AU2007232925A1 - Starting method of liquid fuel synthesizing system, and liquid fuel synthesizing system - Google Patents

Description

DECLARATION I, Toru ISHIKAWA of c/o SHIGA INTERNATIONAL PATENT OFFICE, GranTokyo South Tower, 1-9-2, Marunouchi, Chiyoda-ku,Tokyo, Japan, understand both English and Japanese, am the translator of the English document attached, and do hereby declare and state that the attached English document contains an accurate translation of PCT International Application PCT/JP2007/056922 as filed on March 29, 2007, and that all statements made herein are true to the best of my knowledge. Declared in Tokyo, Japan This 19th day of September, 2008 Toru ISHIKAWA OSP-27777AU SPECIFICATION STARTING METHOD OF LIQUID FUEL SYNTHESIZING SYSTEM, AND LIQUID FUEL SYNTHESIZING SYSTEM 5 TECHNICAL FIELD [0001] The present invention relates to a starting method of a liquid fuel synthesizing system, and the liquid fuel synthesizing system. Priority is claimed on Japanese Patent Application No. 2006-96015, filed March 10 30, 2006, the content of which is incorporated herein by reference. BACKGROUND ART OF THE INVENTION [0002] As one of the methods for synthesizing liquid fuel from natural gas, a GTL (Gas-To-Liquid: liquid fuel synthesis) technique of reforming natural gas to produce 15 synthesis gas including carbon monoxide gas (CO) and hydrogen gas (H 2 ) as main components, synthesizing liquid hydrocarbons using this synthesis gas as a source gas by the Fischer-Tropsch synthesis reaction (hereinafter referred to as "FT synthesis reaction"), and further hydrogenating and hydrocracking the liquid hydrocarbons to manufacture liquid fuel products, such as naphtha (rough gasoline), kerosene, gas oil, and wax, has 20 recently been developed. [0003] In a conventional liquid fuel synthesizing system using the GTL technique, an oxygen plant or a carbon-dioxide-gas removal facility was required in order to manufacture and refine synthesis gas, and a hydrogen concentration adjusting apparatus was required in order to obtain a H 2 /CO ratio suitable for the FT synthesis reaction. In a 25 liquid fuel synthesizing system using the GTL technique, which was developed by the OSP-27777AU 2 present inventors, a carbon-dioxide-gas reforming method is utilized, so that synthesis gas containing a composition (H 2 /CO ratio) suitable for the FT synthesis reaction can be obtained in a single reaction, using natural gas including carbon dioxide gas as it is as a raw material. Therefore, the hydrogen concentration adjusting apparatus is unnecessary. 5 DISCLOSURE OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION [0004] Meanwhile, the above conventional liquid fuel synthesizing system using the GTL technique includes a reformer that reforms natural gas to produce carbon monoxide 10 gas and hydrogen gas, and various hydrogen-utilizing reaction apparatuses (for example, a desulfurizing reactor for desulfurizing natural gas, a hydrogenation reactor for hydrogenating synthesized liquid hydrocarbons, etc.) that utilize the hydrogen gas produced by this reformer. However, in the conventional liquid fuel synthesizing system, the above hydrogen-utilizing reaction apparatuses cannot be started up until the 15 reformer starts up to produce carbon monoxide gas and hydrogen gas. Thus, startup of the above hydrogen-utilizing reaction apparatuses is late. For this reason, a substantial amount of time is required until the whole system starts up to initiate manufacture of liquid fuel products, which causes a deterioration in production efficiency. [0005] The present invention has been made in view of such a problem, and aims at 20 providing a starting method of a liquid fuel synthesizing system, and a liquid fuel synthesizing system capable of rapidly starting hydrogen-utilizing reaction apparatuses to improve production efficiency. MEANS FOR SOLVING THE PROBLEMS 25 [0006] A starting method for a liquid fuel synthesizing system of the present invention OSP-27777AU 3 is a starting method having a reformer that reforms a hydrocarbon raw material to produce synthesis gas including carbon monoxide gas and hydrogen gas as main components, a reactor that synthesizes liquid hydrocarbons from the carbon monoxide gas and hydrogen gas included in the synthesis gas, and a hydrogen-utilizing reaction 5 apparatus that performs a predetermined reaction using the hydrogen gas included in the synthesis gas produced by the reformer, includes: separating a part of the hydrogen gas included in the synthesis gas produced by the reformer from the other part of the hydrogen gas at the normal operation of the liquid fuel synthesizing system; storing the part of the hydrogen gas separated; and supplying the hydrogen gas stored in the 10 hydrogen storage apparatus to the hydrogen-utilizing reaction apparatus at the startup of the liquid fuel synthesizing system. [0007] In the liquid fuel synthesizing system, the supply means enables to provide the hydrogen gas stored in the hydrogen storage apparatus to the hydrogen-utilizing reaction apparatus at the time of starting the liquid fuel synthesizing system. According to the 15 liquid fuel synthesizing system of the present invention, the hydrogen-utilizing reaction apparatus provided in the liquid fuel synthesizing system can be started rapidly, and the production efficiency of liquid fuel can be improved. [0008] In the starting method for a liquid fuel synthesizing system of the present invention, the hydrogen-utilizing reaction apparatus may include at least any one of a 20 hydrogenation reactor that hydrogenates the liquid hydrocarbons synthesized in the reactor, and a desulfurizing reactor that hydrogenates and desulfurizes the hydrocarbon raw material to be supplied to the reformer. [0009] In the starting method for a liquid fuel synthesizing system of the present invention, the hydrogen gas may be separated by at least any one method of a pressure 25 swing adsorption method, a hydrogen storing alloy adsorption method, and a membrane OSP-27777AU 4 separation method. [0010] In the starting method for a liquid fuel synthesizing system of the present invention, the reactor may be a slurry bubble column reactor. [0011] A liquid fuel synthesizing system of the present invention includes: a reformer 5 that reforms a hydrocarbon raw material to produce synthesis gas including carbon monoxide gas and hydrogen gas as main components; a reactor that synthesizes liquid hydrocarbons from the carbon monoxide gas and hydrogen gas included in the synthesis gas; a hydrogen-utilizing reaction apparatus that performs a predetermined reaction using the hydrogen gas included in the synthesis gas produced by the reformer; a hydrogen 10 separating apparatus that separates part of the hydrogen gas included in the synthesis gas produced by the reformer; a hydrogen storage apparatus that stores the hydrogen gas separated by the hydrogen separating apparatus; and a control means that supplies the hydrogen gas stored in the hydrogen storage apparatus to the hydrogen-utilizing reaction apparatus at the startup of the liquid fuel synthesizing system. 15 [0012] In the liquid fuel synthesizing system of the present invention, the hydrogen-utilizing reaction apparatus may include at least any one of a hydrogenation reactor that hydrogenates the liquid hydrocarbons synthesized in the reactor, and a desulfurizing reactor that hydrogenates and desulfurizes the hydrocarbon raw material to be supplied to the reformer. 20 [0013] In the liquid fuel synthesizing system of the present invention, the hydrogen separating apparatus may separate the hydrogen gas by at least any one method of a pressure swing adsorption method, a hydrogen storing alloy adsorption method, and a membrane separation method. [0014] In the liquid fuel synthesizing system of the present invention, the reactor may 25 be a slurry bubble column reactor.

OSP-27777AU 5 ADVANTAGEOUS EFFECTS OF THE INVENTION [0015] According to the liquid fuel synthesizing system of the present invention, the hydrogen-utilizing reaction apparatus provided in the liquid fuel synthesizing system can 5 be started rapidly, and the production efficiency of liquid fuel can be improved. BRIEF DESCRIPTION OF THE DRAWINGS [0016] [FIG. 1] FIG 1 is a schematic diagram showing the overall configuration of a liquid fuel synthesizing system according to an embodiment of the present invention. 10 [FIG. 2] FIG. 2 is a timing chart showing a conventional starting method for a liquid fuel synthesizing system. [FIG. 3] FIG. 3 is a schematic diagram showing a starting method for the liquid fuel synthesizing system according to the above embodiment. [FIG. 4] FIG 4 is a block diagram showing an exemplary configuration of a 15 hydrogen storage apparatus in the liquid fuel synthesizing system according to the embodiment. [FIG. 5] FIG. 5 is a block diagram showing another exemplary configuration of the hydrogen storage apparatus in the liquid fuel synthesizing system according to the embodiment. 20 DESCRIPTION OF THE REFERENCE SYMBOLS [0017] 1: LIQUID FUEL SYNTHESIZING SYSTEM 3: SYNTHESIS GAS PRODUCTION UNIT 5: FT SYNTHESIS UNIT 25 7: UPGRADING UNIT OSP-27777AU 6 10: DESULFURIZING REACTOR 12: REFORMER 14: WASTE HEAT BOILER 16 and 18: GAS-LIQUID SEPARATORS 5 20: CO 2 REMOVAL UNIT 22: ABSORPTION COLUMN 24: REGENERATION COLUMN 26: HYDROGEN SEPARATING APPARATUS 30: BUBBLE COLUMN REACTOR 10 32: HEAT TRANSFER PIPE 34 and 38: GAS-LIQUID SEPARATERS 36: SEPARATOR 40: FIRST RECTIFYING COLUMN 50: WAX COMPONENT HYDROCRACKING REACTOR 15 52: KEROSENE AND GAS OIL FRACTION HYDROTREATING REACTOR 54: NAPHTHA FRACTION HYDROTREATING REACTOR 56, 58 and 60: GAS-LIQUID SEPARATERS 70: SECOND RECTIFYING COLUMN 20 72: NAPHTHA STABILIZER 80: HYDROGEN STORAGE APPARATUS 81 and 101: STORAGE TANKS 82,83 and 104: HYDROGEN COMPRESSORS 84 and 105: CONTROLLERS 25 86, 87, 106 and 107: VALVES OSP-27777AU 7 91, 92, 93, 94 and 95: PIPELINES 102: LIQUEFYING APPARATUS 103: VAPORIZING APPARATUS 5 DESCRIPTION OF THE PREFERRED EMBODIMENTS [0018] Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In addition, in the present specification and drawings, duplicate description is omitted by giving the same reference numerals to constituent parts having substantially the same functional configurations. 10 [0019] First, with reference to FIG. 1, the overall configuration and operation of a liquid fuel synthesizing system 1 which carries out a GTL (Gas-To-Liquid) process according to an embodiment of the present invention will be described. FIG. 1 is a schematic diagram showing the overall configuration of the liquid fuel synthesizing system 1 according to the present embodiment. 15 [0020] As shown in FIG. 1, the liquid fuel synthesizing system I according to the present embodiment is a plant facility which carries out the GTL process which converts a hydrocarbon raw material, such as natural gas, into liquid fuels. This liquid fuel synthesizing system 1 includes a synthesis gas production unit 3, an FT synthesis unit 5, and an upgrading unit 7. The synthesis gas production unit 3 reforms natural gas, which 20 is a hydrocarbon raw material, to produce synthesis gas including carbon monoxide gas and hydrogen gas. The FT synthesis unit 5 produces liquid hydrocarbons from the above synthesis gas by the Fischer-Tropsch synthesis reaction (hereinafter referred to as "FT synthesis reaction"). The upgrading unit 7 hydrogenates and hydrocracks the liquid hydrocarbons produced by the FT synthesis reaction to manufacture liquid fuel products 25 (naphtha, kerosene, gas oil, wax, etc.). Hereinafter, constituent parts of each of these OSP-27777AU 8 units will be described. [0021] First, the synthesis gas production unit 3 will be described. The synthesis gas production unit 3 mainly includes, for example, a desulfurizing reactor 10, a reformer 12, a waste heat boiler 14, gas-liquid separators 16 and 18, a CO 2 removal unit 20, and a 5 hydrogen separating apparatus 26. The desulfurizing reactor 10 is composed of a hydrogenation desulfurizer, etc., and removes a sulfur component from natural gas as a raw material. The reformer 12 reforms the natural gas supplied from the desulfurizing reactor 10, to produce synthesis gas including carbon monoxide gas (CO) and hydrogen gas (H 2 ) as main components. The waste heat boiler 14 recovers heat duty of the 10 synthesis gas produced by the reformer 12, to manufacture high-pressure steam. The gas-liquid separator 16 separates the water heated by heat exchange with the synthesis gas in the waste heat boiler 14 into gas (high-pressure steam) and liquid. The gas-liquid separator 18 removes condensate components from the synthesis gas cooled down in the waste heat boiler 14, and supplies a gas component to the CO 2 removal unit 20. The 15 CO 2 removal unit 20 has an absorption column 22 which removes carbon dioxide gas from the synthesis gas supplied from the gas-liquid separator 18 by absorption, and a regeneration column 24 which diffuses and regenerates the carbon dioxide gas from the absorbent including the carbon dioxide gas. The hydrogen separating apparatus 26 separates a part of the hydrogen gas included in the synthesis gas, from the synthesis gas, 20 the carbon dioxide gas of which has been separated by the CO 2 removal unit 20. It is to be noted herein that the above CO 2 removal unit 20 may not be provided depending on circumstances. [0022] Among them, the reformer 12 reforms natural gas by using carbon dioxide and steam to produce high-temperature synthesis gas including carbon monoxide gas and 25 hydrogen gas as main components, by a steam and carbon-dioxide-gas reforming method OSP-27777AU 9 expressed by the following chemical reaction formulas (1) and (2). In addition, the reforming method in this reformer 12 is not limited to the example of the above steam and carbon-dioxide-gas reforming method. For example, a steam reforming method, a partial oxidation method (POX) using oxygen, an autothermal reforming method (ATR) 5 that is a combination of the partial oxidation method and the steam reforming method, a carbon-dioxide-gas reforming method, and the like can also be utilized. [0023] CH 4 + H 2 0 CO + 3H 2 ... (1)

CH

4 + CO 2 2CO + 2H 2 ... (2) [0024] Further, the hydrogen separating apparatus 26 is provided on a line branched 10 from a main pipe which connects the CO 2 removal unit 20 or gas-liquid separator 18 with the bubble column reactor 30. This hydrogen separating apparatus 26 can be composed of, for example, a hydrogen PSA (Pressure Swing Adsorption) device which performs adsorption and desorption of hydrogen by using a pressure difference. This hydrogen PSA device has adsorbents (zeolitic adsorbent, activated carbon, alumina, silica gel, etc.) 15 within a plurality of adsorption columns (not shown) which are arranged in parallel. By sequentially repeating processes including pressurizing, adsorption, desorption (pressure reduction), and purging of hydrogen in each of the adsorption columns, high-purity (for example, about 99.999%) hydrogen gas separated from the synthesis gas can be continuously supplied to a reactor. 20 [0025] In addition, the hydrogen gas separating method in the hydrogen separating apparatus 26 is not limited to the example of the pressure swing adsorption method as in the above hydrogen PSA apparatus. For example, there may be a hydrogen storing alloy adsorption method, a membrane separation method, or a combination thereof. [0026] The hydrogen storing alloy method is, for example, a technique of separating 25 hydrogen gas using a hydrogen storing alloy (TiFe, LaNis, TiFeo.

7 to 0.9, Mno.

3 to 0.1, OSP-27777AU 10 TiMn 5 , etc.) having a property which adsorbs or diffuses hydrogen by being cooled or heated. By providing a plurality of adsorption columns in which a hydrogen storing alloy is accommodated, and alternately repeating, in each of the adsorption columns, adsorption of hydrogen by cooling of the hydrogen storing alloy and diffusion of 5 hydrogen by heating of the hydrogen storing alloy, hydrogen gas in synthesis gas can be separated and recovered. [0027] Further, the membrane separation method is a technique of separating hydrogen gas having excellent membrane permeability out of a mixed gas, using a membrane made of a polymeric material, such as aromatic polyimide. Since this membrane separation 10 method is not accompanied with a phase change, less energy for running is required, and its running cost is reduced. Further, since the structure of a membrane separation device is simple and compact, the required cost of the facility is low and the required area of the facility is also less. Moreover, since there is no driving device in a separation membrane, and a stable running range is wide, there is an advantage in that maintenance 15 and management is easy. [0028] Next, the FT synthesis unit 5 will be described. The FT synthesis unit 5 mainly includes, for example, the bubble column reactor 30, a gas-liquid separator 34, a separator 36, a gas-liquid separator 38, and a first rectifying column 40. The bubble column reactor 30 carries out an FT synthesis reaction of the synthesis gas generated in 20 the above synthesis gas production unit 3, i.e., carbon monoxide gas and hydrogen gas, to produce liquid hydrocarbons. The gas-liquid separator 34 separates the water circulated and heated through a heat transfer pipe 32 disposed in the bubble column reactor 30 into steam (medium-pressure steam) and liquid. The separator 36 is connected to a central part of the bubble column reactor 30, and separates a catalyst and a liquid hydrocarbon 25 product. The gas-liquid separator 38 is connected to an upper part of the bubble column OSP-27777AU 11 reactor 30, and cools down unreacted synthesis gas and gaseous hydrocarbon product. The first rectifying column 40 distills the liquid hydrocarbons supplied via the separator 36 and the gas-liquid separator 38 from the bubble column reactor 30, and separates and refines the liquid hydrocarbons into individual product fractions according to boiling 5 points. [0029] Among them, the bubble column reactor 30, which is an example of a reactor which converts synthesis gas to liquid hydrocarbons, functions as a reactor which produces liquid hydrocarbons from synthesis gas by the FT synthesis reaction. This bubble column reactor 30 is composed of, for example, a slurry bubble column reactor in 10 which slurry consisting of a catalyst and medium oil is reserved inside a column. This bubble column reactor 30 produces liquid hydrocarbons from synthesis gas by the FT synthesis reaction. In detail, in this bubble column reactor 30, the synthesis gas as source gas is supplied as bubbles from a dispersing plate at the bottom of the bubble column reactor 30, and passes through the slurry consisting of a catalyst and medium oil, 15 and in a suspended state, hydrogen gas and carbon monoxide gas cause a synthesis reaction with catalyst, as shown in the following chemical reaction formula (3). [0030] 2nH 2 + nCO - (-CH 2 -)n + nH 2 0 - (3) [0031] Since this FT synthesis reaction is an exothermic reaction, the bubble column reactor 30, which is a heat exchanger-type reactor within which the heat transfer pipe 32 20 is disposed, is adapted such that, for example, water (BFW: Boiler Feed Water) is supplied as a refrigerant so that reaction heat of the above FT synthesis reaction can be recovered as medium-pressure steam by heat exchange between slurry and water. [0032] Finally, the upgrading unit 7 will be described. The upgrading unit 7 includes, for example, a WAX component hydrocracking reactor 50, a kerosene and gas oil 25 fraction hydrotreating reactor 52, a naphtha fraction hydrotreating reactor 54, gas-liquid OSP-27777AU 12 separators 56, 58 and 60, a second rectifying column 70, and a naphtha stabilizer 72. The WAX component hydrocracking reactor 50 is connected to a lower part of the first rectifying column 40. The kerosene and gas oil fraction hydrotreating reactor 52 is connected to a central part of the first rectifying column 40. The naphtha fraction 5 hydrotreating reactor 54 is connected to an upper part of the first rectifying column 40. The gas-liquid separators 56, 58 and 60 are provided so as to correspond to the hydrogenation reactors 50, 52 and 54, respectively. The second rectifying column 70 separates and refines the liquid hydrocarbons supplied from the gas-liquid separators 56 and 58 according to boiling points. The naphtha stabilizer 72 rectifies liquid 10 hydrocarbons of a naphtha fraction supplied from the gas-liquid separator 60 and the second rectifying column 70. Then, the naphtha stabilizer 72 discharges components lighter than butane towards flare gas (emission gas), and to separate and recover components having a carbon number of five or more as a naphtha product. [0033] Next, a process (GTL process) of synthesizing liquid fuel from natural gas by 15 the liquid fuel synthesizing system 1 configured as above will be described. [0034] Natural gas (whose main component is CH 4 ) as a hydrocarbon raw material is supplied to the liquid fuel synthesizing system 1 from an external natural gas supply source (not shown), such as a natural gas field or a natural gas plant. The above synthesis gas production unit 3 reforms this natural gas to manufacture synthesis gas 20 (mixed gas including carbon monoxide gas and hydrogen gas as main components). [0035] Specifically, first, the above natural gas is supplied to the desulfurizing reactor 10 along with the hydrogen gas separated by the hydrogen separating apparatus 26. The desulfurizing reactor 10 hydrogenates and desulfurizes a sulfur component included in the natural gas using the hydrogen gas, with a ZnO catalyst. By desulfurizing natural 25 gas in advance in this way, it is possible to prevent from decreasing activity of a catalyst OSP-27777AU 13 used in the reformer 12, the bubble column reactor 30, etc. because of sulfur. [0036] The natural gas (may also contain carbon dioxide) desulfurized in this way is supplied to the reformer 12 after the carbon dioxide (CO 2 ) gas supplied from a carbon-dioxide supply source (not shown) and the steam generated in the waste heat 5 boiler 14 are mixed to the desulfurized natural gas. The reformer 12 reforms natural gas by using carbon dioxide and steam to produce high-temperature synthesis gas including carbon monoxide gas and hydrogen gas as main components, by the above steam and carbon-dioxide-gas reforming method. At this time, the reformer 12 is supplied with, for example, fuel gas for a burner disposed in the reformer 12 and air, and reaction heat 10 required for the above steam and carbon-dioxide-gas reforming reaction, which is an endothermic reaction is provided by the heat of combustion of the fuel gas in the burner. [0037] The high-temperature synthesis gas (for example, 900 0 C, 2.0 MPaG) produced in the reformer 12 in this way is supplied to the waste heat boiler 14, and is cooled down by the heat exchange with the water which circulates through the waste heat boiler 14 15 (for example, 400 0 C), thereby exhausting and recovering heat. At this time, the water heated by the synthesis gas in the waste heat boiler 14 is supplied to the gas-liquid separator 16. From this gas-liquid separator 16, a gas component is supplied to the reformer 12 or other external devices as high-pressure steam (for example, 3.4 to 10.0 MPaG), and water as a liquid component is returned to the waste heat boiler 14. 20 [0038] Meanwhile, the synthesis gas cooled down in the waste heat boiler 14 is supplied to the absorption column 22 of the CO 2 removal unit 20, or the bubble column reactor 30, after condensate components are separated and removed from the synthesis gas in the gas-liquid separator 18. The absorption column 22 absorbs carbon dioxide gas included in the synthesis gas into the circulated absorbent, to remove the carbon 25 dioxide gas from the synthesis gas. The absorbent including the carbon dioxide gas OSP-27777AU 14 within this absorption column 22 is introduced into the regeneration column 24, the absorbent including the carbon dioxide gas is heated and subjected to stripping treatment with, for example, steam, and the resulting diffused carbon dioxide gas is delivered to the reformer 12 from the regeneration column 24, and is reused for the above reforming 5 reaction. [0039] The synthesis gas produced in the synthesis gas production unit 3 in this way is supplied to the bubble column reactor 30 of the above FT synthesis unit 5. At this time, the composition ratio of the synthesis gas supplied to the bubble column reactor 30 is adjusted to a composition ratio (for example, H 2 : CO = 2:1 (molar ratio)) suitable for the 10 FT synthesis reaction. In addition, the pressure of the synthesis gas supplied to the bubble column reactor 30 is raised to be suitable (for example, 3.6 MPaG) for the FT synthesis reaction by a compressor (not shown) provided in a pipe which connects the

CO

2 removal unit 20 with the bubble column reactor 30. [0040] Further, a part of the synthesis gas, the carbon dioxide gas of which has been 15 separated by the above CO 2 removal unit 20, is also supplied to the hydrogen separating apparatus 26. The hydrogen separating apparatus 26 separates the hydrogen gas included in the synthesis gas, by the adsorption and desorption (hydrogen PSA) utilizing a pressure difference as described above. This separated hydrogen is continuously supplied from a gas holder (not shown), etc. via a compressor (not shown) to various 20 hydrogen-utilizing reaction devices (for example, the desulfurizing reactor 10, the WAX component hydrocracking reactor 50, the kerosene and gas oil fraction hydrotreating reactor 52, the naphtha fraction hydrotreating reactor 54, etc.) which perform predetermined reactions utilizing hydrogen within the liquid fuel synthesizing system 1. [0041] Next, the above FT synthesis unit 5 produces liquid hydrocarbons by the FT 25 synthesis reaction from the synthesis gas produced by the above synthesis gas production OSP-27777AU 15 unit 3. [0042] Specifically, the synthesis gas produced by the above synthesis gas production unit 3 flows into the bubble column reactor 30 from the bottom of the reactor 30,, and flows up through the catalyst slurry reserved in the bubble column reactor 30. At this 5 time, within the bubble column reactor 30, the carbon monoxide and hydrogen gas which are included in the synthesis gas react with each other by the FT synthesis reaction, thereby producing hydrocarbons. Moreover, by circulating water through the heat transfer pipe 32 in the bubble column reactor 30 at the time of this synthesis reaction, the heat of the FT synthesis reaction is removed, and the water heated by this heat exchange 10 is vaporized into steam. As for this water vapor, the water separated in the gas-liquid separator 34 is returned to the heat transfer pipe 32, and the vapor is supplied to an external device as medium-pressure steam (for example, 1.0 to 2.5 MPaG). [0043] The liquid hydrocarbons synthesized in the bubble column reactor 30 in this way are removed from the central part of the bubble column reactor 30, and are introduced 15 into the separator 36. The separator 36 separates the introduced liquid hydrocarbons into a catalyst (solid component) in the extracted slurry, and a liquid component including a liquid hydrocarbon product. A part of the separated catalyst is supplied to the bubble column reactor 30, and a liquid component thereof is supplied to the first rectifying column 40. From the top of the bubble column reactor 30, unreacted 20 synthesis gas, and a gas component of the synthesized hydrocarbons are introduced into the gas-liquid separator 38. The gas-liquid separator 38 cools down these gases, and then separates some condensed liquid hydrocarbons to introduce them into the first rectifying column 40. Meanwhile, as the gas component separated in the gas-liquid separator 38, unreacted synthesis gases (CO and H 2 ) are put into the bottom of the bubble 25 column reactor 30, and reused for the FT synthesis reaction. Further, the emission gas OSP-27777AU 16 (flare gas) other than target products, which contains as a main component hydrocarbon gas having a low carbon number (C 4 or less), is introduced into an external combustion facility (not shown), is combusted therein, and is then discharged to the atmosphere. [0044] Next, the first rectifying column 40 heats the liquid hydrocarbons (whose carbon 5 numbers are various) supplied via the separator 36 and the gas-liquid separator 38 from the bubble column reactor 30 as described above, to fractionally distill the liquid hydrogen using a difference in boiling point. Thereby, the first rectifying column 40 separates and refines the liquid hydrogen into a naphtha fraction (whose boiling point is less than about 315 0 C), a kerosene and gas oil fraction (whose boiling point is about 315 10 to 800 0 C), and a WAX component (whose boiling point is greater than about 800 0 C). The liquid hydrocarbons (mainly C 21 or more) as the WAX component extracted from the bottom of the first rectifying column 40 are transferred to the WAX component hydrocracking reactor 50, the liquid hydrocarbons (mainly C 11 to C 20 ) as the kerosene and gas oil fraction removed from the central part of the first rectifying column 40 are 15 transferred to the kerosene and gas oil fraction hydrotreating reactor 52, and the liquid hydrocarbons (mainly C 5 to Co 10 ) as the naphtha fraction extracted from the upper part of the first rectifying column 40 are transferred to the naphtha fraction hydrotreating reactor 54. [0045] The WAX component hydrocracking reactor 50 hydrocracks the liquid 20 hydrocarbons as the WAX component with a large carbon number (approximately C 2 1 or more), which have been supplied from the lower part of the first rectifying column 40, by using the hydrogen gas supplied from the above hydrogen separating apparatus 26, to reduce the carbon number to less than C 20 . In this hydrocracking reaction, hydrocarbons with a large carbon number and with low molecular weight are generated 25 by cleaving C-C bonds of hydrocarbons with a large carbon number, using a catalyst and OSP-27777AU 17 heat. A product including the liquid hydrocarbons hydrocracked by this WAX component hydrocracking reactor 50 is separated into gas and liquid in the gas-liquid separator 56, the liquid hydrocarbons of which are transferred to the second rectifying column 70, and the gas component (including hydrogen gas) of which is transferred to 5 the kerosene and gas oil fraction hydrotreating reactor 52 and the naphtha fraction hydrotreating reactor 54. [0046] The kerosene and gas oil fraction hydrotreating reactor 52 hydrotreats liquid hydrocarbons (approximately Cl to C 2 0 ) as the kerosene and gas oil fractions having an approximately middle carbon number, which have been supplied from the central part of 10 the first rectifying column 40, by using the hydrogen gas supplied via the WAX component hydrocracking reactor 50 from the hydrogen separating apparatus 26. This hydrotreating reaction is a reaction which adds hydrogen to unsaturated bonds of the above liquid hydrocarbons, to saturate the liquid hydrocarbons and to generate straight-chain saturated hydrocarbons. As a result, a product including the hydrotreated 15 liquid hydrocarbons is separated into gas and liquid in the gas-liquid separator 58, the liquid hydrocarbons of which are transferred to the second rectifying column 70, and the gas component (including hydrogen gas) of which is reused for the above hydrogenation reaction. [0047] The naphtha fraction hydrotreating reactor 54 hydrotreats liquid hydrocarbons 20 (approximately CI 0 or less) as the naphtha fraction with a low carbon number, which have been supplied from the upper part of the first rectifying column 40, by using the hydrogen gas supplied via the WAX component hydrocracking reactor 50 from the hydrogen separating apparatus 26. As a result, a product including the hydrotreated liquid hydrocarbons is separated into gas and liquid in the gas-liquid separator 60, the 25 liquid hydrocarbons of which are transferred to the naphtha stabilizer 72, and the gas OSP-27777AU 18 component (including hydrogen gas) of which is reused for the above hydrogenation reaction. [0048] Next, the second rectifying column 70 distills the liquid hydrocarbons supplied from the WAX component hydrocracking reactor 50 and the kerosene and gas oil fraction 5 hydrotreating reactor 52 as described above. Thereby, the second rectifying column 70 separates and refines the liquid hydrogen into a naphtha fraction (whose boiling point is less than about 315 0 C) with a carbon number of 10 or less, kerosene (whose boiling point is about 315 to 450 0 C), and gas oil (whose boiling point is about 450 to 800 0 C). The gas oil is extracted from a lower part of the second rectifying column 70, and the 10 kerosene is extracted from a central part thereof. Meanwhile, a hydrocarbon gas with a carbon number of 10 or more is extracted from the top of the second rectifying column 70, and is supplied to the naphtha stabilizer 72. [0049] Moreover, the naphtha stabilizer 72 distills the hydrocarbons with a carbon number of 10 or less, which have been supplied from the above naphtha fraction 15 hydrotreating reactor 54 and second rectifying column 70. Thereby, the naphtha stabilizer 72 separates and refines naphtha (C 5 to Cl 0 ) as a product. Accordingly, high-purity naphtha is extracted from a lower part of the naphtha stabilizer 72. Meanwhile, the emission gas (flare gas) other than products, which contains as a main component hydrocarbons with a carbon number lower than or equal to a predetermined 20 number or less (lower than or equal to C 4 ) is discharged from the top of the naphtha stabilizer 72. Further, the emission gas is introduced into an external combustion facility (not shown), is combusted therein, and is then discharged to the atmosphere. [0050] The process (GTL process) of the liquid fuel synthesizing system 1 has been described hitherto. By the GTL process, natural gas can be easily and economically 25 converted into clean liquid fuels, such as high-purity naphtha (C 5 to CIo: rough gasoline), OSP-27777AU 19 kerosene (C 11 to Cs 15 : kerosene), and gas oil (C 16 to C 20 : gas oil). Moreover, in the present embodiment, the above steam and carbon-dioxide-gas reforming method is adopted in the reformer 12. Thus, there are advantages in that carbon dioxide contained in natural gas to be used as a raw material can be effectively utilized, the composition 5 ratio (for example, H 2 :CO = 2:1 (molar ratio)) of a synthesis gas suitable for the above FT synthesis reaction can be efficiently produced in one reaction of the reformer 12, and a hydrogen concentration adjustor, etc. is unnecessary. [0051] Next, in the liquid fuel synthesizing system 1 according to the present embodiment, a supply system of hydrogen gas to a hydrogen-utilizing reaction apparatus 10 which performs a predetermined reaction using hydrogen gas will be described in detail. [0052] In the above liquid fuel synthesizing system 1, at the time of normal operation (at the time of steady operation after lapse of a predetermined time from system startup), the hydrogen separating apparatus 26 separates part of the hydrogen gas in the synthesis gas produced by the reformer 12 to continuously supply this separated hydrogen gas to a 15 hydrogen-utilizing reaction apparatus (for example, the desulfurizing reactor 10 of the synthesis gas production unit 3, the WAX component hydrocracking reactor 50, the kerosene and gas oil fraction hydrotreating reactor 52, and the naphtha fraction hydrotreating reactor 54 (hereinafter generically referred to as " hydrogenation reactors 50, 52 and 54)) of the upgrading unit 7. 20 [0053] Meanwhile, only in such a supply system of hydrogen gas, at the time of startup of the liquid fuel synthesizing system 1 (also including each startup of the units 3, 5 and 7), normal operation is not performed after the reformer 12 is started up. As a result, hydrogen gas is not supplied to the hydrogenation reactors 50, 52 and 54 of the above upgrading unit 7 until synthesis gas is stably produced and supplied. Thus, the 25 hydrogenation reactors 50, 52 and 54 cannot be started up. For this reason, there is OSP-27777AU 20 conventionally a problem in that the whole liquid fuel synthesizing system 1 may be started up, and a substantial amount of time may be required until liquid fuel products are manufactured, which results in poor production efficiency. [0054] Startup delay of the hydrogenation reactors 50, 52 and 54 of this upgrading unit 5 7 will be concretely described with reference to FIG. 2. As shown in FIG. 2, conventionally, when the liquid fuel synthesizing system 1 is started up, first, the reformer 12 of the synthesis gas production unit 3 is started up, thereby initiating the production reaction of synthesis gas. The day when this reformer 12 operates normally so that it can stably supply the synthesis gas is the 4th day from the startup. Further, if 10 the FT synthesis unit 5 is started up, for example, one day after the startup of the synthesis gas production unit 3 to perform adjustment of apparatuses and preparation for the FT synthesis reaction, the FT synthesis unit can stably execute the FT synthesis reaction from the same day (i.e. the 4th day) as the day when the synthesis gas production unit 3 operates normally. 15 [0055] Meanwhile, as for the upgrading unit 7, it is possible to start up the hydrogenation reactors 50, 52 and 54 to initiate preparation for catalytic reduction or hydrogenation reaction only after (the 4th day or later) the hydrogen gas produced by the reformer 12 is supplied to the hydrogenation reactors 50, 52 and 54. For this reason, the day when the upgrading unit 7 can stably execute hydrogenation and refining reactions is 20 the 8th day from the startup of the synthesis gas production unit 3, which requires a long startup period. Therefore, there is a problem in that the time to when the whole liquid fuel synthesizing system 1 is fully started up so that it can stably manufacture liquid fuel products is extremely late, i.e., the 8th day from the startup of the synthesis gas production unit 3 (the 4th day after initiation of the steady operation of the synthesis gas 25 production unit 3), which results in low production efficiency.

OSP-27777AU 21 [0056] Moreover, although the FT synthesis unit 5 normally operates on the 4th day to the 7th day after the startup of the synthesis gas production unit, the upgrading unit 7 does not operate normally. Thus, there is also a problem in that a raw product storage tank (not shown) for storing the liquid hydrocarbons (raw products before being 5 hydrogenated and refined) produced by the FT synthesis reaction is required. [0057] Thus, in order to solve these problems, the liquid fuel synthesizing system 1 according to the present embodiment, as shown in FIG. 1, is provided with a hydrogen storage apparatus 80 which stores the hydrogen gas separated and recovered from synthesis gas by the hydrogen separating apparatus 26 so that the hydrogen gas stored in 10 this hydrogen storage apparatus 80 can be supplied to the desulfurizing reactor 10 of the synthesis gas production unit 3, the hydrogenation reactors 50, 52 and 54 of the upgrading unit 7, etc. That is, a supply system which once stores hydrogen gas from the hydrogen separating apparatus 26 in the hydrogen storage apparatus 80 and supplies it indirectly is provided separately from the above-described supply system which directly 15 supplies hydrogen gas from the hydrogen separating apparatus 26 to hydrogen-utilizing reaction apparatuses, such as the desulfurizing reactor 10 and the hydrogenation reactors 50, 52 and 54. [0058] In such a configuration, at the time of the normal operation of the liquid fuel synthesizing system 1, the full amount of the hydrogen gas separated from synthesis gas 20 by the hydrogen separating apparatus 26 is not fully supplied to hydrogen-utilizing reaction apparatuses, such as the desulfurizing reactor 10 and the hydrogenation reactors 50, 52 and 54, but part of the hydrogen gas is stored in the hydrogen storage apparatus 80. Also, at the time of the restart, etc. of the liquid fuel synthesizing system 1 after the normal operation, when the hydrogenation reactors 50, 52 and 54 are restarted, the 25 hydrogen gas stored in the hydrogen storage apparatus 80 is immediately supplied to the OSP-27777AU 22 hydrogenation reactors 50, 52 and 54, the desulfurizing reactor 10, etc. This makes it possible to rapidly start up hydrogen-utilizing reaction apparatuses, such as the hydrogenation reactors 50, 52 and 54 and the desulfurizing reactor 10, before the reformer 12 is started up to stably supply hydrogen gas. 5 [0059] Specifically, as shown in FIG 3, when the liquid fuel synthesizing system 1 according to the present embodiment is restarted, first, the hydrogen gas stored in the hydrogen storage apparatus 80 is supplied to the hydrogenation reactors 50, 52 and 54 of the upgrading unit 7. Accordingly, before startup of the reformer 12, the hydrogenation reactors 50, 52 and 54 can be started up so as to initiate preparation for catalytic 10 reduction or hydrogenation reaction. Next, one day after the startup of the hydrogenation reactors 50, 52 and 54, the synthesis gas production unit 3 is started up to supply the hydrogen gas stored in the hydrogen storage apparatus 80 to the desulfurizing reactor 10, and the reformer 12 is started up. Further, after one day, the FT synthesis unit 5 is started up to perform preparation for apparatus adjustment and FT synthesis 15 reaction. Accordingly, for example, on the 5th day from the above startup of the hydrogenation reactors 50, 52 and 54, the reformer 12 can be normally started up to stably supply synthesis gas, and liquid hydrocarbons can be stably produced by the FT synthesis reaction in the bubble column reactor 30. Moreover, at this time (on the 5th day), the preparation operation of the hydrogenation reactors 50, 52 and 54, etc. is 20 completed in the upgrading unit 7. Thus, the upgrading unit 7 can stably execute the hydrogenation reaction (the reduction reaction or hydrocracking reaction) and refining reaction of the liquid hydrocarbons from the FT synthesis unit, thereby initiating manufacture of liquid fuel products. [0060] As such, in the present embodiment, the hydrogen gas stored in the hydrogen 25 storage apparatus 80 is supplied to the hydrogenation reactors 50, 52 and 54, or the OSP-27777AU 23 desulfurizing reactor 10, at the time of restart of the liquid fuel synthesizing system 1. Since this can shorten the startup time of the whole system to initiate manufacture of liquid fuel products early, production efficiency can be improved. [0061] Subsequently, an exemplary configuration of the hydrogen storage apparatus 80 5 in the liquid fuel synthesizing system according to the present embodiment will be described in detail, referring to FIGS. 4 and 5. FIGS. 4 and 5 are respectively block diagrams showing exemplary configurations of the hydrogen storage apparatus 80 in the liquid fuel synthesizing system 1 according to the present embodiment. In addition, in FIGS. 4 and 5, for convenience of description, only main constituent parts of the liquid 10 fuel synthesizing system 1 in FIG. I are illustrated, and illustration of some constituent parts is omitted. [0062] As shown in FIGS. 4 and 5, in the liquid fuel synthesizing system 1, the hydrogen separating apparatus 26 and the hydrogen storage apparatus 80 are connected to each other via a pipeline 91, and the hydrogen storage apparatus 80 and the 15 desulfurizing reactor 10, and the hydrogen storage apparatus and the hydrogenation reactors 50, 52 and 54 are connected to each other via pipelines 92 and 93, respectively. [0063] First, the hydrogen storage apparatus 80 of the example of FIG 4 will be described in detail. As shown in FIG 4, the hydrogen storage apparatus 80 includes a storage tank 81 composed of, for example, proof-pressure containers, such as a spherical 20 storage tank, a hydrogen compressor 82 to which the pipeline 91 from the above hydrogen separating apparatus 26 is connected, and which is connected to the inlet side of the storage tank 81, a hydrogen compressor 83 which is connected to the outlet side of the storage tank 81 and is connected to the desulfurizing reactor 10 and the hydrogenation reactors 50, 52 and 54 via the above pipelines 92 and 93, respectively, and 25 a controller 84 which controls each part of the hydrogen storage apparatus 80. In OSP-27777AU 24 addition, the controller 84 is an example of a control means which controls the operation (for example, storage operation of hydrogen gas, operation of supply of stored hydrogen gas to a hydrogen-utilizing reaction apparatus, etc.) of the hydrogen storage apparatus 80. [0064] The operation of the hydrogen storage apparatus 80 in FIG. 4 having such a 5 configuration will be described. At the time of the normal operation of the above liquid fuel synthesizing system 1, part of the hydrogen gas is separated and recovered by the hydrogen separating apparatus 26 from the synthesis gas produced by the reformer 12, and is supplied to the desulfurizing reactor 10 or the hydrogenation reactors 50, 52 and 54 via pipelines 94 and 95. At the time of this normal operation, for example, a storage 10 instruction signal based on input by an operator or a storage instruction signal from a controller (not shown) of the liquid fuel synthesizing system 1 is input to the controller 84 of the hydrogen storage apparatus 80. Then, in order to store hydrogen gas in the storage tank 81, the controller 84 controls operation of the hydrogen compressor 82, and controls opening of a valve 86 on the inlet side of the storage tank 81 and closing of a 15 valve 87 on the outlet side of the storage tank. Accordingly, part of the hydrogen gas emitted from the hydrogen separating apparatus 26 is supplied to the hydrogen compressor 82 via the pipeline 91, and the hydrogen compressor 82 compresses the supplied hydrogen gas, and stores the hydrogen gas in the storage tank 81 with a predetermined storage pressure (for example, 3 MPaG). Thereafter, when a sufficient 20 amount of hydrogen gas is stored, the controller 84 stops the operation of the hydrogen compressor 82 and closes the valve 86 on the inlet side of the storage tank 81, thereby completing the storage operation. [0065] Meanwhile, at the startup of the liquid fuel synthesizing system 1, a supply instruction signal based on input by an operator, or a supply instruction signal from a 25 controller (not shown) of the liquid fuel synthesizing system 1 is input to the controller OSP-27777AU 25 84 of the hydrogen storage apparatus 80. Then, in order to supply the hydrogen gas stored in the storage tank 81 as described above, the controller 84 controls to operation of the hydrogen compressor 83, and controls opening of the valve 87 on the outlet side of the storage tank 81 with the valve 86 on the inlet side of the storage tank closed. 5 Thereby, the pressure of the hydrogen gas stored in the storage tank 81 is raised to a predetermined pressure (for example, 3.6 MPaG) suitable for the bubble column reactor 30 by the hydrogen compressor 83, and the hydrogen gas, the pressure of which is raised, is supplied to the desulfurizing reactor 10 and the hydrogenation reactors 50, 52 and 54 via the pipelines 92 and 93. As such, in the example of FIG. 4, the hydrogen storage 10 apparatus 80 having a comparatively simple apparatus configuration can be used to immediately supply the hydrogen gas stored in the storage tank 81 to a required place. [0066] Next, the hydrogen storage apparatus 80 of the example of FIG. 5 will be described in detail. The hydrogen storage apparatus of this FIG. 5 is constituted of a liquefied hydrogen storage apparatus which liquefies and stores hydrogen gas in order to 15 store a larger volume of hydrogen. [0067] As shown in FIG 5, the hydrogen storage apparatus 80 includes a storage tank 101 composed of, for example, proof-pressure containers, such as a spherical storage tank, a hydrogen compressor 102 to which the pipeline 91 from the above hydrogen separating apparatus 26 is connected, and which is connected to the inlet side of the 20 storage tank 101, a vaporizing apparatus which is connected to the outlet side of the storage tank 101, a hydrogen compressor 104 which is connected to the desulfurizing reactor 10 and the hydrogenation reactors 50, 52 and 54 via the above pipelines 92 and 93, respectively, and a controller 105 which controls each part of the hydrogen storage apparatus 80. Among them, the liquefying apparatus 102 can liquefy hydrogen gas 25 depending on, for example, a thermodynamic cycle, such as a Joule-Thomson cycle, an OSP-27777AU 26 isoentropic expansion cycle, or a helium Brighton cycle. Further, the vaporizing apparatus 103 has a heat exchanger, etc., and can heat and evaporate the liquefied hydrogen supplied from the storage tank 101 into hydrogen gas. In addition, the controller 105 is an example of a control means which controls the operation (for 5 example, storage operation of hydrogen gas, operation of supply of stored hydrogen gas to a hydrogen-utilizing reaction apparatus, etc.) of the hydrogen storage apparatus 80. [0068] The operation of the hydrogen storage apparatus 80 in FIG 5 having such a configuration will be described. At the time of the normal operation of the above liquid fuel synthesizing system 1, similarly to the example of FIG. 4, a storage instruction signal 10 is input to the controller 105 of the hydrogen storage apparatus 80. Then, in order to store hydrogen gas in the storage tank 101, the controller 105 controls to operation of the liquefying apparatus 102, and controls opening of a valve 106 on the inlet side of the storage tank 101 and closing of a valve 107 on the outlet side of the storage tank. Accordingly, part of the hydrogen gas emitted from the hydrogen separating apparatus 26 15 is supplied to the liquefying apparatus 102 via the pipeline 91, and the liquefying apparatus 102 liquefies the supplied hydrogen gas, and stores the liquefied hydrogen in the storage tank 101 with predetermined storage pressure (for example, 0.5 MPaG). Thereafter, when a sufficient amount of liquefied hydrogen is stored, the controller 105 stops the operation of the liquefying apparatus 102, and closes the valve 106 on the inlet 20 side of the storage tank 101, thereby completing the storage operation. [0069] Meanwhile, at the time of the startup of the liquid fuel synthesizing system 1, similarly to the example of FIG 4, a supply instruction signal is input to the controller 105 of the hydrogen storage apparatus 80. Then, in order to evaporate the hydrogen gas stored in the storage tank 101 as described above into hydrogen gas to supply it, the 25 controller 105 controls operation of the vaporizing apparatus 103 and the hydrogen OSP-27777AU 27 compressor 104, and controls opening of the valve 106 on the outlet side of the storage tank 101 with the valve 106 on the inlet side of the storage tank closed. Thereby, the liquefied hydrogen stored in the storage tank 101 is vaporized and turned into hydrogen gas by the vaporizing apparatus 103. As a result, the pressure of the hydrogen gas is 5 raised to a predetermined pressure (for example, 3.6 MPaG) of the bubble column reactor 30 by the hydrogen compressor 83, and the hydrogen gas, the pressure of which is raised, is supplied to the desulfurizing reactor 10 and the hydrogenation reactors 50, 52 and 54 via the pipelines 92 and 93. As such, in the example of FIG 5, hydrogen gas is liquefied and stored, so that a large amount of hydrogen can be stored in the storage tank 10 101, and at the time of startup of the liquid fuel synthesizing system 1, the hydrogen gas stored as liquefied hydrogen in the storage tank 101 is vaporized and can be supplied to a required place instantaneously in large quantities. [0070] The liquid fuel synthesizing system 1 according to the present embodiment, and the starting method of this liquid fuel synthesizing system I has been described in detail. 15 According to the present embodiment, the hydrogen storage apparatus 80 is provided. Accordingly, at the time of the normal operation of the liquid fuel synthesizing system 1, part of the hydrogen gas in the synthesis gas produced by the reformer 12 is stored in the hydrogen storage apparatus 80, so that a predetermined amount or more of hydrogen can be secured, and when hydrogen gas is needed, the hydrogen gas can be supplied 20 instantaneously from the hydrogen storage apparatus 80. For this reason, the hydrogen gas stored in the hydrogen storage apparatus 80 can be immediately supplied to hydrogen-utilizing reaction apparatuses, such as the hydrogenation reactors 50, 52 and 54, or the desulfurizing reactor 10, at the time of the restart, etc. of the liquid fuel synthesizing system 1. Thus, the time required to start and steadily operate these 25 hydrogen-utilizing reaction apparatuses can be shortened to the minimum. Accordingly, OSP-27777AU 28 since the startup time of the whole liquid fuel synthesizing system 1 can be shortened significantly, the production efficiency of liquid fuel products, such as naphtha, kerosene, and gas oil, can be improved. [0071] Although the preferred embodiments of the present invention have been 5 described with reference to the accompanying drawings, it is needless to say that the present invention is not limited to such embodiments. It is apparent to those skilled in the art that various alternations or modifications can be made in the scope as set forth in the claims, and it will be understood that these alternations or modifications naturally belong to the technical scope of the present invention. 10 [0072] For example, in the above embodiments, natural gas is used as a hydrocarbon raw material to be supplied to the liquid fuel synthesizing system 1. However, the present invention is not limited to such an example. For example, other hydrocarbon raw materials, such as asphalt and residual oil, may be used. [0073] Further, in the above embodiments, liquid hydrocarbons are synthesized by the 15 FT synthesis reaction as a synthesis reaction in the bubble column reactor 30. However, the present invention is not limited to this example. Specifically, the present invention can also be applied to, for example, oxo synthesis (hydroformylation reaction)

"R-CH=CH

2 + CO + H 2 -_+ R-CH 2

CH

2 CHO", methanol synthesis "CO + 2H 2

-

CH

3 OH", dimethylether (DME) synthesis "3CO + 3H 2 -_+ CH 3

OCH

3 + CO 2 ", etc., as the 20 synthesis reaction in the bubble column reactor. [0074] Further, in the above embodiment, the desulfurizing reactor 10, the WAX component hydrocracking reactor 50, the kerosene and gas oil fraction hydrotreating reactors 52, and the naphtha fraction hydrotreating reactors 54 are given as examples of the hydrogen-utilizing reaction apparatus. However, the present invention is not limited 25 to such examples. Any apparatuses other than the above ones may be adopted as long OSP-27777AU 29 as they perform a predetermined reaction utilizing hydrogen gas in a liquid fuel synthesizing system. Specifically, the hydrogen-utilizing reaction apparatus may be, for example, a fuel cell, an apparatus which performs hydrogenation reaction (naphthalene -4 decalin) of naphthalene, an apparatus which performs hydrogenation reaction 5 (benzene -* cyclohexane, etc.) of aromatic hydrocarbons (benzene), or an apparatus which performs hydrogenation reaction on unsaturated fatty acid. [0075] Further, in the above embodiments, the slurry bubble column reactor is used as the reactor which synthesizes synthesis gas into liquid hydrocarbons. However, the present invention is not limited to such an example. For example, an FT synthesis 10 reaction using a fixed bed type reactor, etc. may be performed. INDUSTRIAL APPLICABILITY [0076] The present invention relates to a starting method for a liquid fuel synthesizing system having a reformer that reforms a hydrocarbon raw material to produce synthesis 15 gas including carbon monoxide gas and hydrogen gas as main components, a reactor that synthesizes liquid hydrocarbons from the carbon monoxide gas and hydrogen gas included in the synthesis gas, and a hydrogen-utilizing reaction apparatus that performs a predetermined reaction using the hydrogen gas included in the synthesis gas produced by the reformer, including: separating a part of the hydrogen gas included in the synthesis 20 gas produced by the reformer from the other part of the hydrogen gas at the normal operation of the liquid fuel synthesizing system; storing the part of the hydrogen gas separated; and supplying the hydrogen gas stored in the hydrogen storage apparatus to the hydrogen-utilizing reaction apparatus at the startup of the liquid fuel synthesizing system. 25 According to the liquid fuel synthesizing system of the present invention, production OSP-27777AU 30 efficiency can be improved by rapidly starting up the hydrogen-utilizing reaction apparatus.

Claims (8)

1. A starting method for a liquid fuel synthesizing system having a reformer that reforms a hydrocarbon raw material to produce synthesis gas including carbon monoxide 5 gas and hydrogen gas as main components, a reactor that synthesizes liquid hydrocarbons from the carbon monoxide gas and hydrogen gas included in the synthesis gas, and a hydrogen-utilizing reaction apparatus that performs a predetermined reaction using the hydrogen gas included in the synthesis gas produced by the reformer, comprising: separating a part of the hydrogen gas included in the synthesis gas produced by 10 the reformer from the other part of the hydrogen gas at the normal operation of the liquid fuel synthesizing system; storing the part of the hydrogen gas separated; and supplying the hydrogen gas stored in the hydrogen storage apparatus to the hydrogen-utilizing reaction apparatus at the startup of the liquid fuel synthesizing system. 15

2. The starting method for a liquid fuel synthesizing system according to Claim 1, wherein the hydrogen-utilizing reaction apparatus includes at least any one of a hydrogenation reactor that hydrogenates the liquid hydrocarbons synthesized in the 20 reactor, and a desulfurizing reactor that hydrogenates and desulfurizes the hydrocarbon raw material to be supplied to the reformer.

3. The starting method for a liquid fuel synthesizing system according to Claim 1, wherein 25 the hydrogen gas is separated by at least any one method of a pressure swing OSP-27777AU 32 adsorption method, a hydrogen storing alloy adsorption method, and a membrane separation method.

4. The starting method for a liquid fuel synthesizing system according to Claim 1, 5 wherein the reactor is a slurry bubble column reactor.

5. A liquid fuel synthesizing system comprising: a reformer that reforms a hydrocarbon raw material to produce synthesis gas 10 including carbon monoxide gas and hydrogen gas as main components; a reactor that synthesizes liquid hydrocarbons from the carbon monoxide gas and hydrogen gas included in the synthesis gas; a hydrogen-utilizing reaction apparatus that performs a predetermined reaction using the hydrogen gas included in the synthesis gas produced by the reformer; 15 a hydrogen separating apparatus that separates part of the hydrogen gas included in the synthesis gas produced by the reformer from the other part of the hydrogen gas; a hydrogen storage apparatus that stores the hydrogen gas separated by the hydrogen separating apparatus; and a control means that supplies the hydrogen gas stored in the hydrogen storage 20 apparatus to the hydrogen-utilizing reaction apparatus at the startup of the liquid fuel synthesizing system.

6. The liquid fuel synthesizing system according to Claim 5, wherein the hydrogen-utilizing reaction apparatus includes at least any one of a 25 hydrogenation reactor that hydrogenates the liquid hydrocarbons synthesized in the OSP-27777AU 33 reactor, and a desulfurizing reactor that hydrogenates and desulfurizes the hydrocarbon raw material to be supplied to the reformer.

7. The liquid fuel synthesizing system according to Claim 5, wherein 5 the hydrogen separating apparatus separates the hydrogen gas by at least any one method of a pressure swing adsorption method, a hydrogen storing alloy adsorption method, and a membrane separation method.

8. The liquid fuel synthesizing system according to Claim 5, wherein 10 the reactor is a slurry bubble column reactor.