WO2007114276A1

WO2007114276A1 - Method for start-up of liquid fuel synthesis system, and liquid fuel synthesis system

Info

Publication number: WO2007114276A1
Application number: PCT/JP2007/056922
Authority: WO
Inventors: Yasuhiro Onishi; Osamu Wakamura; Kenichiro Fujimoto
Original assignee: Nippon Steel Engineering Co., Ltd.
Priority date: 2006-03-30
Filing date: 2007-03-29
Publication date: 2007-10-11
Also published as: CN101432393B; ZA200808244B; MY149999A; AU2007232925C1; JPWO2007114276A1; CN101432393A; RU2008141284A; AU2007232925B2; RU2430954C2; AU2007232925A1

Abstract

Disclosed is a liquid fuel synthesis system which comprises: a reformer (12) for reforming a hydrocarbon raw material to produce a synthetic gas composed mainly of a carbon monoxide gas and a hydrogen gas; a bubble column reactor (30) for synthesizing a liquid hydrocarbon from the carbon monoxide gas and the hydrogen gas contained in the synthetic gas produced in the reformer (12); hydrogen-utilizing reactors (10, 50, 52, 54) for conducting a given reaction by utilizing the hydrogen gas contained in the synthetic gas produced in the reformer (12); a hydrogen-separation unit (26) for separating a part of the hydrogen gas contained in the synthetic gas produced in the reformer (12); and a hydrogen storage unit (80) for storing the hydrogen gas separated by the hydrogen-separation unit (26). Upon starting up the system, the hydrogen gas stored in the hydrogen storage unit (80) is supplied into the hydrogen-utilizing reactors (10, 50, 52, 54).

Description

Specification

Technical field of starting liquid fuel synthesis system and liquid fuel synthesis system

The present invention relates to a method for starting a liquid fuel synthesis system and a liquid fuel synthesis system.

This application claims priority on Japanese Patent Application No. 2006-96015 filed on Mar. 30, 2006, the contents of which are incorporated herein by reference.

Background art

[0002] In recent years, as one of the methods for synthesizing liquid fuel from natural gas, the natural gas is reformed to produce synthesis gas mainly composed of carbon monoxide gas (CO) and hydrogen gas (H). And this

2

By synthesizing liquid hydrocarbons using Fischer's Tropsch synthesis reaction (hereinafter referred to as “FT synthesis reaction”) using the synthesized gas as raw material gas, and then hydrolyzing this liquid hydrocarbon to refine it, naphtha (crude gasoline) GTL (Gas To Liquid) technology for producing liquid fuel products such as kerosene, light oil and wax has been developed.

[0003] The conventional liquid fuel synthesis system using GTL technology requires an oxygen plant and carbon dioxide removal equipment to produce and purify synthesis gas, and obtain a H / CO ratio suitable for the FT synthesis reaction. Therefore, a hydrogen concentration adjusting device was necessary. In addition, the inventors of the present application

2

In the liquid fuel synthesis system using the developed GTL technology, the composition suitable for the FT synthesis reaction (H / CO) is obtained by using the natural gas containing carbon dioxide as a raw material by using the carbon dioxide reforming method. Ratio) synthesis gas can be obtained in a single reaction, so the hydrogen concentration

2

An adjustment device can be dispensed with.

Disclosure of the invention

Problems to be solved by the invention

[0004] By the way, the above-described conventional liquid fuel synthesis system using GTL technology includes a reformer that reforms natural gas to produce carbon monoxide gas and hydrogen gas, and a hydrogen gas that is produced by the reformer. Equipped with various hydrogen-utilizing reactors (for example, desulfurization reactors for desulfurizing natural gas and hydrogenation reactors for hydrogenating synthesized liquid hydrocarbons) It is. However, in the conventional liquid fuel synthesis system, the hydrogen utilization reactor cannot be activated until the carbon monoxide gas and hydrogen gas are generated after the reformer is activated. The reactor starts slowly. For this reason, it takes time for the entire system to start up and start production of liquid hydrocarbon products, which is a cause of reduced production efficiency.

[0005] The present invention has been made in view of the above problems, and a method for starting a liquid fuel synthesis system capable of quickly starting a hydrogen-using reaction apparatus to improve production efficiency, and liquid fuel The object is to provide a synthesis system.

Means for solving the problem

[0006] A method for starting a liquid fuel synthesizing system of the present invention includes a reformer that reforms a hydrocarbon raw material to generate synthesis gas mainly composed of carbon monoxide gas and hydrogen gas, and the synthesis gas. A reactor for synthesizing liquid hydrocarbons from carbon monoxide gas and hydrogen gas, and a hydrogen-based reaction device for performing a predetermined reaction using the hydrogen gas contained in the synthesis gas generated by the reformer. A method for starting a liquid fuel synthesis system, comprising: separating and storing a part of hydrogen gas contained in synthesis gas generated by the reformer during steady operation of the liquid fuel synthesis system; When the liquid fuel synthesizing system is started, hydrogen gas stored in the hydrogen storage device is supplied to the hydrogen-utilizing reactor.

[0007] According to the method for starting a liquid fuel synthesis system of the present invention, hydrogen gas stored in advance during normal operation of the liquid fuel synthesis system is supplied to the hydrogen-utilizing reactor when the hydrogen-using reactor is started. Therefore, the predetermined reaction using hydrogen can be started immediately in the hydrogen-using reaction apparatus. As a result, the hydrogen-utilizing reactor can be quickly started before the reformer-powered hydrogen gas is supplied, so that the production efficiency of the liquid fuel synthesis system can be improved.

[0008] In the method for starting a liquid fuel synthesizing system of the present invention, the hydrogen-utilizing reaction apparatus is supplied to a hydrogenation reactor for hydrogenating liquid hydrocarbons synthesized in the reactor, or to the reformer. It may contain at least one of desulfurization reactors for hydrodesulfurizing the hydrocarbon feedstock.

[0009] According to the start-up method of the liquid fuel synthesizing system of the present invention, the hydrogen gas has pressure fluctuation It may be separated by at least one of an adsorption method, a hydrogen storage alloy adsorption method or a membrane separation method.

[0010] In the start-up method of the liquid fuel synthesis system of the present invention, the reactor may be a bubble column type slurry bed reactor.

[0011] A liquid fuel synthesizing system of the present invention includes a reformer that reforms a hydrocarbon raw material to generate a synthesis gas mainly composed of carbon monoxide gas and hydrogen gas; and included in the synthesis gas. A reactor that synthesizes liquid hydrocarbons from carbon oxide gas and hydrogen gas; a hydrogen-based reaction device that performs a predetermined reaction using hydrogen gas contained in the synthesis gas generated by the reformer; and the reformer A hydrogen separator for separating a part of the hydrogen gas contained in the synthesis gas produced in step (b); a hydrogen storage device for storing the hydrogen gas separated by the hydrogen separator; and when the liquid fuel synthesis system is started up And control means for supplying the hydrogen gas stored in the hydrogen storage device to the hydrogen-utilizing reaction device.

[0012] In the liquid fuel synthesizing system of the present invention, the hydrogen-utilizing reactor includes a hydrogenation reactor for hydrogenating the liquid hydrocarbon synthesized in the reactor, or a hydrocarbon raw material supplied to the reformer. It may contain at least one of desulfurization reactors for hydrodesulfurization.

In the liquid fuel synthesizing system of the present invention, the hydrogen separation device separates hydrogen gas by at least one of a pressure fluctuation adsorption method, a hydrogen storage alloy adsorption method, and a membrane separation method. Moyore.

[0014] In the liquid fuel synthesis system of the present invention, the reactor may be a bubble column type slurry bed reactor.

The invention's effect

[0015] According to the present invention, the hydrogen utilization reactor provided in the liquid fuel synthesizing system can be started quickly, and the production efficiency of the liquid fuel can be improved.

Brief Description of Drawings

FIG. 1 is a schematic diagram showing an overall configuration of a liquid fuel synthesis system according to an embodiment of the present invention.

[FIG. 2] FIG. 2 is a timing chart showing a conventional starting method of the liquid fuel synthesis system. The

FIG. 3 is a timing chart showing a start-up method of the liquid fuel synthesizing system that is relevant to the embodiment.

FIG. 4 is a block diagram showing a configuration example of a hydrogen storage device in the liquid fuel synthesizing system according to the embodiment.

FIG. 5 is a block diagram showing another configuration example of the hydrogen storage device in the liquid fuel synthesizing system according to the embodiment.

Explanation of symbols

[0017] 1 ... Liquid fuel synthesis system, 3 ... Syngas generation unit, 5— FT synthesis unit, 7 ... Product purification unit, 10 ... Desulfurization reactor, 12 ... Reformer, 14 ... Waste heat boiler, 16 , 18 ··· Gas-liquid separator, 20… Decarbonation device, 22… Absorption tower, 24… Regeneration tower, 26… Hydrogen separation device, 30… Bubble tower reactor, 32… Heat transfer tube, 34, 38… Gas-liquid separator, 36 ... separator, 40 ... first rectification column, 50 ... WAX fraction hydrocracking reactor, 52 ... kerosene, gas oil fraction hydrotreating reactor, 54 ... naphtha fraction hydrogenation Purification reactor, 56, 58, 60 ... Gas-liquid separator, 70 ... Second rectification column, 72 ... Naphtha's stabilizer, 80 ... Hydrogen storage device, 81, 101 ... Storage tank, 82, 83, 104 ... Hydrogen compression 84, 105 ... Controller, 86, 87, 106, 107 ... Valve, 91, 92, 9 3, 94, 95 ... Piping, 102 ... Liquefaction device, 103 ... Vaporization device

BEST MODE FOR CARRYING OUT THE INVENTION

[0018] Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the present specification and drawings, constituent elements having substantially the same functional configuration are denoted by the same reference numerals, and redundant description is omitted.

First, an overall configuration and operation of a liquid fuel synthesizing system 1 that executes a GTL (Gas To Liquid) process that is relevant to an embodiment of the present invention will be described with reference to FIG. FIG. 1 is a schematic diagram showing an overall configuration of a liquid fuel synthesizing system 1 that is useful in the present embodiment.

As shown in FIG. 1, a liquid fuel synthesizing system 1 useful for the present embodiment is a plant facility that executes a GTL process for converting a hydrocarbon feedstock such as natural gas into liquid fuel. The liquid fuel synthesizing system 1 includes a syngas generating unit 3, an FT synthesizing unit 5, and a product refining unit 7. The synthesis gas generation unit 3 is a However, the gas is reformed to produce a 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 purifying the liquid hydrocarbons produced by the FT synthesis reaction. The components of each unit will be described below.

First, the synthesis gas generation unit 3 will be described. 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. Prepare for. The desulfurization reactor 10 is composed of a hydrodesulfurization device or the like, and removes natural gas power sulfur component as a raw material. The reformer ₂ 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 is produced in the reformer 12.

2

High pressure steam is generated by recovering the exhaust heat of the synthesized gas. The gas-liquid separator 16 separates the water heated by the 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 decarbonator 20. The decarboxylation device 20 includes an absorption tower 22 that removes carbon dioxide gas from the synthesis gas supplied from the gas-liquid separator 18 by using the absorption liquid, and a regeneration that diffuses the carbon dioxide gas from the absorption liquid containing the carbon dioxide gas to regenerate. With 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. However, the decarboxylation device 20 may not be required depending on circumstances.

[0022] Among these, the reformer 12 is a natural gas that uses carbon dioxide and steam by, for example, a steam 'carbonate gas reforming method represented by the following chemical reaction formulas (1) and (2). Is reformed to produce a high-temperature synthesis gas mainly composed of carbon monoxide gas and hydrogen gas. Note that the reforming method in the reformer 12 is not limited to the above steam / carbon dioxide reforming method. For example, the water steam reforming method, the partial oxidation reforming method using oxygen (PX ), Autothermal reforming method (ATR), carbon dioxide gas reforming method, etc., which is a combination of partial oxidation reforming method and steam reforming method. [0023] CH + H ○ → CO + 3H · · · · (1)

4 2 2

CH + CO → 2CO + 2H (2)

4 2 2

[0024] The hydrogen separator 26 is provided in a branch line branched from a main pipe connecting the decarboxylation device 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 Ads orption) 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. By repeating the steps of pressurization, adsorption, desorption (decompression), and purge in order, high-purity hydrogen gas (for example, about 99.999%) separated from synthesis gas is continuously supplied to the reactor. be able to.

[0025] 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. For example, the hydrogen storage alloy adsorption method, the membrane separation method, or these Combinations may be used.

[0026] The hydrogen storage alloy method is, for example, a hydrogen storage alloy having the property of adsorbing / releasing hydrogen by being cooled / heated (TiFe, LaNi, TiFe, Mn, TiMn, etc.)

5 0. 7 ~ 0. 9 0. 3 ~ 0. 1 1. 5

) To separate hydrogen gas. A plurality of adsorption towers containing hydrogen storage alloys are provided, and in each adsorption tower, hydrogen adsorption by cooling the hydrogen storage alloy and hydrogen release by heating the hydrogen storage alloy are alternately repeated to synthesize Hydrogen gas in the gas can be separated and recovered.

[0027] The membrane separation method is a method of separating hydrogen gas having excellent membrane permeability from a mixed gas using a membrane made of a polymer material such as aromatic polyimide. This membrane separation method does not involve a phase change, so the energy required for operation is small and the running cost is low. In addition, since the structure of the membrane separation apparatus is simple and out of comparator, the equipment cost is low and the required area of the equipment is small. Furthermore, the separation membrane has the advantage of easy maintenance because it has a wide stable operating range.

[0028] Next, the FT synthesis unit 5 will be described. 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, and a first rectifying column 40. The bubble column reactor 30 is composed of the synthesis gas generated by the synthesis gas generation unit 3. Gas, that is, carbon monoxide gas and hydrogen gas are subjected to FT synthesis reaction to produce liquid hydrocarbons. The gas-liquid separator 34 separates the water heated through the heat transfer tubes 32 disposed in the bubble column reactor 30 into water vapor (medium pressure steam) and liquid. The separator 36 is connected to the center of the bubble column reactor 30 and separates the catalyst and the liquid hydrocarbon product. The gas-liquid separator 38 is connected to the upper part of the bubble column reactor 30 and cools the unreacted synthesis gas and the gaseous hydrocarbon product. The first rectification column 40 distills liquid hydrocarbons supplied from the bubble column reactor 30 via the separator 36 and the gas-liquid separator 38, and separates and purifies each product fraction according to the boiling point. To do.

[0029] Among these, the bubble column reactor 30 is an example of a reactor that synthesizes synthesis gas into liquid hydrocarbons, and is an FT synthesis reactor that synthesizes liquid hydrocarbons from synthesis gas by FT synthesis reaction. Function. The bubble column reactor 30 is constituted by, for example, a bubble column type slurry bed type reactor in which a slurry made of a catalyst and a medium oil is stored inside a column type container. The bubble column reactor 30 generates liquid hydrocarbons from synthesis gas by FT synthesis reaction. Specifically, in this bubble column reactor 30, the synthesis gas, which is a raw material gas, is supplied as bubbles from the dispersion plate at the bottom of the bubble column reactor 30, and passes through the slurry composed of the catalyst and the medium oil. In the suspended state, hydrogen gas and carbon monoxide gas undergo a synthesis reaction as shown in chemical reaction formula (3) below.

[0030] 2nH + nC ○ → (One CH —) + nH O · · · · (3)

2 2 n 2

[0031] Since this FT synthesis reaction is an exothermic reaction, the bubble column reactor 30 is of a heat exchanger type in which a heat transfer tube 32 is provided, and water (BFW: Boiler Feed Watt) is used as a refrigerant. er) and the reaction heat of the FT synthesis reaction can be recovered as an intermediate pressure steam by heat exchange between the slurry and water.

[0032] Finally, the product purification unit 7 will be described. Product purification unit 7 includes, for example, W AX fraction hydrocracking reactor 50, kerosene / light oil fraction hydrotreating reactor 52, naphtha fraction hydrotreating 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 rectification column 40. A kerosene / light oil fraction hydrotreating reactor 52 is connected to the center of the first rectifying column 40. The naphtha fraction hydrotreating reactor 54 is located above the first rectification column 40. It is connected. 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 lighter components than butane to the flare gas (exhaust gas) side, Ingredients whose number is C or more

Five

Is separated and collected as naphtha of the product.

[0033] Next, the process of synthesizing liquid fuel from natural gas (GTL process) by the liquid fuel synthesizing system 1 configured as described above will be described.

[0034] The liquid fuel synthesizing system 1 is supplied with natural gas (the main component is CH 2) as a hydrocarbon feedstock from an external natural gas supply source (not shown) such as a natural gas field or a natural gas plant.

4 is paid. The synthesis gas generation unit 3 reforms the natural gas to produce synthesis gas (a mixed gas mainly composed of carbon monoxide gas and hydrogen gas).

[0035] Specifically, first, 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 the sulfur content contained in the natural gas using, for example, a ZnO catalyst using the hydrogen gas. By desulfurizing 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 from being reduced by sulfur.

[0036] Natural gas desulfurized in this way (including carbon dioxide,...) Is a carbon dioxide (CO 2) gas supplied from a carbon dioxide supply source (not shown) and an exhaust heat boiler. Depart at 14

2

After the raw steam is mixed, it is supplied to the reformer 12. For example, the reformer 12 reforms natural gas using carbon dioxide and water vapor by the steam 'carbon dioxide gas reforming method described above, and generates high-temperature components mainly composed of carbon monoxide gas and hydrogen gas. Generate synthesis gas. At this time, for example, the reformer 12 is supplied with fuel gas and air for the burner provided in the reformer 12, and the steam / carbon dioxide gas is an endothermic reaction by the combustion heat of the fuel gas in the burner. The heat of reaction necessary for the reforming reaction has been provided.

[0037] The high-temperature synthesis gas (for example, 900 ° C, 2. OMPa G) generated in the reformer 12 in this way is supplied to the exhaust heat boiler 14 and is circulated in the exhaust heat boiler 14. It is cooled (for example, 400 ° C) by heat exchange with the heat and recovered. At this time, in the exhaust heat boiler 14 Water heated by the synthesis gas is supplied to the gas-liquid separator 16, and the gas component from the gas-liquid separator 16 is converted into high-pressure steam (eg, 3.4-10. OMPaG) to the reformer 12 or other external device. The liquid water is returned to the exhaust heat boiler 14.

[0038] On the other hand, the synthesis gas cooled in the exhaust heat boiler 14 is separated and removed in the gas-liquid separator 18 by the condensate, and then the absorption tower 22 of the decarboxylation device 20 or the bubble column reactor. Supplied to 30. The absorption tower 22 removes 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 stripped by heating with, for example, steam. To the reformer 12 for reuse in the reforming reaction.

In this way, 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. At this time, the composition ratio of the synthesis gas supplied to the bubble column reactor 30 is the composition ratio suitable for the FT synthesis reaction (for example, H: CO = 2: 1 (molar ratio)

2

)) Is adjusted. The synthesis gas supplied to the bubble column reactor 30 is FT 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 a pressure suitable for the synthesis reaction (eg, 3.6 MPaG).

Further, a part of the synthesis gas from which the carbon dioxide gas has been separated by the decarbonation device 20 is also supplied to the hydrogen separation device 26. The hydrogen separator 26 separates hydrogen gas contained in the synthesis gas by adsorption and desorption (hydrogen PSA) using a 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 synthesis system 1 from a gas holder (not shown) or the like via a compressor (not shown). (For example, desulfurization reactor 10, WAX hydrocracking reactor 50, kerosene / light oil fraction hydrotreating reactor 52, naphtha fraction hydrotreating reactor 54, etc.) .

[0041] Next, 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.

Specifically, the synthesis gas produced by the synthesis gas production unit 3 flows from the bottom of the bubble column reactor 30 and passes through the catalyst slurry stored in the bubble column reactor 30. To rise. At this time, in the bubble column reactor 30, the synthesis is performed by the FT synthesis reaction described above. Carbon monoxide and hydrogen gas contained in the generated gas react to generate hydrocarbons. Furthermore, at the time of this synthesis reaction, water is circulated through the heat transfer tube 32 of the bubble column reactor 30 to remove the reaction heat of the FT synthesis reaction, and the water heated by this heat exchange evaporates to form water. It becomes steam. The water vapor liquefied by the gas-liquid separator 34 is returned to the heat transfer tube 32, and the gas component is supplied to the external device as medium-pressure steam (for example, 1.0 to 2.5 MPaG).

[0043] In this way, the liquid hydrocarbon synthesized in the bubble column reactor 30 is taken out from the center of the bubble column reactor 30 and introduced into the separator 36. The separator 36 separates the catalyst (solid content) in the removed slurry into the liquid content containing the liquid hydrocarbon product. A part of the separated catalyst is returned to the bubble column reactor 30, and the liquid is supplied to the first rectifying column 40. From the top of the bubble column reactor 30, 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 condensed liquid hydrocarbons, and introduces them into the first fractionator 40. On the other hand, for the gas components separated by the gas-liquid separator 38, the unreacted synthesis gas (CO and H) is reintroduced into the bottom of the bubble column reactor 30 and reused for the FT synthesis reaction.

2

In addition, the main component is a hydrocarbon gas with a low carbon number (C or less) that is not covered by the product.

Four

Exhaust gas (flare gas) is introduced into an external combustion facility (not shown), burned, and released into the atmosphere.

[0044] Next, the first rectifying column 40 receives liquid hydrocarbons (having various carbon numbers) supplied from the bubble column reactor 30 through the separator 36 and the gas-liquid separator 38 as described above. Heat and fractionate using different boiling points, naphtha fraction (boiling point less than about 315 ° C), kerosene 'light oil fraction (boiling point about 315-800 ° C), WAX fraction Separate and purify (boiling point greater than about 800 ° C). The liquid hydrocarbons (mainly C or more) of WAX taken out from the bottom of the first rectifying column 40 are

twenty one

The liquid hydrocarbons (mainly C to C) of kerosene / light oil fraction transferred to the WAX fraction hydrocracking reactor 50 and taken out from the center of the first rectification tower 40 are kerosene / light oil fraction hydrotreating

11 20

The liquid hydrocarbon (mainly C to C) of the naphtha fraction that is transferred to the reactor 52 and taken out from the upper part of the first rectifying column 40 is transferred to the naphtha fraction hydrotreating reactor 54.

5 10

[0045] The WAX fraction hydrocracking reactor 50 is fed from the hydrogen separator 26 with liquid hydrocarbons (generally C or more) having a large number of carbon atoms supplied from the lower part of the first rectifying column 40. Hydrocracking using the generated hydrogen gas to reduce the carbon number to C or less. This hydrogenation

20

In the decomposition reaction, the catalyst and heat are used to cleave C C bonds of hydrocarbons with a large number of carbons to produce low molecular weight hydrocarbons with a small number of carbons. The product containing liquid hydrocarbons hydrocracked by this WAX hydrocracking reactor 50 is separated into gas and liquid by gas-liquid separator 56, of which liquid hydrocarbons are separated by the 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.

[0046] Kerosene · Gas oil fraction hydrotreating reactor 52 is a liquid hydrocarbon (generally C to C) of kerosene · gas oil fraction supplied from the center of the first rectification column 40 with a medium carbon number. ), Hydrogen content

11 20

Hydrotreating is performed using hydrogen gas supplied from the separation device 26 through the WAX hydrocracking reactor 50. This hydrorefining reaction is a reaction in which hydrogen is added to the unsaturated bond of the liquid hydrocarbon to saturate to produce a linear saturated hydrocarbon. As a result, the hydrogenated and purified product containing liquid hydrocarbons is separated into a gas and a liquid by the gas-liquid separator 58, and the liquid hydrocarbons are transferred to the second rectification column 70 for gas separation. (Including hydrogen gas) is reused in the hydrogenation reaction.

[0047] The naphtha fraction hydrotreating reactor 54 supplies liquid hydrocarbons (generally C or less) of the naphtha fraction having a low carbon number supplied from the upper part of the first rectification column 40 to the WA separator 26 from the WA.

Ten

Hydrorefining using the hydrogen gas supplied via the X-fraction 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.

[0048] Next, 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. Hydrocarbons with a carbon number of C or less (boiling point less than about 315 ° C) and kerosene (boiling point about 315 to 450 ° C)

Ten

Separating and refining it into diesel oil (boiling point approx. 450-800 ° C). Gas oil is taken out from the lower part of the second rectification tower 70, and kerosene is taken out from the center. On the other hand, hydrocarbon gas having a carbon number of C or less is taken out from the top of the second rectifying column 70 and is supplied to the naphtha stabilizer 72.

Ten

Supplied. [0049] Further, the naphtha's stabilizer 72 distills hydrocarbons having a carbon number of C or less supplied from the naphtha fraction hydrotreating reactor 54 and the second rectifying column 70 as a product.

Ten

The naphtha (C to C) is separated and purified. This allows the bottom of the naphtha stabilizer 72

5 10

From which high-purity naphtha is extracted. On the other hand, from the top of Naphtha's Stabilizer 72, the main component of the exhaust is hydrocarbons whose main component is a carbon number not exceeding the specified number (C or less).

Four

Gas (flare gas) is discharged. This exhaust gas is introduced into an external combustion facility (not shown), burned, and released into the atmosphere.

[0050] The operation (GTL process) of the liquid fuel synthesis system 1 has been described above. By this GTL process, natural gas is converted into high-purity naphtha (C ~ C: crude gasoline), kerosene (C ~

5 10 11

C: kerosene) and light liquids (c-c: gas oil)

15 16 20

Can be converted economically. Further, in the present embodiment, the reformer 12 employs the steam / carbon dioxide reforming method, so that carbon dioxide contained in natural gas as a raw material is effectively used, and the FT Efficient generation of synthesis gas composition ratio suitable for synthesis reaction (eg, H: CO = 2: l (molar ratio)) in one reaction of the reformer 12

2

There is an advantage that a hydrogen concentration adjusting device or the like is unnecessary.

[0051] Next, in the liquid fuel synthesizing system 1 according to the present embodiment, a hydrogen gas supply system for a hydrogen-using reaction apparatus that performs a predetermined reaction using hydrogen gas will be described in detail.

[0052] In the liquid fuel synthesizing system 1 described above, during steady operation (at the rated operation after a predetermined time has elapsed since the start of the system), a part of the hydrogen gas in the syngas produced by the reformer 12 is hydrogenated. The hydrogen gas separated by the separation device 26 is separated into hydrogen-utilized reaction devices (for example, the desulfurization reactor 10 of the synthesis gas generation unit 3 and the WAX hydrocracking reactor 50 of the product purification unit 7 and kerosene. · Continuous supply to gas oil fraction hydrotreating reactor 52 and naphtha fraction hydrotreating reactor 54 (hereinafter collectively referred to as “hydrogenation reactors 50, 52, 54”) It is.

[0053] However, with such a hydrogen gas supply system alone, when the liquid fuel synthesizing system 1 is started up (including when the units 3, 5, and 7 are started up), the reformer 12 is started up after the start-up. Until the product is operated and the synthesis gas is stably generated and supplied, Since hydrogen gas is not supplied to the hydrogenation reactors 50, 52, 54, the hydrogenation reactors 50, 52, 54 cannot be started. For this reason, conventionally, the entire liquid fuel synthesizing system 1 was started up, and it took a considerable amount of time S to produce a liquid fuel product, which had the problem of poor production efficiency.

[0054] The start-up delay of the hydrogenation reactors 50, 52, 54 of the product purification unit 7 will be specifically described with reference to FIG. As shown in FIG. 2, conventionally, when the liquid fuel synthesizing system 1 is started, first, the reformer 12 of the syngas generating unit 3 is started to start the synthesis gas generation reaction. The reformer 12 is in a steady operation and can stably supply the synthesis gas, for example, on the fourth day from the start-up. Also, for the FT synthesis unit 5, when the synthesis gas generation unit 3 is started up, for example, one day after the start-up, and the apparatus is adjusted for preparation of the FT synthesis reaction, the same date as when the synthesis gas generation unit 3 is rated. From the 4th day, the FT synthesis reaction can be performed stably.

[0055] However, for the product refining unit 7, the hydrogenation reaction must be performed after the hydrogen gas generated in the reformer 12 is supplied to the hydrogenation reactors 50, 52, 54 (after the fourth day). It is not possible to start up the catalyst reduction or hydrogenation reaction by starting the vessels 50, 52, 54. For this reason, the product purification unit 7 can stably carry out the hydrogenation and purification reaction, for example, on the 8th day from the start of the synthesis gas generation unit 3, with a long startup time. It was necessary. Therefore, the entire liquid fuel synthesizing system 1 is completely up and the liquid fuel product can be manufactured stably on the 8th day from the start of the syngas generation unit 3 (the rating of the syngas generation unit 3). On the fourth day after the start of operation), there was a problem that production efficiency was very slow.

[0056] Further, the starting power of the synthesis gas generation unit 3 is also on the fourth day, and on the seventh day, the force that the FT synthesis unit 5 is operating normally The product purification unit 7 is not operating normally Therefore, there is also a problem that a semi-finished product storage tank (not shown) for storing liquid hydrocarbons produced by the FT synthesis reaction (semi-finished product before being hydrogenated and purified) is required. there were.

[0057] Therefore, in order to solve these problems, in the liquid fuel synthesizing system 1 that is useful in the present embodiment, as shown in FIG. 1, the hydrogen gas separated and recovered from the syngas by the hydrogen separator 26 is used. Hydrogen storage device 80 for storing is provided, and hydrogen stored in this hydrogen storage device 80 The gas can be supplied to the desulfurization reactor 10 of the synthesis gas generation unit 3 and the hydrogenation reactors 50, 52, and 54 of the product purification unit 7. That is, apart from the supply system for supplying hydrogen gas directly from the hydrogen separator 26 as described above to the hydrogen utilizing reactors such as the desulfurization reactor 10 and the hydrogenation reactors 50, 52, 54, etc. Hydrogen separator A supply system that temporarily stores 26-force hydrogen gas in the hydrogen storage device 80 and indirectly supplies it is installed.

[0058] In such a configuration, during the steady operation of the liquid fuel synthesis system 1, the hydrogen separator

A part of the hydrogen gas is stored in the hydrogen without being supplied to the hydrogen-utilizing reactors such as the desulfurization reactor 10 and the hydrogenation reactors 50, 52, 54. Store in device 80. Then, when the hydrogenation reactors 50, 52, 54 are restarted, for example, when the liquid fuel synthesizing system 1 is restarted thereafter, the hydrogen gas stored in the hydrogen storage device 80 is replaced with the hydrogenation reactor 50. , 52, 54 and desulfurization reactor 10 are supplied immediately. As a result, before the reformer 12 is started and hydrogen gas is stably supplied from the reformer 12, the hydrogenation of the hydrogenation reactors 50, 52, 54 and desulfurization reactor 10 is used. The reactor can be activated quickly.

Specifically, as shown in FIG. 3, when the liquid fuel synthesizing system 1 that is useful in the present embodiment is restarted, first, the hydrogen gas stored in the hydrogen storage device 80 is converted into the product purification unit 7. To the hydrogenation reactors 50, 52, and 54. Thus, before the reformer 12 is started, the hydrogenation reactors 50, 52, and 54 can be started to start preparation for catalytic reduction or hydrogenation reaction. Next, one day after the start of the hydrogenation reactors 50, 52, 54, the synthesis gas generation unit 3 is started to supply the hydrogen gas stored in the hydrogen storage device 80 to the desulfurization reactor 10, and Start the internal organs 12 and start up, and one day later, start the FT synthesis unit 5 to prepare the equipment and prepare for the FT synthesis reaction. Thus, for example, on the fifth day from the start of the hydrogenation reactors 50, 52, 54, the reformer 12 can be stably operated to stably supply the synthesis gas, and the bubble column reactor 30 can Liquid hydrocarbons can be stably generated by the synthesis reaction. Further, at this time (day 5), since the preparation operation of the hydrogenation reactors 50, 52, 54, etc. is completed in the product purification unit 7, the product purification unit 7 is supplied from the FT synthesis unit 5. Liquid charcoal Production of liquid fuel products can be started by stably performing hydrogenation hydrogenation (reduction / hydrocracking) and purification reactions.

Thus, in this embodiment, when the liquid fuel synthesizing system 1 is restarted, the hydrogen gas stored in the hydrogen storage device 80 is converted into hydrogenation reactors 50, 52, 54 and desulfurization reactors 10. By supplying to, the start-up time of the entire system can be shortened and the production of liquid fuel products can be started at an early stage, so that the production efficiency can be improved.

Here, with reference to FIG. 4 and FIG. 5, a configuration example of the hydrogen storage device 80 in the liquid fuel synthesizing system 1 that is effective in the present embodiment will be described in detail. FIG. 4 and FIG. 5 are block diagrams respectively showing configuration examples of the hydrogen storage device 80 in the liquid fuel synthesizing system 1 that is useful in the present embodiment. 4 and 5, only the main components of the liquid fuel synthesizing system 1 of FIG. 1 are shown for convenience of explanation, and some of the components are not shown.

As shown in FIGS. 4 and 5, in the liquid fuel synthesis system 1, the hydrogen separator 26 and the hydrogen storage device 80 are connected via a pipe 91, and the hydrogen storage device 80 and the desulfurization reactor 10 and And hydrogenation reactors 50, 52 and 54 are connected through pipes 92 and 93, respectively.

First, the hydrogen storage device 80 in the example of FIG. 4 will be described in detail. As shown in FIG. 4, the hydrogen storage device 80 is connected to a storage tank 81 composed of a pressure vessel such as a spherical storage tank and a pipe 91 from the hydrogen separation device 26, and is connected to the storage tank 81. Connected to the hydrogen compressor 82 connected to the inlet side and the outlet side of the storage tank 81, and connected to the desulfurization reactor 10 and the hydrogenation reactors 50, 52, 54 through the pipes 92, 93, respectively. A hydrogen compressor 83, and a controller 84 for controlling each part of the hydrogen storage device 80. The controller 84 is an example of a control unit that controls the operation of the hydrogen storage device 80 (for example, the storage operation of hydrogen gas or the supply operation of the stored hydrogen gas to the hydrogen utilization reactor).

[0064] The operation of the hydrogen storage device 80 of Fig. 4 having such a configuration will be described. During steady operation of the liquid fuel synthesis system 1 described above, a part of the hydrogen gas is separated and recovered from the synthesis gas generated in the reformer 12 by the hydrogen separator 26 and is connected via the pipes 94 and 95. Supplied to desulfurization reactor 10 and hydrogenation reactors 50, 52, 54. During this steady operation, hydrogen storage For example, a storage instruction signal based on an operator input or a storage instruction signal from a controller (not shown) of the liquid fuel synthesis system 1 is input to the controller 84 of the apparatus 80. Then, the controller 84 operates the hydrogen compressor 82 to store the hydrogen gas in the storage tank 81, opens the valve 86 on the inlet side of the storage tank 81, and closes the valve 87 on the outlet side. To control. As a result, a part of the hydrogen gas discharged from the hydrogen separator 26 is supplied to the hydrogen compressor 82 via the pipe 91, and the hydrogen compressor 82 compresses the supplied hydrogen gas to produce a storage tank 81. At a predetermined storage pressure (eg 3 MPaG). Thereafter, when a sufficient amount of hydrogen gas is stored, the controller 84 stops the operation of the hydrogen compressor 82, closes the valve 86 on the inlet side of the storage tank 81, and ends the storage operation.

On the other hand, when the liquid fuel synthesizing system 1 is started, the controller 84 of the hydrogen storage device 80 is supplied with a supply instruction signal based on an operator input or a controller (not shown) of the liquid fuel synthesizing system 1, for example. The supply instruction signal from is input. Then, the controller 84 operates the hydrogen compressor 83 to supply the hydrogen gas stored in the storage tank 81 as described above, and keeps the valve 86 on the inlet side of the storage tank 81 closed. Then, the outlet valve 87 is controlled to be opened. As a result, the hydrogen gas stored in the storage tank 81 is raised to a predetermined pressure (eg, 3.6 MPaG) suitable for the bubble column reactor 30 by the hydrogen compressor 83, and the pressurized hydrogen gas is connected to the pipe 92 , 93 to the desulfurization reactor 10 and the hydrogenation reactors 50, 52, 54. As described above, in the example of FIG. 4, the hydrogen gas stored in the storage tank 81 is supplied to the required location when the liquid fuel synthesizing system 1 is started using the hydrogen storage device 80 having a relatively simple device configuration. Can be supplied immediately.

Next, the hydrogen storage device 80 in the example of FIG. 5 will be described in detail. The hydrogen storage device of FIG. 5 is configured as a liquefied hydrogen storage device that liquefies and stores hydrogen gas in order to store a larger amount of hydrogen.

As shown in FIG. 5, a hydrogen storage device 80 is connected to a storage tank 101 composed of a pressure vessel such as a spherical storage tank and a pipe 91 from the hydrogen separator 26, and the storage tank 101 The liquefier 102 connected to the inlet side of the tank, the vaporizer 103 connected to the outlet side of the storage tank 101, and connected to the vaporizer 103, and removed via the pipes 92, 93. A hydrogen compressor 104 connected to each of the sulfur reactor 10 and the hydrogenation reactors 50, 52, and 54, and a controller 105 that controls each part of the hydrogen storage device 80 are provided. Among these, the liquefying device 102 can liquefy hydrogen gas by a thermodynamic cycle such as a Joule-Thomson cycle, an isentropic expansion cycle, or a helium brighton cycle. The vaporizer 103 includes a heat exchanger or the like, and can heat and vaporize the liquefied hydrogen supplied from the storage tank 101 to produce hydrogen gas. The controller 105 is an example of a control unit that controls the operation of the hydrogen storage device 80 (for example, the storage operation of hydrogen gas or the supply operation of the stored hydrogen gas to the hydrogen-utilizing reactor).

[0068] The operation of the hydrogen storage device 80 of Fig. 5 having such a configuration will be described. During steady operation of the liquid fuel synthesizing system 1, a storage instruction signal is input to the controller 105 of the hydrogen storage device 80, as in the example of FIG. Then, in order to store the hydrogen gas in the storage tank 101, the controller 105 operates the liquefaction device 102, and controls to open the valve 106 on the inlet side of the storage tank 101 and close the valve 107 on the outlet side. To do. As a result, a part of the hydrogen gas discharged from the hydrogen separator 26 is supplied to the liquefier 102 via the pipe 91, and the liquefier 102 liquefies the supplied hydrogen gas and converts this liquefied hydrogen into Store in the storage tank 101 at a 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, closes the valve 106 on the inlet side of the storage tank 101, and ends the storage operation.

On the other hand, when the liquid fuel synthesizing system 1 is started, a supply instruction signal is input to the controller 105 of the hydrogen storage device 80 as in the example of FIG. Then, the controller 105 operates the vaporizer 103 and the hydrogen compressor 104 in order to vaporize and supply the liquefied hydrogen stored in the storage tank 101 as described above to hydrogen gas. The outlet valve 107 is controlled to be opened while the valve 106 is closed. As a result, the liquefied hydrogen stored in the storage tank 101 is vaporized by the vaporizer 103 to become hydrogen gas. Further, the hydrogen compressor 83 converts this hydrogen gas into a predetermined pressure (for example, the bubble column reactor 30). The pressure is increased to 3.6 MPaG), and the pressurized hydrogen gas is supplied to the desulfurization reactor 10 and the hydrogenation reactors 50, 52, 54 through the pipes 92, 93. Thus, in the example of FIG. 5, by storing hydrogen gas in a liquefied state, a large amount of hydrogen can be stored in the storage tank 101, and liquid fuel can be stored. When the fuel composition system 1 is started, the hydrogen gas obtained by vaporizing the liquefied hydrogen stored in the storage tank 101 can be supplied immediately and in large quantities to the necessary location.

As described above, the liquid fuel synthesizing system 1 according to the present embodiment and the starting method of the liquid fuel synthesizing system 1 have been described in detail. According to the present embodiment, by providing the hydrogen storage device 80, during the steady operation of the liquid fuel synthesis system 1, a part of the hydrogen gas in the synthesis gas generated by the reformer 12 is transferred to the hydrogen storage device 80. The hydrogen can be stored to secure a predetermined amount or more, and when the hydrogen gas is needed, the hydrogen gas can be instantaneously supplied from the hydrogen storage device 80. For this reason, when the liquid fuel synthesis system 1 is restarted, the hydrogen gas stored in the hydrogen storage device 80 is immediately supplied to the hydrogen-using reactors such as the hydrogenation reactors 50, 52, 54 and desulfurization reactor 10. As a result, the time required to start up these hydrogen-utilizing reactors and start steady operation can be reduced to a minimum. Therefore, since the start-up time of the entire liquid fuel synthesizing system 1 can be greatly shortened, the production efficiency of liquid fuel products such as naphtha, kerosene, and light oil can be improved.

[0071] While the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, it goes without saying that the present invention is not limited to such examples. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the claims, and these are naturally within the technical scope of the present invention. Understood to belong

[0072] For example, in the above embodiment, natural gas is used as the hydrocarbon raw material supplied to the liquid fuel synthesizing system 1, but it is not limited to a powerful example, and other carbonization such as asphalt and residual oil is used. Use hydrogen raw materials.

[0073] In the above embodiment, as the synthesis reaction in the bubble column reactor 30, the liquid hydrocarbon is synthesized by the FT synthesis reaction, but the present invention is not limited to a powerful example. Examples of synthesis reactions in bubble column reactors include oxo synthesis (hydroformyl ミル reaction) “R • CH = CH + CO + H → R-CH CH CHO”, methanol synthesis “CO + 2H → CH 2 O

2 2 2 2 2 3

H ”, suitable for dimethyl ether (DME) synthesis“ 3CO + 3H → CH ○ CH + CO ”

2 3 3 2

Power to use s.

[0074] Further, in the above-described embodiment, the desulfurization reactor 10, WAX diversion is used as the hydrogen-utilizing reactor. Examples of hydrocracking reactor 50, kerosene / light oil fraction hydrotreating reactor 52, and naphtha fraction hydrotreating reactor 54 were given, but the examples are not limited to powerful examples. Any apparatus other than those described above may be used as long as the apparatus performs a predetermined reaction using hydrogen gas. Specifically, hydrogen-based reactors include, for example, fuel cells, naphthalene hydrogenation reactors (phthalene → decalin), aromatic hydrocarbon (benzene) hydrogenation reactions (benzene → cyclohexane, etc.) Or a device for performing a hydrogenation reaction on an unsaturated fatty acid.

[0075] In the above embodiment, a bubble column type slurry bed type reactor is used as a reactor for synthesizing synthesis gas into liquid hydrocarbons, but the present invention is not limited to a powerful example. The FT synthesis reaction may be performed using a fixed bed reactor or the like.

Industrial applicability

[0076] The present invention includes a reformer for reforming a hydrocarbon raw material to generate a synthesis gas mainly composed of carbon monoxide gas and hydrogen gas, and a carbon monoxide gas and a hydrogen gas contained in the synthesis gas. A method for starting a liquid fuel synthesis system comprising: a reactor that synthesizes liquid hydrocarbons; and a hydrogen-based reaction device that performs a predetermined reaction using hydrogen gas contained in the synthesis gas generated by the reformer. Then, during steady operation of the liquid fuel synthesis system, a part of hydrogen gas contained in the synthesis gas generated by the reformer is separated and stored, and when the liquid fuel synthesis system is started up, The present invention relates to a method for starting a liquid fuel synthesis system that supplies hydrogen gas stored in the hydrogen storage device to the hydrogen-utilizing reactor. According to the start-up method of the liquid fuel synthesis system of the present invention, it is possible to quickly start the hydrogen-utilizing reactor and improve the production efficiency.

Claims

The scope of the claims

[1] A reformer that reforms a hydrocarbon raw material to generate synthesis gas mainly composed of carbon monoxide gas and hydrogen gas, and carbon monoxide gas and hydrogen gas power contained in the synthesis gas. Liquid hydrocarbon A method for starting a liquid fuel synthesis system comprising: a reactor for synthesizing a hydrogen gas; and a hydrogen-based reaction device that performs a predetermined reaction using hydrogen gas contained in the synthesis gas generated by the reformer,

During steady operation of the liquid fuel synthesizing system, a part of hydrogen gas contained in the synthesis gas generated by the reformer is separated and stored in shellfish.

A method for starting a liquid fuel synthesizing system, wherein the hydrogen gas stored in the hydrogen storage device is supplied to the hydrogen-using reaction device when the liquid fuel synthesizing system is started.

[2] The hydrogen-utilizing reactor is a hydrogenation reactor that hydrogenates liquid hydrocarbons synthesized in the reactor, or a desulfurization reaction that hydrodesulfurizes a hydrocarbon raw material supplied to the reformer. 2. The method for starting a liquid fuel synthesis system according to claim 1, comprising at least four of the vessels.

[3] The method for starting the liquid fuel synthesis system according to claim 1, wherein the hydrogen gas is separated by at least one of a pressure fluctuation adsorption method, a hydrogen storage alloy adsorption method, and a membrane separation method.

4. The method for starting a liquid fuel synthesis system according to claim 1, wherein the reactor is a bubble column type slurry bed type reactor.

[5] a reformer that reforms a hydrocarbon raw material to generate synthesis gas mainly composed of carbon monoxide gas and hydrogen gas;

A reactor for synthesizing carbon monoxide gas and hydrogen gas power liquid hydrocarbon contained in the synthesis gas;

A hydrogen-based reaction apparatus that performs a predetermined reaction using hydrogen gas contained in the synthesis gas generated by the reformer;

A hydrogen separator for separating part of the hydrogen gas contained in the synthesis gas produced by the reformer;

A hydrogen storage device for storing hydrogen gas separated by the hydrogen separation device; Control means for supplying hydrogen gas stored in the hydrogen storage device to the hydrogen-using reaction device when the liquid fuel synthesis system is activated.

[6] The hydrogen-utilizing reactor includes a hydrogenation reactor that hydrogenates liquid hydrocarbons synthesized in the reactor, or a desulfurization reaction that hydrodesulfurizes a hydrocarbon raw material supplied to the reformer. 6. The liquid fuel synthesis system according to claim 5, comprising at least one of the vessels.

7. The liquid fuel synthesis system according to claim 5, wherein the hydrogen separation device separates hydrogen gas by at least one of a pressure fluctuation adsorption method, a hydrogen storage alloy adsorption method, and a membrane separation method.

8. The liquid fuel synthesis system according to claim 5, wherein the reactor is a bubble column type slurry bed type reactor.