter, it becomes possible to wash other filters not used for the filtration. Then, the hydrocarbon compound can be continuously filtered by exchanging the filter for filtering the hydrocarbon compound by switching the opening and closing of the supply pipe line by the valve.
- the synthesis reaction system may include a differential pressure gauge that measures a differential pressure between the upstream side and the downstream side of the filter in the process in which the hydrocarbon compound is filtered by the filter.
- a differential pressure gauge that measures a differential pressure between the upstream side and the downstream side of the filter in the process in which the hydrocarbon compound is filtered by the filter.
- the filter includes a filtration container connected to the supply pipe, and a filter that is disposed in the filtration container and filters the hydrocarbon compound.
- a discharge conduit for discharging the filtered hydrocarbon compound to the outside of the filtration container may be connected.
- the hydrocarbon compound can be filtered by passing through the filter so that the hydrocarbon compound is directed from the inside of the filtration container toward the discharge pipe side.
- the cleaning means is connected to the discharge conduit and includes a cleaning fluid supply section that supplies a cleaning fluid to the filter via the discharge conduit, the cleaning fluid is supplied from the discharge conduit side. It can pass through the filter so as to face the inside of the filtration container. That is, since the cleaning fluid flows in the direction opposite to the direction in which the hydrocarbon compound passes in the filter, the powdered particles can be reliably removed from the filter. Moreover, it can prevent that a chemical reaction arises between a hydrocarbon compound and powdered particle
- the filter is composed of a wire mesh sintered filter obtained by stacking and sintering a plurality of wire meshes, and the diameter of the holes formed in the wire mesh sintered filter is determined by averaging the powdered particles. It is preferable that the particle size is equal to or smaller than the particle size, or larger than 0 ⁇ m and equal to or smaller than 10 ⁇ m. By setting the diameter of the hole in this way, the powdered particles can be reliably captured in the filter.
- the wire mesh sintered filter is constructed by sintering, when the hydrocarbon compound or the cleaning fluid passes through the filter, it can sufficiently withstand even if the pressure applied to the filter is large. The filter can be used for a long time.
- the pulverized particles may be captured by the filter.
- powdered particles having a particle size larger than the pore size of the filter can be directly captured by the filter, and as a result, a particle layer made of powdered particles is formed on the surface of the filter.
- the substantial pore size by the particle layer is sufficiently smaller than the average particle size of the powdered particles, even if the particle size is smaller than the pore size of the filter, it is ensured in the particle layer. Can be captured.
- the method for removing pulverized particles according to the present invention comprises carbonization synthesized by a chemical reaction between a synthesis gas mainly composed of hydrogen and carbon monoxide and a slurry in which solid catalyst particles are suspended in a liquid.
- a method for removing pulverized catalyst particles which is carried out after removing a hydrogen compound from the slurry, wherein the catalyst is pulverized by passing the hydrocarbon compound in one direction of a filter provided in a filter.
- the mixture reaction of the pulverized particles into the hydrocarbon compound used in the manufacturing process of the liquid fuel product is suppressed similarly to the above-described synthesis reaction system, It is possible to prevent quality deterioration of the liquid fuel product. Moreover, since the powdered particles can be surely removed from the filter by performing the washing step, the same filter can be used repeatedly for filtering hydrocarbon compounds.
- a plurality of the filters are arranged in parallel to the hydrocarbon compound to be passed therethrough, and when the filtering step is performed in one filter, another filter is used.
- the cleaning step is simultaneously performed on one filter when the cleaning step is simultaneously performed and the filtering step is performed on the other filter.
- the hydrocarbon compound can be continuously filtered by simultaneously performing the filtration step and the washing step on the plurality of filters.
- the differential pressure between the upstream side and the downstream side of the filter is measured in the process in which the hydrocarbon compound is filtered by the filter, and the measurement result of the differential pressure is When it becomes more than a predetermined threshold, it is good to switch the process implemented in the filter from the filtration process to the washing process.
- the measured differential pressure increases as the amount of powdered particles captured by the filter increases. Therefore, when the differential pressure exceeds a predetermined threshold value, the filter is subjected to a cleaning process, so that the filter cleaning time can be accurately grasped, and the filtration performance (efficiency) of the hydrocarbon compound in the filter can be improved. It is possible to efficiently suppress the decrease.
- the threshold is set to be greater than 0 kPa and not greater than 150 kPa. That is, when the differential pressure becomes equal to or higher than the threshold value, the filtration process by the corresponding filter is stopped, so that the hydrocarbon compound can be prevented from being vaporized and the hydrocarbon compound can be prevented from being reduced.
- the pulverized particles contained in the hydrocarbon compound separated from the separator can be removed, it is possible to suppress mixing of the pulverized particles into the hydrocarbon compound used in the manufacturing process of the liquid fuel product. It is possible to prevent the quality deterioration of the liquid fuel product.
- FIG. 1 is a schematic diagram showing the overall configuration of a liquid fuel synthesizing system according to an embodiment of the present invention.
- FIG. 2 is a schematic view showing a filtration unit constituting the liquid fuel synthesizing system shown in FIG.
- FIG. 3 is a schematic view showing a filter constituting the filtration unit shown in FIG.
- Liquid fuel synthesis system (hydrocarbon synthesis reaction system) 30 ... Bubble column reactor (Bubble column type hydrocarbon synthesis reactor) 36 ... Separator 91 ... Filter 92 ... Supply line 93 ... Discharge line 95 ... Valve 98 ... Differential pressure gauge 100 ... Cleaning means 101 ... Gas supply part (cleaning fluid supply part) 911 ... Filtration container 912 ... Filter
- a liquid fuel synthesis system (hydrocarbon synthesis reaction system) 1 is a plant facility that executes a GTL process for converting a hydrocarbon raw material such as natural gas into liquid fuel.
- the liquid fuel synthesis system 1 includes a synthesis gas generation unit 3, an FT synthesis unit 5, and a product purification unit 7.
- the synthesis gas generation unit 3 reforms natural gas that is a hydrocarbon raw material to generate synthesis gas containing carbon monoxide gas and hydrogen gas.
- the FT synthesis unit 5 generates liquid hydrocarbons from the generated synthesis gas by a Fischer-Tropsch synthesis reaction (hereinafter referred to as “FT synthesis reaction”).
- the product refining unit 7 produces liquid fuel products (naphtha, kerosene, light oil, wax, etc.) by hydrogenating and refining the liquid hydrocarbons produced by the FT synthesis reaction.
- liquid fuel products nophtha, kerosene, light oil, wax, etc.
- the synthesis gas generation unit 3 mainly includes, for example, a desulfurization reactor 10, a reformer 12, an exhaust heat boiler 14, gas-liquid separators 16 and 18, a decarboxylation device 20, and a hydrogen separation device 26.
- the desulfurization reactor 10 is composed of a hydrodesulfurization device or the like, and removes sulfur components from natural gas as a raw material.
- the reformer 12 reforms the natural gas supplied from the desulfurization reactor 10 to generate a synthesis gas containing carbon monoxide gas (CO) and hydrogen gas (H 2 ) as main components.
- the exhaust heat boiler 14 recovers the exhaust heat of the synthesis gas generated in the reformer 12 and generates high-pressure steam.
- the gas-liquid separator 16 separates water heated by heat exchange with the synthesis gas in the exhaust heat boiler 14 into a gas (high-pressure steam) and a liquid.
- the gas-liquid separator 18 removes the condensate from the synthesis gas cooled by the exhaust heat boiler 14 and supplies the gas to the decarboxylation device 20.
- the decarboxylation device 20 uses an absorption liquid from the synthesis gas supplied from the gas-liquid separator 18 to remove the carbon dioxide gas, and regenerates the carbon dioxide gas from the absorption liquid containing the carbon dioxide gas for regeneration.
- Tower 24 The hydrogen separation device 26 separates a part of the hydrogen gas contained in the synthesis gas from the synthesis gas from which the carbon dioxide gas has been separated by the decarbonation device 20.
- the decarboxylation device 20 may not be provided depending on circumstances.
- the reformer 12 reforms natural gas using carbon dioxide and steam by, for example, the steam / carbon dioxide reforming method represented by the following chemical reaction formulas (1) and (2).
- a high-temperature synthesis gas mainly composed of carbon monoxide gas and hydrogen gas is generated.
- the reforming method in the reformer 12 is not limited to the steam / carbon dioxide reforming method described above, but includes, for example, a steam reforming method, a partial oxidation reforming method (POX) using oxygen, and a partial oxidation method.
- An autothermal reforming method (ATR), a carbon dioxide gas reforming method, or the like, which is a combination of the reforming method and the steam reforming method, can also be used.
- the hydrogen separator 26 is provided on a branch line branched from a main pipe connecting the decarbonator 20 or the gas-liquid separator 18 and the bubble column reactor 30.
- the hydrogen separator 26 can be constituted by, for example, a hydrogen PSA (Pressure Swing Adsorption) device that performs adsorption and desorption of hydrogen using a pressure difference.
- This hydrogen PSA apparatus has an adsorbent (zeolite adsorbent, activated carbon, alumina, silica gel, etc.) in a plurality of adsorption towers (not shown) arranged in parallel, and hydrogen is added to each adsorption tower.
- adsorbent zeolite adsorbent, activated carbon, alumina, silica gel, etc.
- the hydrogen gas separation method in the hydrogen separator 26 is not limited to the pressure fluctuation adsorption method such as the hydrogen PSA device described above, and for example, a hydrogen storage alloy adsorption method, a membrane separation method, or a combination thereof. There may be.
- the FT synthesis unit 5 mainly includes, for example, a bubble column reactor 30, a gas-liquid separator 34, a separator 36, a gas-liquid separator 38, a first rectifying column 40, and a filtration unit 90.
- the bubble column reactor 30 is an example of a reactor that synthesizes synthesis gas into liquid hydrocarbons, and functions as a reactor for FT synthesis that synthesizes liquid hydrocarbons from synthesis gas by an FT synthesis reaction.
- the bubble column reactor 30 mainly includes a reactor main body 80 and a cooling pipe 81.
- the reactor main body 80 is a substantially cylindrical metal container in which a slurry in which solid catalyst particles are suspended in liquid hydrocarbon (the product of the FT synthesis reaction) is accommodated. Yes.
- synthesis gas mainly containing hydrogen and carbon monoxide is injected into the slurry.
- the synthesis gas blown into the slurry becomes bubbles and flows from the lower side in the height direction (vertical direction) of the reactor main body 80 toward the upper side in the slurry.
- the synthesis gas is dissolved in the liquid hydrocarbon, and a liquid hydrocarbon synthesis reaction (FT synthesis reaction) is performed by a contact reaction in contact with the catalyst particles.
- FT synthesis reaction a liquid hydrocarbon synthesis reaction
- hydrogen gas and carbon monoxide gas cause a synthesis reaction.
- n is a positive integer.
- the cooling pipe 81 is provided inside the reactor main body 80 and cools the slurry whose temperature has been raised by heat generated by the FT synthesis reaction.
- the cooling pipe 81 may be formed by bending a single pipe and reciprocating up and down a plurality of times along the vertical direction.
- a plurality of cooling pipes having a double pipe structure called a bayonet type may be arranged inside the reactor main body 80. That is, the shape and the number of the cooling pipes 81 are not limited to the above shape and the number, and any cooling tube 81 may be used as long as it can be arranged uniformly in the reactor main body 80 and contribute to cooling the slurry evenly.
- cooling pipe 81 cooling water supplied from the gas-liquid separator 34 (for example, water having a difference from the temperature in the reactor main body 80 of about ⁇ 50 to 0 ° C.) flows.
- the slurry in reactor body 80 is cooled by exchanging heat between the slurry and the pipe wall of cooling pipe 81.
- a part of the cooling water is converted into water vapor, discharged to the gas-liquid separator 34, and recovered as intermediate pressure steam.
- the medium for cooling the slurry is not limited to the cooling water as described above, and examples thereof include C 4 to C 10 linear and branched paraffins, naphthenes, olefins, low molecular weight silanes, silyl ethers, Silicon oil or the like can be used.
- the gas-liquid separator 34 separates water heated through circulation in the cooling pipe 81 disposed in the bubble column reactor 30 into water vapor (medium pressure steam) and liquid, and the liquid is cooling water. Is supplied to the cooling pipe 81 again.
- the separator 36 is connected to the upper and lower parts of the bubble column reactor 30 and separates the slurry flowing out from the upper part into a liquid hydrocarbon and a slurry containing a large amount of catalyst particles. Then, the slurry containing a large amount of catalyst particles is returned into the bubble column reactor 30 from the lower part of the separator 36.
- the gas-liquid separator 38 is connected to an unreacted gas outlet 806 of the bubble column reactor 30 and cools unreacted synthesis gas and gaseous hydrocarbons.
- the first rectifying column 40 distills the liquid hydrocarbons supplied from the bubble column reactor 30 through the separator 36 and the gas-liquid separator 38, and separates and purifies each fraction according to the boiling point.
- the filtration unit 90 filters the liquid hydrocarbons flowing out from the separator 36 and captures the pulverized particles contained therein.
- the filtration unit 90 includes a plurality of filters 91 (4 in the illustrated example). One).
- the pulverized particles are particles obtained by pulverizing the catalyst particles by friction between the catalyst particles or the inner wall of the reactor main body 80, thermal damage due to the FT synthesis reaction, or the like.
- the separator 36 and the plurality of filters 91 are individually connected by a supply pipe 92 that exits from the separator 36 and branches in the middle, and liquid hydrocarbons from the separator 36 pass through the supply pipe 92. It can be introduced into each filter 91 via the above.
- the plurality of filters 91 and the first rectifying tower 40 are connected to each other by a discharge pipe 93 that is gathered on the way from each filter 91 side, and the liquid hydrocarbons filtered in each filter 91 are connected to each other. It can be transferred to the first rectification column 40.
- a supply-side main valve 94 that opens and closes the supply pipe 92 at the position is provided at a position before branching of the supply pipe 92 located on the separator 36 side, and is further provided on each filter 91 side.
- Each branch part of the supply pipe line 92 is provided with a valve 95 for opening and closing the part.
- a valve 96 that opens and closes at the position before the aggregation of the discharge pipe 93 positioned on each filter 91 side is provided, and further, a discharge pipe positioned on the first rectifying tower 40 side.
- a discharge-side main stopper valve 97 is provided at the post-aggregation position 93.
- the filtration unit 90 also includes a differential pressure gauge 98 that measures the differential pressure between the upstream side and the downstream side of the filter 91 in the process in which the hydrocarbon compound is filtered by the filter 91. Specifically, the pressure of the liquid hydrocarbon before flowing into the filter 91 is measured at a position before the supply pipe line 92 branches, and the pressure of the liquid hydrocarbon after being discharged from the filter 91 is discharged. It is measured at a position after the pipes 93 are collected. In this differential pressure gauge 98, the resistance of the filter 91 against the flow of liquid hydrocarbons passing through the filter 91 can be measured. The magnitude of this resistance increases as the amount of powdered particles captured in the filter 91 increases.
- each filter 91 mainly includes a filtration container 911 and a plurality of filters 912.
- the filtration container 911 is connected to the supply pipe line 92 so as to introduce liquid hydrocarbons from the separator 36 into the inside.
- Each filter 912 is disposed inside the filtration container 911 and plays a role of capturing powdered particles by filtering the liquid hydrocarbons in the filtration container 911 through the filter 911.
- a discharge pipe 93 is connected to the filter 912, and the liquid hydrocarbon filtered in the filter 912 can be discharged directly to the outside of the filtration container 911.
- the filter 912 is constituted by, for example, a wire mesh sintered filter.
- a wire mesh sintered filter is obtained by stacking a plurality of wire meshes and performing high-temperature sintering in a vacuum.
- the size of the hole formed in the wire mesh sintered filter is adjusted according to the size of the mesh and the number of laminated layers. can do.
- the diameter of the hole formed in the wire mesh sintered filter may be a size that allows liquid hydrocarbons to pass but does not allow the pulverized particles to pass through the filter 912, and is introduced into the filter 91. What is necessary is just to change according to the flow volume of liquid hydrocarbon, and the magnitude
- the filter 912 having a pore diameter of 10 ⁇ m may be sufficiently filtered. It can. That is, the diameter of a specific hole formed in the filter 912 may be set to be larger than 0 ⁇ m and 10 ⁇ m or less. However, the smaller the hole diameter of the filter 912, the smaller the particle diameter of the powdered particles that can pass through the filter 912. Therefore, the diameter of the hole is more preferably set to be greater than 0 ⁇ m and 5 ⁇ m or less.
- the particle size of the pulverized particles contained in the liquid hydrocarbon that has passed through the filter 912 is 8 ⁇ m or less, which is smaller than the pore size.
- the particle size is smaller than the pore size of the filter 912. It is conceivable that large powdered particles are captured on the surface of the filter 912. That is, when powdered particles having a particle size of 10 ⁇ m or more are captured on the surface of the filter 912, a particle layer made of powdered particles is formed on the surface of the filter 912.
- the size of the substantial pore diameter by the particle layer is sufficiently smaller than the diameter size of the filter 912, even if the particle diameter is a pulverized particle smaller than the diameter of the pore of the filter 912, The particle layer can be reliably captured.
- the pore size of the filter 912 is not limited to the numerical range described above, and may be set to be equal to or less than the average particle size of the powdered particles, for example. Even in this case, the pulverized particles contained in the liquid hydrocarbon introduced into the filter 91 are captured on the surface of the filter 912, and thereby the surface of the filter 912 is sufficiently larger than the average particle size of the pulverized particles. A particle layer having a small pore size will be formed. Therefore, even if the pore size of the filter 912 is set to be equal to or smaller than the average particle size of the powdered particles, the powdered particles can be reliably captured as described above.
- each filter 91 includes a cleaning unit 100 that removes powdered particles adhering to the filter 912 from the filter 912.
- the cleaning means 100 is connected to a discharge pipe 93, and a gas supply unit that supplies an inert gas (cleaning fluid) such as nitrogen or argon to the filter 912 through the discharge pipe 93 at a high pressure ( (Cleaning fluid supply unit) 101.
- an inert gas cleaning fluid
- the inert gas passes through the filter 912 so as to go from the discharge pipe 93 side to the inside of the filtration container 911.
- the inert gas flows in the direction opposite to the direction in which the hydrocarbon compound passes in the filter 912, the powdered particles can be reliably removed from the filter 912. Note that even if the inert gas is blown into the filtration container 911, unnecessary chemical reaction does not occur between the inert gas and the liquid hydrocarbon or powdered particles.
- the valve 95 and the discharge of the supply pipe 92 are connected.
- the inert gas can be supplied to the filter 912 in a state where the supply line 92 and the discharge line 93 are closed by the valve 96 of the line 93, that is, in a state where filtration of the liquid hydrocarbon is stopped. Then, the inert gas that has passed through the filter 912 and has reached the inside can be discharged to the outside from the gas discharge line 103 connected to the upper part of the filtration container 911.
- the pulverized particles removed from the filter 912 can be discharged to the outside through the particle discharge pipe 104 connected to the lower end of the filtration container 911.
- the gas supply line 102, the gas discharge line 103, and the particle discharge line 104 are provided with valves 105, 106, and 107 for opening and closing them. There is nothing.
- the product purification unit 7 includes, for example, a WAX fraction hydrocracking reactor 50, a kerosene / light oil fraction hydrocracking reactor 52, a naphtha fraction hydrocracking reactor 54, and gas-liquid separators 56, 58. , 60, a second rectifying tower 70, and a naphtha stabilizer 72.
- the WAX fraction hydrocracking reactor 50 is connected to the lower part of the first fractionator 40.
- the kerosene / light oil fraction hydrotreating reactor 52 is connected to the center of the first fractionator 40.
- the naphtha fraction hydrotreating reactor 54 is connected to the upper part of the first fractionator 40.
- the gas-liquid separators 56, 58 and 60 are provided corresponding to the hydrogenation reactors 50, 52 and 54, respectively.
- the second rectifying column 70 separates and purifies the liquid hydrocarbons supplied from the gas-liquid separators 56 and 58 according to the boiling point.
- the naphtha stabilizer 72 rectifies the liquid hydrocarbons of the naphtha fraction supplied from the gas-liquid separator 60 and the second rectifying column 70, and discharges components lighter than butane to the flare gas side, and has 5 carbon atoms. The above components are separated and recovered as naphtha of the product.
- the liquid fuel synthesis system 1 is supplied with natural gas (main component is CH 4 ) as a hydrocarbon feedstock from an external natural gas supply source (not shown) such as a natural gas field or a natural gas plant.
- the synthesis gas generation unit 3 reforms the natural gas to produce a synthesis gas (a mixed gas containing carbon monoxide gas and hydrogen gas as main components).
- the natural gas is supplied to the desulfurization reactor 10 together with the hydrogen gas separated by the hydrogen separator 26.
- the desulfurization reactor 10 hydrodesulfurizes sulfur contained in natural gas using the hydrogen gas, for example, with a ZnO catalyst.
- a ZnO catalyst By desulfurizing the natural gas in advance in this way, it is possible to prevent the activity of the catalyst used in the reformer 12 and the bubble column reactor 30 or the like from being reduced by sulfur.
- the natural gas (which may contain carbon dioxide) desulfurized in this way is generated in carbon dioxide (CO 2 ) gas supplied from a carbon dioxide supply source (not shown) and the exhaust heat boiler 14.
- CO 2 carbon dioxide
- the reformer 12 is supplied.
- the reformer 12 reforms the natural gas using carbon dioxide and steam by the steam / carbon dioxide reforming method described above, so that the reformer 12 has a high temperature mainly composed of carbon monoxide gas and hydrogen gas. Generate synthesis gas.
- the fuel gas and air for the burner included in the reformer 12 are supplied to the reformer 12, and the combustion heat of the fuel gas in the burner and the radiant heat in the furnace of the reformer 12 are supplied.
- the reaction heat necessary for the steam / CO 2 reforming reaction which is an endothermic reaction, is provided.
- the high-temperature synthesis gas (for example, 900 ° C., 2.0 MPaG) generated in the reformer 12 in this manner is supplied to the exhaust heat boiler 14 and is exchanged by heat exchange with the water flowing in the exhaust heat boiler 14. It is cooled (for example, 400 ° C.) and the exhaust heat is recovered. At this time, the water heated by the synthesis gas in the exhaust heat boiler 14 is supplied to the gas-liquid separator 16, and the gas component from the gas-liquid separator 16 is reformed as high-pressure steam (for example, 3.4 to 10.0 MPaG). The water in the liquid is returned to the exhaust heat boiler 14 after being supplied to the vessel 12 or other external device.
- high-temperature synthesis gas for example, 900 ° C., 2.0 MPaG
- the synthesis gas cooled in the exhaust heat boiler 14 is supplied to the absorption tower 22 or the bubble column reactor 30 of the decarboxylation device 20 after the condensed liquid is separated and removed in the gas-liquid separator 18.
- the absorption tower 22 separates carbon dioxide from the synthesis gas by absorbing the carbon dioxide contained in the synthesis gas in the stored absorption liquid.
- the absorption liquid containing carbon dioxide gas in the absorption tower 22 is introduced into the regeneration tower 24, and the absorption liquid containing carbon dioxide gas is heated and stripped by, for example, steam, and the released carbon dioxide gas is removed from the regeneration tower 24.
- the reformer 12 and reused in the reforming reaction is supplied to the absorption tower 22 or the bubble column reactor 30 of the decarboxylation device 20 after the condensed liquid is separated and removed in the gas-liquid separator 18.
- the absorption tower 22 separates carbon dioxide from the synthesis gas by absorbing the carbon dioxide contained in the synthesis gas in the stored absorption liquid.
- the absorption liquid containing carbon dioxide gas in the absorption tower 22
- the synthesis gas produced by the synthesis gas production unit 3 is supplied to the bubble column reactor 30 of the FT synthesis unit 5.
- the synthesis gas supplied to the bubble column reactor 30 is subjected to an FT synthesis reaction by a compressor (not shown) provided in a pipe connecting the decarboxylation device 20 and the bubble column reactor 30.
- the pressure is increased to an appropriate pressure (for example, 3.6 MPaG).
- the compressor may not be provided.
- a part of the synthesis gas from which the carbon dioxide gas is separated by the decarboxylation device 20 is also supplied to the hydrogen separation device 26.
- the hydrogen separator 26 separates the hydrogen gas contained in the synthesis gas by adsorption and desorption (hydrogen PSA) using the pressure difference as described above.
- the separated hydrogen is subjected to various hydrogen utilization reactions in which a predetermined reaction is performed using hydrogen in the liquid fuel synthesizing system 1 from a gas holder (not shown) or the like via a compressor (not shown).
- Continuously supplied to the apparatus for example, desulfurization reactor 10, WAX fraction hydrocracking reactor 50, kerosene / light oil fraction hydrotreating reactor 52, naphtha fraction hydrotreating reactor 54, etc.
- the FT synthesis unit 5 synthesizes liquid hydrocarbons from the synthesis gas produced by the synthesis gas production unit 3 by an FT synthesis reaction.
- the synthesis gas produced by the synthesis gas production unit 3 flows from the bottom of the reactor main body 80 constituting the bubble column reactor 30 and is stored in the slurry stored in the reactor main body 80. To rise. At this time, in the reactor main body 80, carbon monoxide and hydrogen gas contained in the synthesis gas react by the above-described FT synthesis reaction to generate hydrocarbons. Furthermore, at the time of this synthesis reaction, water is circulated in the cooling pipe 81 to remove the reaction heat of the FT synthesis reaction, and the water heated by this heat exchange is vaporized to become steam. As for this water vapor, the water liquefied by the gas-liquid separator 34 is returned to the cooling pipe 81, and the gas component is supplied to the external device as medium pressure steam (for example, 1.0 to 2.5 MPaG).
- medium pressure steam for example, 1.0 to 2.5 MPaG
- the liquid hydrocarbon synthesized in the bubble column reactor 30 is taken out from the bubble column reactor 30 as a slurry and introduced into the separator 36.
- the separator 36 separates the extracted slurry into a solid content such as catalyst particles and a liquid content containing liquid hydrocarbons. Part of the solid content such as the separated catalyst particles is returned to the bubble column reactor 30, and the liquid content is supplied to the first rectifying column 40 via a filtration unit 90 described later.
- the unreacted synthesis gas and the synthesized hydrocarbon gas are introduced into the gas-liquid separator 38.
- the gas-liquid separator 38 cools these gases, separates some of the condensed liquid hydrocarbons, and introduces them into the first fractionator 40.
- the unreacted synthesis gas (CO and H 2 ) is reintroduced into the bottom of the bubble column reactor 30 and reused for the FT synthesis reaction.
- flare gas mainly composed of hydrocarbon gas with a low carbon number (C 4 or less) that is not a product target is introduced into an external combustion facility (not shown) and burned to the atmosphere after being burned.
- the liquid hydrocarbon separated from the slurry in the separator 36 is introduced into the filtration unit 90, and the pulverized particles contained in the liquid hydrocarbon are removed.
- a method for removing powdered particles will be described.
- the liquid hydrocarbon introduced into the filtration container 911 through the supply pipe line 92 is filtered from the inside of the filtration container 911 toward the discharge pipe line 93.
- the filter 912 captures the pulverized particles contained in the liquid hydrocarbon (filtration step).
- the supply pipe 92 and the discharge pipe 93 before and after the filter 91 are closed by the supply plug valve 94 and the discharge plug valve 97, thereby removing powder particles adhering to the filter 912.
- an inert gas is blown out from the gas supply unit 101 and is passed through the filter 912 so as to be directed from the discharge conduit 93 side toward the inside of the filtration container 911. That is, the inert gas is allowed to pass through the filter 912 in a direction opposite to the direction in which the liquid hydrocarbons are passed in the filtration step.
- the powdered particles are removed from the filter 912 and descend to the lower end side of the filtration container 911.
- the powdered particles that have reached the lower end of the filtration container 911 can be discharged to the outside through the particle discharge line 104 by opening the valve 107.
- the differential pressure across the filter 91 is measured by the differential pressure gauge 98, and the filtration is performed when the measurement result of the differential pressure exceeds a predetermined threshold value.
- the filtration process performed in the unit 90 is stopped and switched to the cleaning process. Since the differential pressure measured by the differential pressure gauge 98 increases as the amount of powdered particles captured by the filter 912 of the filter 91 increases, it is possible to accurately grasp the timing for switching to the cleaning process.
- the threshold value of the differential pressure for switching from the filtration process to the cleaning process is preferably set to 150 kPa, for example. This is because when the differential pressure is 150 kPa or more, liquid hydrocarbons are vaporized in the discharge pipe 93, and as a result, the raw material of the liquid fuel product is reduced.
- the filtration unit 90 is provided with a plurality of filters 91, and valves for opening and closing the supply pipes 92 and the discharge pipes 93 which are individually connected before and after each filter 91 are opened and closed. Since 95 and 96 are provided, respectively, for example, while the filtration process is performed in one filter 91A, 91B, the washing process can be performed in another filter 91C, 91D. In this case, the supply source plug valve 94 and the discharge source plug valve 97 are opened, and the valves 95A, 95B, 96A, and 96B before and after the one filter 91A and 91B are opened, and at the same time, the other filter.
- the valves 95C, 95D, 96C and 96D before and after 91C and 91D may be closed. Thereby, the liquid hydrocarbons from the separator 36 are introduced into the one filter 91 ⁇ / b> A, 91 ⁇ / b> B, the liquid hydrocarbon is filtered, and the filtered liquid hydrocarbon is transferred to the first fractionator 40. Can do. Further, since liquid hydrocarbons are not introduced into the other filters 91C and 91D, powdered particles adhering to the filter 912 can be removed.
- the differential pressure before and after the one filter 91A, 91B is measured by the differential pressure gauge 98, and the measurement result becomes a predetermined threshold value or more.
- the valves 95A, 95B, 96A, and 96B are closed, and the cleaning process is performed on the one filter 91A and 91B.
- the valves 95C, 95D, 96C, and 96D are opened, and the filtration process is performed by the other filters 91C and 91D.
- the first fractionator 40 is a liquid hydrocarbon (carbon number) supplied from the bubble column reactor 30 through the separator 36 and the filtration unit 90 or the gas-liquid separator 38 as described above. Is heated and fractionated using the difference in boiling point, naphtha fraction (boiling point is less than about 150 ° C), kerosene / light oil fraction (boiling point is about 150 to 350 ° C), WAX distillate Separate and purify in minutes (boiling point greater than about 350 ° C).
- the first fractionator 40 WAX fraction of liquid hydrocarbons withdrawn from the bottom of the (mainly C 21 or more) are transferred to the WAX fraction hydrocracking reactor 50, the central portion of the first fractionator 40
- the liquid hydrocarbon (mainly C 11 to C 20 ) of the kerosene / light oil fraction taken out is transferred to the kerosene / light oil fraction hydrotreating reactor 52 and taken out from the upper part of the first rectifying tower 40.
- Liquid hydrocarbons (mainly C 5 -C 10 ) are transferred to the naphtha fraction hydrotreating reactor 54.
- the WAX fraction hydrocracking reactor 50 is supplied with liquid hydrocarbons (approximately C 21 or more) of the WAX fraction having a large number of carbons supplied from the lower part of the first fractionator 40 from the hydrogen separator 26.
- the hydrogen gas is hydrocracked using the hydrogen gas to reduce the carbon number to 20 or less.
- this hydrocracking reaction using a catalyst and heat, the C—C bond of a hydrocarbon having a large number of carbon atoms is cleaved to generate a low molecular weight hydrocarbon having a small number of carbon atoms.
- the product containing liquid hydrocarbon hydrocracked by the WAX fraction hydrocracking reactor 50 is separated into a gas and a liquid by a gas-liquid separator 56, and the liquid hydrocarbon is separated into a second rectification fraction.
- the gas component (including hydrogen gas) is transferred to the tower 70 and transferred to the kerosene / light oil fraction hydrotreating reactor 52 and the naphtha fraction hydrotreating reactor 54.
- the kerosene / light oil fraction hydrotreating reactor 52 is a liquid hydrocarbon (approximately C 11 to C 20 ) of the kerosene / light oil fraction having a medium carbon number supplied from the center of the first fractionator 40. Is hydrorefined using the hydrogen gas supplied from the hydrogen separator 26 through the WAX fraction hydrocracking reactor 50. In this hydrorefining reaction, in order to obtain mainly a side chain saturated hydrocarbon, the liquid hydrocarbon is isomerized, and hydrogen is added to the unsaturated bond of the liquid hydrocarbon to be saturated.
- the hydrorefined liquid hydrocarbon-containing product is separated into a gas and a liquid by the gas-liquid separator 58, and the liquid hydrocarbon is transferred to the second rectifying column 70, where the gas component (hydrogen Gas is reused) in the hydrogenation reaction.
- the naphtha fraction hydrotreating reactor 54 supplies liquid hydrocarbons (generally C 10 or less) of the naphtha fraction with a small number of carbons supplied from the upper part of the first rectification column 40 from the hydrogen separator 26 to the WAX fraction. Hydrorefining is performed using the hydrogen gas supplied through the hydrocracking reactor 50. As a result, the hydrorefined liquid hydrocarbon-containing product is separated into a gas and a liquid by the gas-liquid separator 60, and the liquid hydrocarbon is transferred to the naphtha stabilizer 72, where the gas component (hydrogen gas is removed). Is reused in the hydrogenation reaction.
- liquid hydrocarbons generally C 10 or less
- the second fractionator 70 distills the liquid hydrocarbons supplied from the WAX fraction hydrocracking reactor 50 and the kerosene / light oil fraction hydrotreating reactor 52 as described above to obtain a carbon number.
- Light oil is taken out from the lower part of the second fractionator 70, and kerosene is taken out from the center.
- a hydrocarbon gas having a carbon number of 10 or less is taken out from the top of the second rectifying column 70 and supplied to the naphtha stabilizer 72.
- the naphtha stabilizer 72 distills hydrocarbons having a carbon number of 10 or less supplied from the naphtha fraction hydrotreating reactor 54 and the second rectifying tower 70 to obtain naphtha (C 5 as a product). ⁇ C 10 ) is separated and purified. Thereby, high-purity naphtha is taken out from the lower part of the naphtha stabilizer 72. Meanwhile, from the top of the naphtha stabilizer 72, flare gas carbon number of target products composed mainly of hydrocarbons below predetermined number (C 4 or less) is discharged. This flare gas is introduced into an external combustion facility (not shown), burned, and then released into the atmosphere.
- the pulverized particles are removed in the filter 91. Capturing particles can be removed from liquid hydrocarbons by capturing them, so that mixing of powdered particles into liquid hydrocarbons used in the production process of liquid fuel products as a raw material for liquid fuel products can be achieved. It becomes possible to prevent the product quality from deteriorating.
- the catalyst used in the production of the liquid fuel product such as the WAX fraction hydrocracking reactor 50, does not deteriorate based on the pulverized particles, the liquid fuel product is produced using liquid hydrocarbons.
- the product purification unit 7 (device) to be manufactured can be easily cleaned and can be continuously operated stably for a long time. Further, the amount of catalyst particles and pulverized particles contained in the liquid hydrocarbon separated in the separator 36 is affected by the flow rate of the slurry circulating between the reactor 30 and the separator 36, but the filter 91. Is not included in this circulation portion, the filter 91 can filter liquid hydrocarbons without being affected by the slurry flow rate described above.
- the filter 91 for filtering the liquid hydrocarbons is exchanged by switching the opening and closing of the branch portions of the supply pipe line 92 and the discharge pipe line 93 by the valves 95A to 95D and 96A to 96D.
- the liquid hydrocarbon can be continuously filtered.
- by measuring the differential pressure of liquid hydrocarbons before and after the filtration unit 90 with a differential pressure gauge it is possible to accurately grasp the switching time, so that continuous filtration of liquid hydrocarbons is performed in a good state. Can do.
- the filter 91 with the cleaning means 100 and performing the cleaning process, the powdered particles can be reliably removed from the filter 912 without removing the filter 912 from the filtration container 911.
- 912 can be used repeatedly for the filtration of liquid hydrocarbons. Further, since the filter 912 is formed by sintering, even if a high pressure is applied to the filter 912 by liquid hydrocarbon or inert gas in the filtration process or the cleaning process, the filter 912 can sufficiently withstand the same filter 912. Can be used for a long time.
- half of the plurality of filters 91 are set as one group, and each group is switched between the filtration process and the washing process.
- the present invention is not limited to this. It is possible to switch to the filtration step and the washing step by dividing the set into two groups. For example, the filtration process is performed with only one filter 91 (one filter), and at the same time, the washing process is performed for the remaining plurality of filters 91 (other filters).
- the filtration process is switched to the cleaning process, one of the plurality of filters 91 performing the cleaning process may be switched to the filtration process.
- the washing process is performed only on one filter 91 (other filter), and at the same time, the filtering process is performed using the remaining plurality of filters 91 (one filter).
- one filter 91 that has performed the cleaning process may be switched to the filtration process.
- the branch portions of the supply pipe line 92 and the discharge pipe line 93 are appropriately opened and closed by the valves 95A to 95D and 96A to 96D.
- the number of filter 91 can be adjusted according to changes in the concentration of pulverized particles in the liquid hydrocarbon introduced from the separator 36, the supply flow rate of the liquid hydrocarbon, and the like. It becomes possible to keep the flow rate of the liquid hydrocarbon passing through the vessel 91 constant. That is, the liquid hydrocarbon can be stably filtered in each filter 91.
- cleaning means 100 was provided in each filter 91, for example, only one may be provided with respect to the several filter 91.
- the gas supply line 102 may be branched so as to be connected to each branch portion of the discharge line 93.
- a valve 105 is provided at each branch portion of the gas supply pipe line 102, and a filter 91 that supplies an inert gas is selected by selectively opening and closing the branch part of the gas supply pipe line 102 by these valves 105. can do.
- the cleaning fluid for removing the powdered particles from the filter 912 is not limited to an inert gas such as nitrogen or argon, but may be a liquid that does not chemically react with liquid hydrocarbons or (catalyst particles) powdered particles.
- the liquid include liquid hydrocarbons separated and purified in the first fractionator 40 and liquid hydrocarbons hydrocracked and hydrorefined in the hydrogenation reactors 50, 52, and 54.
- the product, liquid hydrocarbons separated in the gas-liquid separators 56, 58, and 60, and liquid fuel products such as kerosene and light oil separated and refined in the second fractionator 70 may be used.
- the cleaning means 100 for removing the powdered particles adhering to the filter 912 the gas supply unit 101 is cited.
- the cleaning means 100 is a vibration means for vibrating the filter 912 to shake off the powdered particles from the filter 912. May be. Even in this case, the powdered particles can be removed from the filter 912 without removing the filter 912 from the filtration container 911 as in the above embodiment.
- each filter 91 is provided with a plurality of filters 912, it may be increased or decreased according to the required filtration performance, that is, only one filter 912 may be provided.
- the plurality of filters 91 are not limited to be arranged in parallel with respect to the separator 36 and the first rectifying column 40, and for example, in series between the separator 36 and the first rectifying column 40. It may be arranged. In this case, for example, the hole diameter of the filter 912 in the filter 91 on the separator 36 side may be increased, and the hole diameter may be decreased in the filter 91 on the first fractionator 40 side.
- the filtration unit 90 is configured to include a plurality of filters 91, when the liquid hydrocarbon is not continuously filtered, for example, the filter unit 90 may be configured to include only one filter 91. Good.
- the present invention is a hydrocarbon synthesis that synthesizes a hydrocarbon compound by a chemical reaction between a synthesis gas containing at least hydrogen and carbon monoxide as a main component and a slurry. It can be applied to reaction systems.
- the hydrocarbon synthesis reaction system may have, for example, a main configuration including the FT synthesis unit 5, and mainly includes the bubble column reactor 30, the separator 36, the filtration unit 90, and the filter 91. It may be a thing.
- the separator 36 is installed outside the bubble column reactor 30, but may be included in the bubble column reactor 30, for example. That is, in the bubble column reactor 30, the liquid hydrocarbon contained in the slurry may be separated from the slurry.
- the present invention provides a synthesis reaction in which a hydrocarbon compound synthesized by a chemical reaction between a synthesis gas mainly composed of hydrogen and carbon monoxide and a slurry in which solid catalyst particles are suspended in a liquid is extracted from the slurry.
- a reactor for containing the slurry and synthesizing the hydrocarbon compound; a separator for separating the hydrocarbon compound contained in the slurry inside the reactor from the slurry; and the separator.
- the present invention relates to a synthesis reaction system comprising: a filter that captures powdered particles formed by powdering the catalyst particles by filtering the extracted hydrocarbon compound.
- ADVANTAGE OF THE INVENTION According to this invention, mixing suppression of the powdered particle
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本願は、2008年3月14日に出願された特願2008-66154について優先権を主張し、その内容をここに援用する。
また、液体燃料製品の製造工程において使用する触媒が、粉化粒子に基づいて劣化することも無いため、液体燃料製品を製造する装置のメンテナンスも容易に行うことができ、且つ、前記装置を長時間安定的に連続して運転することができる。
さらに、分離器において分離された炭化水素化合物に含まれる触媒粒子や粉化粒子の量は、反応器と分離器との間で循環するスラリーの流量の影響を受けるが、濾過器はこの循環部分に含まれないため、濾過器においては、前述したスラリー流量に影響されずに炭化水素化合物の濾過を実施することができる。
このように構成した場合には、分離器から取り出された炭化水素化合物を複数の濾過器に分割して供給することができるため、分離器から取り出される炭化水素化合物に粉化粒子が多量に含まれていても、十分に除去することが可能となる。
そして、バルブにより供給管路の開閉を切り替えて炭化水素化合物を濾過する濾過器を交換することで、炭化水素化合物の濾過を継続的に行うことができる。
このように差圧を計測する計器を設けることで、濾過器を通過する炭化水素化合物の流れに対する濾過器の抵抗を計測することができる。この抵抗の大きさは、濾過器において捕捉された粉化粒子の量が多くなる程大きくなるため、濾過器の洗浄時期を的確に把握することができる。
なお、前述したように、複数の濾過器を備えると共に全ての濾過器において同時に炭化水素化合物を濾過しないように、バルブにより各供給管路を適宜開閉している場合には、炭化水素化合物の濾過に使用する濾過器の交換時期を的確に把握することができ、継続的な炭化水素化合物の濾過を良好な状態で行うことができる。
この構成においては、炭化水素化合物が濾過容器の内側から排出管路側に向かうようにフィルタ内を通過することで、炭化水素化合物を濾過することができる。
さらに、前記洗浄手段が前記排出管路に接続されると共に、当該排出管路を介して前記フィルタに洗浄用流体を供給する洗浄流体供給部を備える場合には、洗浄用流体が排出管路側から濾過容器の内側に向かうようにフィルタ内を通過することができる。すなわち、洗浄用流体は、フィルタ内において炭化水素化合物が通過する方向とは逆向きに流れるため、粉化粒子を確実にフィルタから取り除くことができる。
また、洗浄用流体を不活性ガスとすることで、炭化水素化合物や粉化粒子との間で化学反応が生じることを防止できる。
このように孔の径寸法を設定することにより、フィルタにおいて確実に粉化粒子を捕捉することができる。
また、金網焼結フィルタは焼結して構成されているため、炭化水素化合物や洗浄用流体がフィルタを通過する際に、フィルタにかかる圧力が大きくても十分に耐えることができるため、同一のフィルタを長時間にわたって使用することができる。
すなわち、粒径がフィルタの孔径寸法よりも大きい粉化粒子は、フィルタにおいて直接捕捉することができ、結果として、フィルタの表面に粉化粒子からなる粒子層が形成されることになる。ここで、粒子層による実質的な孔径寸法は粉化粒子の平均粒径よりも十分に小さくなるため、粒径がフィルタの孔径寸法よりも小さい粉化粒子であっても、粒子層において確実に捕捉することができる。
また、洗浄工程を行うことで、粉化粒子を確実にフィルタから取り除くことができるため、同一のフィルタを繰り返し炭化水素化合物の濾過に使用することができる。
このように、複数のフィルタに対して濾過工程及び洗浄工程を同時に行うことで、炭化水素化合物の濾過を継続的に行うことができる。
なお、計測される差圧は、フィルタにおいて捕捉される粉化粒子の量が増加するほど大きくなる。したがって、この差圧が所定の閾値以上となった際に、フィルタに対して洗浄工程を実施することで、フィルタの洗浄時期を的確に把握し、フィルタにおける炭化水素化合物の濾過性能(効率)の低下を効率よく抑えることが可能となる。
また、前記粉化粒子の除去方法においては、前記閾値を0kPaよりも大きく、かつ、150kPa以下に設定することが特に好ましい。すなわち、前記差圧が前記閾値以上となった際に該当するフィルタによる濾過工程を停止することで、炭化水素化合物が気化することを抑えて、炭化水素化合物が目減りすることを防止できる。
30…気泡塔型反応器(気泡塔型炭化水素合成反応器)
36…分離器
91…濾過器
92…供給管路
93…排出管路
95…バルブ
98…差圧計
100…洗浄手段
101…ガス供給部(洗浄流体供給部)
911…濾過容器
912…フィルタ
図1に示すように、本実施形態にかかる液体燃料合成システム(炭化水素合成反応システム)1は、天然ガス等の炭化水素原料を液体燃料に転換するGTLプロセスを実行するプラント設備である。この液体燃料合成システム1は、合成ガス生成ユニット3と、FT合成ユニット5と、製品精製ユニット7とから構成される。合成ガス生成ユニット3は、炭化水素原料である天然ガスを改質して一酸化炭素ガスと水素ガスを含む合成ガスを生成する。FT合成ユニット5は、生成された合成ガスからフィッシャー・トロプシュ合成反応(以下、「FT合成反応」という。)により液体炭化水素を生成する。製品精製ユニット7は、FT合成反応により生成された液体炭化水素を水素化・精製して液体燃料製品(ナフサ、灯油、軽油、ワックス等)を製造する。以下、これら各ユニットの構成要素について説明する。
CH4+CO2→2CO+2H2 ・・・(2)
この反応器本体80の下部においては、水素および一酸化炭素を主成分とする合成ガスがスラリー中に噴射される。そして、スラリー中に吹き込まれた合成ガスは、気泡となってスラリー中を反応器本体80の高さ方向(鉛直方向)下方から上方へ向かって流れる。その過程で、合成ガスは液体炭化水素中に溶解し、触媒粒子と接触する接触反応により、液体炭化水素の合成反応(FT合成反応)が行われる。具体的には、下記化学反応式(3)に示すように水素ガスと一酸化炭素ガスとが合成反応を起こす。
分離器36と複数の濾過器91とは、分離器36側から出て途中で分岐する供給管路92によって個別に接続されており、分離器36からの液体炭化水素はこの供給管路92を介して各濾過器91に導入することができるようになっている。また、複数の濾過器91と第1精留塔40とは、各濾過器91側から途中で集約される排出管路93によって接続されており、各濾過器91において濾過された液体炭化水素を第1精留塔40に移送できるようになっている。
そして、濾過ユニット90は、炭化水素化合物が濾過器91によって濾過される過程において濾過器91の上流側と下流側との差圧を計測する差圧計98も備えている。具体的に、濾過器91に流入する前の液体炭化水素の圧力は、供給管路92が分岐する前の位置において計測され、濾過器91から排出された後の液体炭化水素の圧力は、排出管路93が集約された後の位置において計測される。この差圧計98においては、濾過器91を通過する液体炭化水素の流れに対する濾過器91の抵抗を計測することができる。この抵抗の大きさは、濾過器91において捕捉される粉化粒子の量が多くなるほど大きくなる。
濾過容器911は、供給管路92に接続されて分離器36からの液体炭化水素を内部に導入できるように構成されている。各フィルタ912は、濾過容器911の内部に配されており、濾過容器911内の液体炭化水素を通過させることで濾過して、粉化粒子を捕捉する役割を果たす。そして、このフィルタ912には排出管路93が接続されており、フィルタ912において濾過された液体炭化水素を直接濾過容器911の外側に排出することができる。
このフィルタ912は、例えば金網焼結フィルタによって構成されている。金網焼結フィルタは、金網を複数枚重ね合わせて真空中で高温焼結したものであり、金網のメッシュの大きさや積層枚数に応じて当該金網焼結フィルタに形成される孔径の大きさを調整することができる。ここで、金網焼結フィルタに形成される孔の径寸法は、液体炭化水素は通過するが粉化粒子がフィルタ912を通過しない大きさに形成されていればよく、濾過器91に導入される液体炭化水素の流量や、当該液体炭化水素に含まれる粉化粒子の大きさに応じて変化させればよい。例えば、粉化粒子の大きさが小さい場合には、孔の径寸法を当該粉化粒子の大きさよりも小さくすればよい。
その結果、フィルタ912を通過した液体炭化水素に含まれる粉化粒子の濃度が、孔の径寸法に関わらず、測定下限値(4wt.ppm)以下まで減少した。また、フィルタ912を通過した液体炭化水素に含まれる粉化粒子の粒径は測定できない程度に小さく、大きなものでも8μm以下であることが判明した。
なお、フィルタ912の孔径10μmの場合でも、フィルタ912を通過した液体炭化水素に含まれる粉化粒子の粒径が上記孔径よりも小さい8μm以下となるのは、粒径がフィルタ912の孔径よりも大きい粉化粒子が、フィルタ912の表面において捕捉されていることが考えられる。すなわち、粒径が10μm以上の粉化粒子がフィルタ912の表面において捕捉されると、フィルタ912の表面に粉化粒子からなる粒子層が形成される。ここで、粒子層による実質的な孔径の寸法は、フィルタ912の孔の径寸法よりも十分に小さくなるため、粒径がフィルタ912の孔の径寸法よりも小さい粉化粒子であっても、この粒子層において確実に捕捉することができる。
そして、フィルタ912を通過して内部に到達した不活性ガスは、濾過容器911の上部に接続されたガス排出管路103から外部に排出することができる。また、フィルタ912から取り除かれた粉化粒子は、濾過容器911の下端に接続された粒子排出管路104を介して外部に排出することができる。なお、ガス供給管路102、ガス排出管路103及び粒子排出管路104には、これらを開閉するバルブ105,106,107がそれぞれ設けられているため、これらが液体炭化水素の濾過を阻害することは無い。
また、気泡塔型反応器30からは、未反応の合成ガスと、合成された炭化水素のガス分とが気液分離器38に導入される。気液分離器38は、これらのガスを冷却して、一部の凝縮分の液体炭化水素を分離して第1精留塔40に導入する。一方、気液分離器38で分離されたガス分については、未反応の合成ガス(COとH2)は、気泡塔型反応器30の底部に再投入されてFT合成反応に再利用される。また、製品対象外である炭素数が少ない(C4以下)炭化水素ガスを主成分とするフレアガスは、外部の燃焼設備(図示せず。)に導入されて、燃焼された後に大気放出される。
粉化粒子を除去する際には、濾過ユニット90において、供給管路92を介して濾過容器911内に導入された液体炭化水素を、濾過容器911の内側から排出管路93側に向かうフィルタ912の一方向に通過させ、当該フィルタ912において液体炭化水素に含まれる粉化粒子を捕捉する(濾過工程)。
また、濾過ユニット90においては、供給元栓バルブ94及び排出元栓バルブ97により濾過器91の前後の供給管路92及び排出管路93を閉じることで、フィルタ912に付着した粉化粒子を除去することができる(洗浄工程)。具体的に、この洗浄工程においては、ガス供給部101から不活性ガスを吹き出し、排出管路93側から濾過容器911の内側に向かうようにフィルタ912内を通過させる。すなわち、フィルタ912に対して、濾過工程において液体炭化水素を通過させる一方向とは逆向きに不活性ガスを通過させる。これにより、粉化粒子がフィルタ912から取り除かれ、濾過容器911の下端側に下降する。なお、濾過容器911の下端に到達した粉化粒子は、バルブ107を開くことで粒子排出管路104を介して外部に排出することができる。
濾過工程から洗浄工程に切り替える差圧の閾値は、例えば150kPaとすることが好ましい。これは、当該差圧が150kPa以上となると、排出管路93において液体炭化水素が気化してしまい、結果として、液体燃料製品の原料が目減りしてしまうためである。
この場合には、供給元栓バルブ94及び排出元栓バルブ97は開いておき、さらに、一の濾過器91A,91Bの前後のバルブ95A,95B,96A,96Bを開いておくと同時に、他の濾過器91C,91Dの前後のバルブ95C,95D,96C,96Dを閉めておけばよい。これにより、一の濾過器91A,91Bには、分離器36からの液体炭化水素が導入され、当該液体炭化水素を濾過し、濾過された液体炭化水素を第1精留塔40に移送することができる。また、他の濾過器91C,91Dには、液体炭化水素が導入されないため、フィルタ912に付着した粉化粒子を除去することができる。
さらに、一の濾過器91A,91Bにより濾過工程を実施している際には、差圧計98により一の濾過器91A,91B前後における差圧を計測し、その計測結果が所定の閾値以上となった際にバルブ95A,95B,96A,96Bを閉じ、一の濾過器91A,91Bに対して洗浄工程を実施する。また、これと同時に、バルブ95C,95D,96C,96Dを開いて他の濾過器91C,91Dにより濾過工程を実施する。
また、WAX留分水素化分解反応器50等のように液体燃料製品の製造に際して使用する触媒が、粉化粒子に基づいて劣化することも無いため、液体炭化水素を使用して液体燃料製品を製造する製品精製ユニット7(装置)の洗浄も容易で且つ長時間安定的に連続運転を行うことができる。
さらに、分離器36において分離された液体炭化水素に含まれる触媒粒子や粉化粒子の量は、反応器30と分離器36との間で循環するスラリーの流量の影響を受けるが、濾過器91はこの循環部分に含まれないため、濾過器91においては、前述したスラリー流量に影響されずに液体炭化水素の濾過を実施することができる。
さらに、バルブ95A~95D,96A~96Dにより供給管路92及び排出管路93の分岐部分の開閉を切り替えて液体炭化水素を濾過する濾過器91を交換すると共に、濾過工程と洗浄工程とを同時に実施することで、液体炭化水素の濾過を継続的に行うことができる。特に、差圧計により濾過ユニット90の前後における液体炭化水素の差圧を計測することで、切り替え時期を的確に把握することができるため、液体炭化水素の継続的な濾過を良好な状態で行うことができる。
例えば、1つの濾過器91(一の濾過器)のみで濾過工程を行うと同時に、残りの複数の濾過器91(他の濾過器)に対して洗浄工程を実施し、1つの濾過器91が濾過工程から洗浄工程に切り替えられた際には洗浄工程を実施している複数の濾過器91の1つを濾過工程に切り替えてもよい。また、例えば、1つの濾過器91(他の濾過器)だけに対して洗浄工程を実施すると同時に、残りの複数の濾過器91(一の濾過器)により濾過工程を行い、1つの濾過器91が濾過工程から洗浄工程に切り替えられた際には洗浄工程を実施していた1つの濾過器91を濾過工程に切り替えてもよい。
また、粉化粒子をフィルタ912から取り除く洗浄用流体は、窒素・アルゴン等の不活性ガスに限らず、例えば、液化炭化水素や(触媒粒子)粉化粒子と化学反応しない液体であってもよい。この液体としては、例えば第1精留塔40において分離・精製された液体炭化水素の各留分、水素化反応器50,52,54において水素化分解・水素化精製された液体炭化水素を含む生成物、気液分離器56,58,60において分離された液体炭化水素、第2精留塔70において分離・精製された灯油・軽油等の液体燃料製品であってもよい。
さらに、フィルタ912に付着した粉化粒子を除去する洗浄手段100としては、ガス供給部101が挙げられているが、例えばフィルタ912を振動させて粉化粒子をフィルタ912から振るい落とす振動手段であっても良い。この場合でも、上記実施形態と同様に、フィルタ912を濾過容器911から取外すことなく、フィルタ912から粉化粒子を除去することができる。
さらに、複数の濾過器91は、分離器36及び第1精留塔40に対して並列に配されることに限らず、例えば、分離器36と第1精留塔40との間で直列に配されても良い。この場合には、例えば、分離器36側の濾過器91におけるフィルタ912の孔径を大きくしておき、第1精留塔40側の濾過器91においては孔径を小さくしても良い。この構成では、粉化粒子の大きさに応じて粉化粒子が複数の段階に分けて除去されるため、各濾過器91において粉化粒子による目詰まりが生じにくくなり、フィルタ912を洗浄・交換することなく、長時間にわたって使用することが可能となる。
また、濾過ユニット90は、複数の濾過器91を備えて構成されているが、液体炭化水素の濾過を継続的に行わない場合には、例えば濾過器91を1つだけ備えて構成されてもよい。
さらに、上記実施形態においては、液体燃料合成システム1について述べたが、本発明は少なくとも水素及び一酸化炭素を主成分とする合成ガスとスラリーとの化学反応によって炭化水素化合物を合成する炭化水素合成反応システムに適用することができる。なお、炭化水素合成反応システムは、例えばFT合成ユニット5を主たる構成としたものであってもよいし、気泡塔型反応器30、分離器36及び濾過ユニット90や濾過器91を主に備えたものであってもよい。
なお、分離器36は、気泡塔型反応器30の外部に設置されるとしたが、例えば気泡塔型反応器30内部に含まれてもよい。すなわち、気泡塔型反応器30において、スラリーに含まれる液体炭化水素がスラリーから分離されてもよい。
本発明によれば、液体燃料製品の製造工程に使用する炭化水素化合物への粉化粒子の混入抑制を図ることができ、液体燃料製品の品質低下を防止することが可能となる。
Claims (15)
- 水素及び一酸化炭素を主成分とする合成ガスと、液体中に固体の触媒粒子を懸濁させてなるスラリーとの化学反応によって炭化水素化合物を合成する反応器と;
前記スラリーから前記炭化水素化合物を分離する分離器と;
前記分離器から取り出された前記炭化水素化合物を濾過し、粉化した触媒粒子を捕捉する濾過器と;
を備える炭化水素化合物の合成反応システム。 - 前記濾過器が複数設けられ、
前記分離器と各濾過器とが、それぞれ前記炭化水素化合物を前記分離器から各濾過器に供給する供給管路によって個別に接続されている請求項1に記載の炭化水素化合物の合成反応システム。 - 前記供給管路の各分岐部分には、これを開閉して各濾過器に対する前記炭化水素化合物の供給を個別に切り替えるバルブが設けられている請求項2に記載の炭化水素化合物の合成反応システム。
- 一の濾過器が前記炭化水素化合物を濾過すると同時に、他の濾過器が前記炭化水素化合物を濾過しないように、前記供給管路の各分岐部分が前記バルブによってそれぞれ開閉される請求項3に記載の炭化水素化合物の合成反応システム。
- 前記炭化水素化合物が前記濾過器によって濾過される過程において前記濾過器の上流側と下流側との差圧を計測する差圧計を備える請求項1から請求項4のいずれか一項に記載の炭化水素化合物の合成反応システム。
- 前記濾過器は、前記供給管路に接続される濾過容器と、該濾過容器内に配されて前記炭化水素化合物を濾過するフィルタとを備え、
当該フィルタには、濾過された前記炭化水素化合物を前記濾過容器の外側に排出する排出管路が接続されている請求項1から請求項5のいずれか1項に記載の炭化水素化合物の合成反応システム。 - 前記濾過器は、前記フィルタに付着した前記粉化した触媒粒子を除去する洗浄手段を備える請求項6に記載の炭化水素化合物の合成反応システム。
- 前記洗浄手段が、前記排出管路に接続されると共に、当該排出管路を介して前記フィルタに洗浄用流体を供給する洗浄流体供給部を備える請求項7に記載の炭化水素化合物の合成反応システム。
- 前記洗浄用流体が不活性ガスである請求項8に記載の炭化水素化合物の合成反応システム。
- 前記フィルタが、金網を複数枚重ね合わせて焼結した金網焼結フィルタからなり、
当該金網焼結フィルタに形成される孔の径寸法が、前記粉化した触媒粒子の平均粒径以下である請求項6から請求項9のいずれか一項に記載の炭化水素化合物の合成反応システム。 - 前記フィルタが、金網を複数枚重ね合わせて焼結した金網焼結フィルタからなり、
当該金網焼結フィルタに形成される孔の径寸法が、0μmよりも大きく、かつ、10μm以下である請求項6から請求項9のいずれか一項に記載の炭化水素化合物の合成反応システム。 - 水素及び一酸化炭素を主成分とする合成ガスと、液体中に固体の触媒粒子を懸濁させてなるスラリーとの化学反応によって合成された炭化水素化合物を前記スラリーから取り出した後に実施される、粉化した触媒粒子の除去方法であって:
前記炭化水素化合物を、濾過器に具備されるフィルタの一方向に通過させて、粉化した触媒粒子を捕捉する濾過工程と;
前記フィルタに前記一方向とは逆向きに洗浄用流体を通過させて、前記フィルタから前記粉化した触媒粒子を除去する洗浄工程と;
を備える粉化粒子の除去方法。 - 前記フィルタが、これに通過させる前記炭化水素化合物に対して複数並列に配され、
一のフィルタにおいて前記濾過工程が行われる際には、他のフィルタに対して前記メンテナンス工程が同時に行われ、また、前記他のフィルタにおいて前記濾過工程が行われる際には、一のフィルタに対して前記洗浄工程が同時に行われると請求項12に記載の粉化粒子の除去方法。 - 前記濾過工程を実施している前記フィルタに対して、当該フィルタに流入する前の前記炭化水素化合物の圧力と、濾過されて前記フィルタから排出された前記炭化水素化合物の圧力との差圧を計測し、
当該差圧の計測結果が、所定の閾値以上となった際に、前記フィルタにおいて実施する工程を前記濾過工程から前記洗浄工程に切り替える請求項12又は請求項13に記載の粉化粒子の除去方法。 - 前記閾値は、0kPaよりも大きく、かつ、150kPa以下である請求項14に記載の粉化粒子の除去方法。
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN200980108669.XA CN101970606B (zh) | 2008-03-14 | 2009-03-12 | 烃化合物的合成反应系统及粉化粒子的除去方法 |
JP2010502869A JP5568462B2 (ja) | 2008-03-14 | 2009-03-12 | 炭化水素化合物の合成反応システム、及び粉化粒子の除去方法 |
US12/736,108 US9162170B2 (en) | 2008-03-14 | 2009-03-12 | Synthesis reaction system for hydrocarbon compound, and method of removing powdered catalyst particles |
EP09720574.4A EP2258812A4 (en) | 2008-03-14 | 2009-03-12 | REACTION SYSTEM FOR THE SYNTHESIS OF A HYDROCARBON COMPOUND AND PROCESS FOR REMOVING FINELY DIVIDED PARTICLES |
AU2009224342A AU2009224342B2 (en) | 2008-03-14 | 2009-03-12 | Synthesis reaction system for hydrocarbon compound and method of removing powdered catalyst particles |
BRPI0908921-7A BRPI0908921B1 (pt) | 2008-03-14 | 2009-03-12 | Sistema de reação de síntese para composto de hidrocarboneto, e método de remoção de partículas de catalisador em pó |
MYPI2010004266A MY162163A (en) | 2008-03-14 | 2009-03-12 | Hydrocarbon compound synthesis reaction system and finely divided particle removal method |
CA2718077A CA2718077C (en) | 2008-03-14 | 2009-03-12 | Synthesis reaction system for hydrocarbon compound, and method of removing powdered catalyst particles |
EA201071008A EA018418B1 (ru) | 2008-03-14 | 2009-03-12 | Реакторная система для синтеза углеводородного соединения и способ удаления частиц порошкообразного катализатора |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008066154 | 2008-03-14 | ||
JP2008-066154 | 2008-03-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009113613A1 true WO2009113613A1 (ja) | 2009-09-17 |
Family
ID=41065273
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2009/054759 WO2009113613A1 (ja) | 2008-03-14 | 2009-03-12 | 炭化水素化合物の合成反応システム、及び粉化粒子の除去方法 |
Country Status (10)
Country | Link |
---|---|
US (1) | US9162170B2 (ja) |
EP (1) | EP2258812A4 (ja) |
JP (1) | JP5568462B2 (ja) |
CN (1) | CN101970606B (ja) |
AU (1) | AU2009224342B2 (ja) |
BR (1) | BRPI0908921B1 (ja) |
CA (1) | CA2718077C (ja) |
EA (1) | EA018418B1 (ja) |
MY (1) | MY162163A (ja) |
WO (1) | WO2009113613A1 (ja) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011208091A (ja) * | 2010-03-30 | 2011-10-20 | Japan Oil Gas & Metals National Corp | 炭化水素の製造方法 |
WO2012023527A1 (ja) * | 2010-08-19 | 2012-02-23 | 独立行政法人石油天然ガス・金属鉱物資源機構 | 炭化水素油の製造方法及び炭化水素油の製造システム |
JP2012041449A (ja) * | 2010-08-19 | 2012-03-01 | Japan Oil Gas & Metals National Corp | 炭化水素油の製造方法及び炭化水素油の製造システム |
WO2012137936A1 (ja) * | 2011-04-08 | 2012-10-11 | 新日鉄エンジニアリング株式会社 | 触媒反応装置 |
JP2012201842A (ja) * | 2011-03-28 | 2012-10-22 | Japan Oil Gas & Metals National Corp | 炭化水素の製造方法 |
JP2013034929A (ja) * | 2011-08-05 | 2013-02-21 | Japan Oil Gas & Metals National Corp | フィルタの洗浄装置 |
WO2014156890A1 (ja) * | 2013-03-26 | 2014-10-02 | 独立行政法人石油天然ガス・金属鉱物資源機構 | 炭化水素合成反応装置 |
JP2014528909A (ja) * | 2011-06-24 | 2014-10-30 | アンガス ケミカル カンパニー | 連続撹拌槽スラリー反応器を使用して、アミノアルコールの製造及び濾過をするための方法及び装置 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6466572B2 (ja) | 2014-12-08 | 2019-02-06 | エルジー・ケム・リミテッド | ポリアルキレンカーボネート樹脂の製造方法 |
EP3247776B1 (en) | 2015-01-20 | 2019-11-13 | The Petroleum Oil and Gas Corporation of South Africa (Pty) Ltd. | Ltft catalyst fines removal |
CN104998491B (zh) * | 2015-07-23 | 2016-12-28 | 北京石油化工工程有限公司 | 一种悬浮床加氢的热高压分离器 |
GB2553771B (en) * | 2016-09-08 | 2018-12-05 | Wilson Bio Chemical Ltd | Removing particulates |
CN106430093B (zh) * | 2016-10-11 | 2018-07-10 | 中国华能集团清洁能源技术研究院有限公司 | 保护燃烧前co2捕集系统变换单元催化剂的系统和方法 |
CN108067165B (zh) * | 2016-11-10 | 2019-12-10 | 国家能源投资集团有限责任公司 | 气液固多相流反应器及其控制系统、方法 |
KR102231760B1 (ko) * | 2018-01-03 | 2021-03-25 | 주식회사 엘지화학 | 공침 반응기 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07800A (ja) * | 1993-01-27 | 1995-01-06 | Sasol Chem Ind Pty Ltd | ガス状反応物から液体及びガス状生成物を製造する方法及び装置 |
US6114399A (en) * | 1993-10-27 | 2000-09-05 | North Carolina State University | Methods and apparatus for separating Fischer-Tropsch catalysts from liquid hydrocarbon product |
US20070014703A1 (en) | 2001-06-25 | 2007-01-18 | Jean-Mare Schweitzer | Apparatus and process for optimising the circulation of a suspension in a facility comprising a three-phase reactor |
JP2007516065A (ja) * | 2003-07-15 | 2007-06-21 | サソール テクノロジー(プロプライエタリー)リミテッド | 液体から触媒を分離する方法 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2780617A (en) * | 1952-05-17 | 1957-02-05 | Standard Oil Co | Ethylene polymerization with conditioned molybdena catalyst |
US4405466A (en) * | 1982-05-03 | 1983-09-20 | Ecodyne Corporation | Backwash method and apparatus |
WO1997000524A1 (de) * | 1995-06-14 | 1997-01-03 | Institut für Festkörper- und Werkstofforschung Dresden e.V. | Verfahren zur herstellung hartmagnetischer teile |
US5811469A (en) * | 1997-05-06 | 1998-09-22 | Exxon Research And Engineering Company | Slurry hydrocarbon synthesis with downcomer fed product filtration (LAW552) |
US6344490B1 (en) * | 1999-01-22 | 2002-02-05 | Exxon Research And Engineering Company | Removable filter for slurry hydrocarbon synthesis process |
AU1177100A (en) * | 1999-11-10 | 2001-06-06 | Hitachi Limited | Gas turbine equipment and gas turbine cooling method |
US6584782B2 (en) | 2000-02-25 | 2003-07-01 | Glatt Gmbh | Method for producing particulate goods |
US20050129608A1 (en) * | 2003-12-16 | 2005-06-16 | Hiroaki Takehara | Method for producing fullerenes |
-
2009
- 2009-03-12 CA CA2718077A patent/CA2718077C/en not_active Expired - Fee Related
- 2009-03-12 BR BRPI0908921-7A patent/BRPI0908921B1/pt not_active IP Right Cessation
- 2009-03-12 MY MYPI2010004266A patent/MY162163A/en unknown
- 2009-03-12 AU AU2009224342A patent/AU2009224342B2/en not_active Ceased
- 2009-03-12 EA EA201071008A patent/EA018418B1/ru not_active IP Right Cessation
- 2009-03-12 CN CN200980108669.XA patent/CN101970606B/zh not_active Expired - Fee Related
- 2009-03-12 JP JP2010502869A patent/JP5568462B2/ja active Active
- 2009-03-12 EP EP09720574.4A patent/EP2258812A4/en not_active Withdrawn
- 2009-03-12 WO PCT/JP2009/054759 patent/WO2009113613A1/ja active Application Filing
- 2009-03-12 US US12/736,108 patent/US9162170B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07800A (ja) * | 1993-01-27 | 1995-01-06 | Sasol Chem Ind Pty Ltd | ガス状反応物から液体及びガス状生成物を製造する方法及び装置 |
US6114399A (en) * | 1993-10-27 | 2000-09-05 | North Carolina State University | Methods and apparatus for separating Fischer-Tropsch catalysts from liquid hydrocarbon product |
US20070014703A1 (en) | 2001-06-25 | 2007-01-18 | Jean-Mare Schweitzer | Apparatus and process for optimising the circulation of a suspension in a facility comprising a three-phase reactor |
JP2007516065A (ja) * | 2003-07-15 | 2007-06-21 | サソール テクノロジー(プロプライエタリー)リミテッド | 液体から触媒を分離する方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2258812A4 * |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8722748B2 (en) | 2010-03-30 | 2014-05-13 | Japan Oil, Gas And Metals National Corporation | Process for producing hydrocarbons |
JP2011208091A (ja) * | 2010-03-30 | 2011-10-20 | Japan Oil Gas & Metals National Corp | 炭化水素の製造方法 |
US8906969B2 (en) | 2010-08-19 | 2014-12-09 | Japan Oil, Gas, And Metals National Corporation | Process for producing hydrocarbon oil and system for producing hydrocarbon oil |
EA023903B1 (ru) * | 2010-08-19 | 2016-07-29 | Джэпэн Ойл, Гэз Энд Металз Нэшнл Корпорейшн | Способ и система для изготовления углеводородного масла |
US9493714B2 (en) | 2010-08-19 | 2016-11-15 | Japan Oil, Gas, And Metals National Corporation | Method for producing hydrocarbon oil and system for producing hydrocarbon oil |
JP2012041449A (ja) * | 2010-08-19 | 2012-03-01 | Japan Oil Gas & Metals National Corp | 炭化水素油の製造方法及び炭化水素油の製造システム |
AU2011291804B2 (en) * | 2010-08-19 | 2016-03-10 | Cosmo Oil Co., Ltd. | Process for producing hydrocarbon oil and system for producing hydrocarbon oil |
CN103228765A (zh) * | 2010-08-19 | 2013-07-31 | 日本石油天然气·金属矿物资源机构 | 烃油的制造方法及烃油的制造系统 |
JP2012041450A (ja) * | 2010-08-19 | 2012-03-01 | Japan Oil Gas & Metals National Corp | 炭化水素油の製造方法及び炭化水素油の製造システム |
WO2012023527A1 (ja) * | 2010-08-19 | 2012-02-23 | 独立行政法人石油天然ガス・金属鉱物資源機構 | 炭化水素油の製造方法及び炭化水素油の製造システム |
JP2012201842A (ja) * | 2011-03-28 | 2012-10-22 | Japan Oil Gas & Metals National Corp | 炭化水素の製造方法 |
WO2012137936A1 (ja) * | 2011-04-08 | 2012-10-11 | 新日鉄エンジニアリング株式会社 | 触媒反応装置 |
JP2014528909A (ja) * | 2011-06-24 | 2014-10-30 | アンガス ケミカル カンパニー | 連続撹拌槽スラリー反応器を使用して、アミノアルコールの製造及び濾過をするための方法及び装置 |
JP2013034929A (ja) * | 2011-08-05 | 2013-02-21 | Japan Oil Gas & Metals National Corp | フィルタの洗浄装置 |
JP2014189603A (ja) * | 2013-03-26 | 2014-10-06 | Nippon Steel & Sumikin Engineering Co Ltd | 炭化水素合成反応装置 |
WO2014156890A1 (ja) * | 2013-03-26 | 2014-10-02 | 独立行政法人石油天然ガス・金属鉱物資源機構 | 炭化水素合成反応装置 |
US20160046870A1 (en) * | 2013-03-26 | 2016-02-18 | Japan Oil, Gas And Metals National Corporation | Hydrocarbon synthesis reaction apparatus |
US9688918B2 (en) | 2013-03-26 | 2017-06-27 | Japan Oil, Gas And Metals National Corporation | Hydrocarbon synthesis reaction apparatus |
EA032165B1 (ru) * | 2013-03-26 | 2019-04-30 | Джэпэн Ойл, Гэз Энд Металз Нэшнл Корпорейшн | Аппарат для осуществления реакции синтеза углеводородов |
Also Published As
Publication number | Publication date |
---|---|
JPWO2009113613A1 (ja) | 2011-07-21 |
CA2718077C (en) | 2014-04-15 |
JP5568462B2 (ja) | 2014-08-06 |
US20110044859A1 (en) | 2011-02-24 |
CN101970606B (zh) | 2016-01-20 |
CA2718077A1 (en) | 2009-09-17 |
AU2009224342B2 (en) | 2012-11-22 |
MY162163A (en) | 2017-05-31 |
EA201071008A1 (ru) | 2011-04-29 |
BRPI0908921B1 (pt) | 2018-01-23 |
BRPI0908921A2 (pt) | 2015-08-18 |
CN101970606A (zh) | 2011-02-09 |
US9162170B2 (en) | 2015-10-20 |
EP2258812A1 (en) | 2010-12-08 |
AU2009224342A1 (en) | 2009-09-17 |
EA018418B1 (ru) | 2013-07-30 |
EP2258812A4 (en) | 2014-01-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5568462B2 (ja) | 炭化水素化合物の合成反応システム、及び粉化粒子の除去方法 | |
JP5364715B2 (ja) | 炭化水素化合物合成反応ユニット及びその運転方法 | |
JP5364717B2 (ja) | 触媒分離システム | |
JP5417446B2 (ja) | 炭化水素合成反応装置、及び炭化水素合成反応システム、並びに液体炭化水素の回収方法 | |
AU2014246133B2 (en) | Hydrocarbon synthesis reaction apparatus | |
JPWO2010038399A1 (ja) | 炭化水素合成反応装置及び炭化水素合成反応システム、並びに炭化水素合成方法 | |
WO2010038392A1 (ja) | 気泡塔型反応器及び気泡塔型反応器の制御方法 | |
JP5501706B2 (ja) | 炭化水素の製造方法及び合成反応システム | |
JP5364714B2 (ja) | 液体燃料合成方法及び液体燃料合成装置 | |
JP5364786B2 (ja) | 触媒分離システム |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200980108669.X Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09720574 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010502869 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2718077 Country of ref document: CA |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009224342 Country of ref document: AU |
|
WWE | Wipo information: entry into national phase |
Ref document number: DZP2010000588 Country of ref document: DZ |
|
WWE | Wipo information: entry into national phase |
Ref document number: 201071008 Country of ref document: EA Ref document number: 2009720574 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: PI 2010004266 Country of ref document: MY |
|
ENP | Entry into the national phase |
Ref document number: 2009224342 Country of ref document: AU Date of ref document: 20090312 Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 12736108 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: PI0908921 Country of ref document: BR Kind code of ref document: A2 Effective date: 20100913 |