JPWO2007119587A1 - Liquid fuel synthesis system - Google Patents

Abstract

This liquid fuel synthesizing system 1 includes a first reformer 12 that reforms a hydrocarbon raw material to produce a syngas mainly composed of carbon monoxide gas and hydrogen gas, and carbon monoxide gas contained in the syngas. And a bubble column reactor 30 for synthesizing liquid hydrocarbons from hydrogen gas, and a first fractionation method for heating the liquid hydrocarbons synthesized in the bubble column reactor 30 to fractionate a plurality of types of liquid fuels having different boiling points. A rectifying column 40, a hydrogen-based reaction device that performs a predetermined reaction on a hydrocarbon raw material or liquid fuel using hydrogen gas contained in the synthesis gas, and a liquid component separated and recovered from the hydrogen-based reaction device The second rectifying column 70 for purifying the gas and the gas discharged from the second rectifying column 70 as a raw material are supplied to at least one of the first reformer 12, the hydrogen utilizing reactor and the bubble column reactor 30. Supply means to supply as part of That.

Description

The present invention relates to a liquid fuel synthesis system for synthesizing a liquid fuel from a hydrocarbon raw material such as natural gas.
This application claims priority about the Japan patent application 2006-95544 for which it applied on March 30, 2006, and uses the content here.

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 ₂ ). By synthesizing liquid hydrocarbons by Fischer-Tropsch synthesis reaction (hereinafter referred to as “FT synthesis reaction”) using this synthesis gas as a raw material gas, and further hydrogenating and purifying the liquid hydrocarbon, naphtha (crude gasoline) ), GTL (Gas To Liquid) technology for producing liquid fuel products such as kerosene, light oil and wax has been developed.

  The liquid hydrocarbon immediately after the synthesis reaction is a mixture of a plurality of liquid hydrocarbons having different boiling points. In order to separate this mixture, an apparatus called a rectifying column is used. The components of liquid fuel products such as naphtha (crude gasoline), kerosene, light oil, etc. having 5 or more carbon atoms are separated and recovered from the exhaust gas (hereinafter referred to as “off-gas”) discharged from the top of this rectifying column. After being done, it was sent to the flare stack, burned, and released into the atmosphere.

  However, the off-gas includes, for example, a hydrocarbon gas having less than 5 carbon atoms. However, in the above-described conventional liquid fuel synthesizing system, in order to burn and discard these off-gases, hydrocarbon gas that can be a raw material for liquid hydrocarbons is wasted. Moreover, not only the raw materials are not effectively used, but also the amount of carbon dioxide emissions accompanying exhaust gas combustion increases.

  Therefore, the present invention has been made in view of such problems, and by effectively using a hydrocarbon component having a small number of carbon atoms contained in the off-gas without discarding, the utilization efficiency of the raw material can be improved, An object of the present invention is to provide a liquid fuel synthesis system capable of reducing carbon dioxide emissions.

  The liquid fuel synthesizing system of the present invention includes a first reformer for reforming a hydrocarbon raw material to produce a syngas mainly composed of carbon monoxide gas and hydrogen gas; and carbon monoxide contained in the syngas A reactor for synthesizing liquid hydrocarbons from gas and hydrogen gas; a first rectifying column for fractionating a plurality of types of liquid fuels having different boiling points by heating the liquid hydrocarbons synthesized in the reactor; Using a hydrogen gas contained in the synthesis gas, a hydrogen-based reaction device that performs a predetermined reaction on the hydrocarbon raw material or the liquid fuel; and a liquid fraction separated and recovered from the hydrogen-based reaction device A second rectifying column to be purified; and a gas discharged from the second rectifying column as a part of a raw material in at least one of the first reformer, the hydrogen-utilizing reactor, and the reactor. A supply means for supplying;

  According to such a configuration, the gas discharged from the second rectification column is supplied as a part of the raw material to at least one of the first reformer, the hydrogen utilization reactor, and the reactor by the supply means. The Since the gas discharged from the second rectifying column contains a hydrocarbon component having 4 or less carbon atoms, the gas discharged from the second rectifying column is more upstream than the second rectifying column. By returning to the apparatus, the utilization efficiency of the hydrocarbon raw material can be improved.

  In the liquid fuel synthesizing system of the present invention, the hydrogen-utilizing reaction apparatus is a hydrogenation reactor for hydrogenating at least one of a plurality of types of liquid fuels, or a hydrocarbon raw material supplied to the first reformer. At least one of desulfurization reactors for hydrodesulfurization may be included.

  The liquid fuel synthesizing system of the present invention includes a naphtha stabilizer provided downstream of the second rectification column, and the gas is discharged from the naphtha stabilizer and the first reformer and the hydrogen utilization reaction. It may be supplied as a part of the raw material to at least one of the apparatus and the reactor. Furthermore, the liquid fuel synthesizing system of the present invention may include a second reformer that reforms the gas discharged from the naphtha stabilizer. With such a configuration, the synthesis gas for the liquid fuel synthesis system can be generated by reforming the gas discharged from the naphtha stabilizer. As a result, it is possible to recover hydrocarbon components having a small number of carbon atoms contained in the gas discharged from the naphtha stabilizer, thereby reducing wasteful consumption of hydrocarbons as raw materials and improving the utilization efficiency of raw materials. it can.

  The liquid fuel synthesizing system of the present invention includes a hydrogen separation device that separates and purifies hydrogen gas from the synthesis gas obtained by the second reformer, and the supply means is a hydrogen gas separated by the hydrogen separation device. May be fed to a reactor or a hydrogen utilizing reactor. With this configuration, the hydrogen separator separates and purifies only hydrogen gas from the synthesis gas obtained by the second reformer, and supplies the hydrogen gas to each device that requires hydrogen gas by the supply means. Can do. Thereby, the usage-amount of the hydrogen gas newly introduce | transduced into a liquid fuel synthesis system can be reduced.

  The liquid fuel synthesizing system of the present invention may include a hydrogen storage device that stores the hydrogen gas separated by the hydrogen separation device.

  In the liquid fuel synthesizing system of the present invention, the supply means may supply the hydrogen gas stored in the hydrogen storage device to the hydrogen utilizing reaction device when the liquid fuel synthesizing system is activated. With this configuration, it is possible to quickly start the hydrogen utilization reactor before hydrogen gas is supplied from the reformer. Therefore, the production efficiency of the liquid fuel synthesis system can be improved.

  According to the present invention, the utilization efficiency of raw materials can be improved and the amount of carbon dioxide emissions can be reduced by effectively utilizing the hydrocarbon component having a small number of carbon atoms contained in the offgas without discarding it.

FIG. 1 is a schematic diagram showing the overall configuration of a liquid fuel synthesis system according to an embodiment of the present invention. FIG. 2 is a block diagram showing a configuration example of supply means for supplying gas discharged from the top of the rectifying column in the liquid fuel synthesizing system according to the embodiment of the present invention. FIG. 3 is a block diagram showing another configuration example of the supply means for supplying the gas discharged from the top of the rectifying column in the liquid fuel synthesizing system according to the embodiment of the present invention. FIG. 4 is a block diagram showing still another configuration example of the supply means for supplying the gas discharged from the top of the rectifying column in the liquid fuel synthesis system according to the embodiment of the present invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Liquid fuel synthesis system, 3 ... Syngas production unit, 5 ... FT synthesis unit, 7 ... Product refinement unit, 10 ... Desulfurization reactor, 12 ... First reformer, 14 ... Waste heat boiler, 16, 18 ... Gas-liquid separator, 20 ... decarbonation device, 22 ... absorption tower, 24 ... regeneration tower, 26 ... hydrogen separator, 30 ... bubble column reactor, 32 ... heat transfer tube, 34, 38 ... gas-liquid separator, 36 ... Separator, 40 ... First fractionator, 50 ... WAX fraction hydrocracking reactor, 52 ... Kerosene / light oil fraction hydrotreating reactor, 54 ... Naphtha fraction hydrocracking reactor, 56, 58, 60 ... Gas-liquid separator, 70 ... Second rectification column, 72 ... Naphtha stabilizer, 100 ... Off-gas recovery / supply path, 102 ... Second reformer, 104 ... Syngas supply path, 106 ... Hydrogen separator, 108 ... Carbon monoxide gas supply path, 110 ... Hydrogen storage equipment , 112 ... hydrogen gas supply path

  Exemplary embodiments of the present invention will be described below in detail with reference to the accompanying drawings. In addition, in this specification and drawing, about the component which has the substantially same function structure, duplication description is abbreviate | omitted by attaching | subjecting the same code | symbol.

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

  As shown in FIG. 1, a liquid fuel synthesis system 1 according to the present embodiment is a plant facility that executes a GTL process for converting a hydrocarbon raw material such as natural gas into liquid fuel. The liquid fuel synthesis system 1 includes a synthesis gas generation unit 3, an FT synthesis unit 5, and a product purification unit 7. The synthesis gas generation unit 3 reforms natural gas that is a hydrocarbon raw material to generate synthesis gas containing carbon monoxide gas and hydrogen gas. The FT synthesis unit 5 generates liquid hydrocarbons from the generated synthesis gas by a Fischer-Tropsch synthesis reaction (hereinafter referred to as “FT synthesis reaction”). The product refining unit 7 produces liquid fuel products (naphtha, kerosene, light oil, wax, etc.) by hydrogenating and refining the liquid hydrocarbons produced by the FT synthesis reaction. Hereinafter, components of each unit will be described.

First, the synthesis gas generation unit 3 will be described. The synthesis gas generation unit 3 includes, for example, a desulfurization reactor 10, a first reformer 12 (hereinafter referred to as “reformer 12”), an exhaust heat boiler 14, and gas-liquid separators 16 and 18. The decarboxylation device 20 and the hydrogen separation device 26 are mainly provided.
The desulfurization reactor 10 is composed of a hydrodesulfurization device or the like and removes sulfur components from natural gas as a raw material. The reformer 12 reforms the natural gas supplied from the desulfurization reactor 10 to generate a synthesis gas containing carbon monoxide gas (CO) and hydrogen gas (H ₂ ) as main components. The exhaust heat boiler 14 recovers the exhaust heat of the synthesis gas generated in the reformer 12 and generates high-pressure steam. The gas-liquid separator 16 separates water heated by heat exchange with the synthesis gas in the exhaust heat boiler 14 into a gas (high-pressure steam) and a liquid. The gas-liquid separator 18 removes the condensate from the synthesis gas cooled by the exhaust heat boiler 14 and supplies the gas to the decarboxylation device 20. The decarboxylation device 20 uses an absorption liquid from the synthesis gas supplied from the gas-liquid separator 18 to remove the carbon dioxide gas, and regenerates the carbon dioxide gas from the absorption liquid containing the carbon dioxide gas for regeneration. Tower 24. The hydrogen separation device 26 separates a part of the hydrogen gas contained in the synthesis gas from the synthesis gas from which the carbon dioxide gas has been separated by the decarbonation device 20.

  Among these, the reformer 12 reforms natural gas using carbon dioxide and steam by, for example, the steam / carbon dioxide reforming method represented by the following chemical reaction formulas (1) and (2). Thus, a high-temperature synthesis gas mainly composed of carbon monoxide gas and hydrogen gas is generated. The reforming method in the reformer 12 is not limited to the steam / carbon dioxide reforming method described above, but includes, for example, a steam reforming method, a partial oxidation reforming method (POX) using oxygen, and a partial oxidation method. An autothermal reforming method (ATR), a carbon dioxide gas reforming method, or the like, which is a combination of the reforming method and the steam reforming method, can also be used.

CH ₄ + H ₂ O → CO + 3H ₂ (1)
CH ₄ + CO ₂ → 2CO + 2H ₂ (2)

  Further, the hydrogen separator 26 is provided on a branch line branched from a main pipe connecting the decarbonator 20 or the gas-liquid separator 18 and the bubble column reactor 30. The hydrogen separator 26 can be constituted by, for example, a hydrogen PSA (Pressure Swing Adsorption) device that performs adsorption and desorption of hydrogen using a pressure difference. This hydrogen PSA apparatus has an adsorbent (zeolite adsorbent, activated carbon, alumina, silica gel, etc.) in a plurality of adsorption towers (not shown) arranged in parallel, and hydrogen is added to each adsorption tower. High-purity hydrogen gas (for example, about 99.999%) separated from the synthesis gas can be continuously supplied to the reactor by sequentially repeating the pressure, adsorption, desorption (decompression), and purge steps. it can.

  Note that the hydrogen gas separation method in the hydrogen separator 26 is not limited to the pressure fluctuation adsorption method such as the hydrogen PSA device described above, and for example, a hydrogen storage alloy adsorption method, a membrane separation method, or a combination thereof. There may be.

The hydrogen storage alloy method is, for example, a hydrogen storage alloy having a property of adsorbing / releasing hydrogen by being cooled / heated (TiFe, LaNi ₅ , TiFe _{0.7 to 0.9} , Mn _{0.3 to 0.1).} Or TiMn _1.5 or the like) to separate hydrogen gas. A plurality of adsorption towers containing hydrogen storage alloys are provided, and in each of the adsorption towers, hydrogen adsorption by cooling the hydrogen storage alloys and hydrogen release by heating the hydrogen storage alloys are alternately repeated, so that the inside of the synthesis gas Of hydrogen gas can be separated and recovered.

  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. Since this membrane separation method does not involve a phase change, the energy required for operation is small, and the running cost is low. Further, since the structure of the membrane separation apparatus is simple and compact, the equipment cost is low and the required area of the equipment is small. Further, the separation membrane has no driving device and has a wide stable operation range, so that there is an advantage that maintenance management is easy.

  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 generates a liquid hydrocarbon by performing an FT synthesis reaction of the synthesis gas produced by the synthesis gas production unit 3, that is, carbon monoxide gas and hydrogen gas. The gas-liquid separator 34 separates water heated through circulation in the heat transfer tube 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 fractionator 40 distills the 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. .

  Among these, the bubble column reactor 30 is an example of a reactor that synthesizes synthesis gas into liquid hydrocarbons, and functions as a reactor for FT synthesis that synthesizes liquid hydrocarbons from synthesis gas by an FT synthesis reaction. The bubble column reactor 30 is constituted by, for example, a bubble column type slurry bed type reactor in which a slurry composed 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 an 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 catalyst and medium oil. Then, as shown in the chemical reaction formula (3) below, the hydrogen gas and the carbon monoxide gas cause a synthesis reaction in the suspended state.

2nH ₂ + nCO → − (CH ₂ ) _n − + nH ₂ O (3)

  Since this FT synthesis reaction is an exothermic reaction, the bubble column reactor 30 is a heat exchanger type in which a heat transfer tube 32 is disposed inside, and supplies, for example, water (BFW: Boiler Feed Water) as a refrigerant. The heat of reaction of the FT synthesis reaction can be recovered as medium pressure steam by heat exchange between the slurry and water.

  Finally, the product purification unit 7 will be described. The product purification unit 7 includes, for example, a WAX fraction hydrocracking reactor 50, a kerosene / light oil fraction hydrotreating reactor 52, a naphtha fraction hydrotreating reactor 54, and gas-liquid separators 56, 58, 60, a second rectifying column 70, and a naphtha stabilizer 72. The WAX fraction hydrocracking reactor 50 is connected to the lower part of the first fractionator 40. The kerosene / light oil fraction hydrotreating reactor 52 is connected to the center of the first fractionator 40. The naphtha fraction hydrotreating reactor 54 is connected to the upper part of the first fractionator 40. The gas-liquid separators 56, 58 and 60 are provided corresponding to the hydrogenation reactors 50, 52 and 54, respectively. The second rectifying column 70 separates and purifies the liquid hydrocarbons supplied from the gas-liquid separators 56 and 58 according to the boiling point. The naphtha stabilizer 72 rectifies the liquid hydrocarbons of the naphtha fraction supplied from the gas-liquid separator 60 and the second rectifying column 70, and discharges lighter components than butane to the flare gas side, and has 5 or more carbon atoms. The components are separated and recovered as naphtha of the product.

  Next, a process (GTL process) of synthesizing liquid fuel from natural gas by the liquid fuel synthesizing system 1 having the above configuration will be described.

The liquid fuel synthesis system 1 is supplied with natural gas (main component is CH ₄ ) as a hydrocarbon feedstock from an external natural gas supply source (not shown) such as a natural gas field or a natural gas plant. The synthesis gas generation unit 3 reforms the natural gas to produce a synthesis gas (a mixed gas containing carbon monoxide gas and hydrogen gas as main components).

  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 sulfur contained in natural gas using the hydrogen gas, for example, with a ZnO catalyst. By desulfurizing the natural gas in advance in this way, it is possible to prevent the activity of the catalyst used in the reformer 12 and the bubble column reactor 30 or the like from being reduced by sulfur.

The natural gas (which may contain carbon dioxide) desulfurized in this way is generated in carbon dioxide (CO ₂ ) gas supplied from a carbon dioxide supply source (not shown) and the exhaust heat boiler 14. After being mixed with water vapor, it is supplied to the reformer 12. For example, the reformer 12 reforms the natural gas using carbon dioxide and steam by the steam / carbon dioxide reforming method described above, so that the reformer 12 has a high temperature mainly composed of carbon monoxide gas and hydrogen gas. Generate synthesis gas. At this time, for example, the fuel gas and air for the burner included in the reformer 12 are supplied to the reformer 12, and the steam / carbon dioxide gas which is an endothermic reaction by the combustion heat of the fuel gas in the burner. The reaction heat necessary for the reforming reaction is covered.

  The high-temperature synthesis gas (for example, 900 ° C., 2.0 MPaG) generated in the reformer 12 in this manner is supplied to the exhaust heat boiler 14 and is exchanged by heat exchange with the water flowing in the exhaust heat boiler 14. It is cooled (for example, 400 ° C.) and the exhaust heat is recovered. At this time, water heated by the synthesis gas in the exhaust heat boiler 14 is supplied to the gas-liquid separator 16, and the gas component is reformed as high-pressure steam (for example, 3.4 to 10.0 MPaG) from the gas-liquid separator 16. The water in the liquid is returned to the exhaust heat boiler 14 after being supplied to the vessel 12 or other external device.

  On the other hand, the synthesis gas cooled in the exhaust heat boiler 14 is supplied to the absorption tower 22 or the bubble column reactor 30 of the decarboxylation device 20 after the condensed liquid is separated and removed in the gas-liquid separator 18. The 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 in the absorption tower 22 is sent to the regeneration tower 24, and the absorption liquid containing carbon dioxide is heated by, for example, steam and stripped. To the reformer 12 and reused 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 adjusted to a composition ratio (for example, H ₂ : CO = 2: 1 (molar ratio)) suitable for the FT synthesis reaction. The synthesis gas supplied to the bubble column reactor 30 is subjected to an FT synthesis reaction by a compressor (not shown) provided in a pipe connecting the decarboxylation device 20 and the bubble column reactor 30. The pressure is increased to an appropriate pressure (for example, about 3.6 MPaG).

  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 the hydrogen gas contained in the synthesis gas by adsorption and desorption (hydrogen PSA) using the pressure difference as described above. The separated hydrogen is subjected to various hydrogen utilization reactions in which a predetermined reaction is performed using hydrogen in the liquid fuel synthesizing system 1 from a gas holder (not shown) or the like via a compressor (not shown). It supplies continuously to the apparatus (for example, desulfurization reactor 10, WAX fraction hydrocracking reactor 50, kerosene / light oil fraction hydrotreating reactor 52, naphtha fraction hydrotreating reactor 54, etc.).

  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 from which the carbon dioxide gas has been separated in the decarboxylation device 20 flows from the bottom of the bubble column reactor 30 and rises in the catalyst slurry stored in the bubble column reactor 30. To do. At this time, in the bubble column reactor 30, the carbon monoxide and hydrogen gas contained in the synthesis gas react with each other by the above-described FT synthesis reaction 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. Become. As for this water vapor, the water 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).

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 sent to the separator 36. The separator 36 separates the catalyst (solid content) in the extracted slurry into a 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. Further, unreacted synthesis gas and synthesized hydrocarbon gas are introduced into the gas-liquid separator 38 from the top of the bubble column reactor 30. The gas-liquid separator 38 cools these gases, separates some of the condensed liquid hydrocarbons, and introduces them into the first fractionator 40. On the other hand, for the gas component separated by the gas-liquid separator 38, the unreacted synthesis gas (CO and H ₂ ) is reintroduced into the bottom of the bubble column reactor 30 and reused in the FT synthesis reaction. In addition, exhaust gas (flare gas) mainly composed of hydrocarbon gas with a low carbon number (C ₄ or less) that is not a product target is introduced into an external combustion facility (not shown) and burned. Released into the atmosphere.

Next, the first rectifying column 40 heats the liquid hydrocarbon (having various carbon numbers) supplied from the bubble column reactor 30 through the separator 36 and the gas-liquid separator 38 as described above. Fractionation using the difference in boiling point, naphtha fraction (boiling point is less than about 315 ° C), kerosene / light oil fraction (boiling point is about 315 to 800 ° C), WAX (boiling point is about 800 ° C or more) Large) and separated and purified. Wax liquid hydrocarbons (mainly C ₂₁ or more) taken out from the bottom of the first fractionator 40 are transferred to the WAX fraction hydrocracking reactor 50 and taken out from the center of the first fractionator 40. The liquid hydrocarbon (mainly C _{11 to} C ₂₀ ) of the kerosene / light oil fraction is transferred to the kerosene / light oil fraction hydrotreating reactor 52 and taken out from the upper part of the first rectifying column 40. Hydrocarbons (mainly C ₅ -C ₁₀ ) are transferred to the naphtha fraction hydrotreating reactor 54.

The WAX fraction hydrocracking reactor 50 is a liquid fed from the lower part of the first rectifying column 40 to a liquid hydrocarbon having a high carbon number (approximately C ₂₁ or more) and hydrogen supplied from the hydrogen separator 26. Hydrocracking using gas to reduce the carbon number to ₂₀ or less. In this hydrocracking reaction, a C—C bond of a hydrocarbon having a large number of carbon atoms is cut using a catalyst and heat to generate a low molecular weight hydrocarbon having a small number of carbon atoms. A product containing liquid hydrocarbons hydrocracked by the WAX hydrocracking reactor 50 is separated into a gas and a liquid by a gas-liquid separator 56, and the liquid hydrocarbons are separated from the second fractionator. The gas component (including hydrogen gas) is transferred to a kerosene / light oil fraction hydrotreating reactor 52 and a naphtha fraction hydrotreating reactor 54.

The kerosene / light oil fraction hydrotreating reactor 52 is a liquid hydrocarbon (generally C _{11 to} C ₂₀ ) of the kerosene / light oil fraction supplied from the center of the first fractionator 40 and having a medium number of carbon atoms. Is hydrorefined using the hydrogen gas supplied from the hydrogen separator 26 via the WAX fraction 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 hydrorefined liquid hydrocarbon-containing product is separated into a gas and a liquid by the gas-liquid separator 58, and the liquid hydrocarbon is transferred to the second rectifying column 70, where the gas component (hydrogen Gas is reused) in the hydrogenation reaction.

The naphtha fraction hydrotreating reactor 54, the upper supplied from the naphtha fraction of liquid hydrocarbons having a small number of carbon atoms of the first fractionator 40 (approximately _of C ₁₀ or less), WAX fraction hydrogen from the hydrogen separator 26 Hydrotreating is performed using the hydrogen gas supplied through the hydrocracking reactor 50. As a result, the hydrorefined liquid hydrocarbon-containing product is separated into a gas and a liquid by the gas-liquid separator 60, and the liquid hydrocarbon is transferred to the naphtha stabilizer 72, where the gas component (hydrogen gas is removed). Is reused in the hydrogenation reaction.

Next, the second rectifying column 70 distills the liquid hydrocarbons supplied from the WAX fraction hydrocracking reactor 50 and the kerosene / light oil fraction hydrotreating reactor 52 as described above to obtain a carbon number. and _of C ₁₀ or less hydrocarbons (having a boiling point of approximately less than 315 ° C.), and kerosene (boiling point of about three hundred fifteen to four hundred fifty ° C.), separated and purified in the gas oil (boiling point of about 450 to 800 ° C.). Light oil is taken out from the lower part of the second fractionator 70, and kerosene is taken out from the center. On the other hand, a hydrocarbon gas having a carbon number of ₁₀ or less is taken out from the top of the second rectifying column 70 and supplied to the naphtha stabilizer 72.

Further, the naphtha stabilizer 72 distills hydrocarbons having a carbon number of ₁₀ or less supplied from the naphtha fraction hydrotreating reactor 54 and the second rectifying tower 70 to obtain naphtha (C ₅ as a product). ~C ₁₀₎ are separated and purified. Thereby, high-purity naphtha is taken out from the lower part of the naphtha stabilizer 72. Meanwhile, from the top of the naphtha stabilizer 72, the exhaust gas carbon number of target products composed mainly of hydrocarbons below predetermined number (C ₄ or less) (off-gas) is discharged. This off gas is usually sent to an external combustion facility (not shown), burned as flare gas, and released into the atmosphere as exhaust gas. However, the liquid fuel synthesis system according to the present embodiment uses this off gas. The hydrocarbons having 4 or less carbon atoms are recovered by using the method described in detail below and reused as a part of the raw material.

The process of the liquid fuel synthesis system 1 (GTL process) has been described above. By such a GTL process, natural gas is clean such as high-purity naphtha (C _{5 to} C ₁₀ : crude gasoline), kerosene (C _{11 to} C ₁₅ : kerosene) and light oil (C _{16 to} C ₂₀ : gas oil). It can be easily and economically converted to liquid fuel. Furthermore, in this embodiment, since the steam / carbon dioxide reforming method is adopted in the reformer 12, carbon dioxide contained in natural gas as a raw material is effectively used, and the FT synthesis is performed. A composition ratio (for example, H ₂ : CO = 2: 1 (molar ratio)) of synthesis gas suitable for the reaction can be efficiently generated by one reaction of the reformer 12, and a hydrogen concentration adjusting device, etc. There is an advantage that is unnecessary.

  Subsequently, using FIG. 2 to FIG. 4, hydrocarbons having 4 or less carbon atoms contained in the off-gas discharged from the top of the naphtha stabilizer are used as raw materials for the liquid fuel synthesis system 1 according to the present embodiment. The supply means supplied as a part will be described in detail.

  FIG. 2 is a block diagram for explaining supply means for supplying off-gas discharged from the top of the naphtha stabilizer 72 to a device upstream of the naphtha stabilizer 72 in the liquid fuel synthesis system according to the present embodiment. FIG. In FIG. 2, for convenience of explanation, main components among the components of the liquid fuel synthesis system 1 of FIG. 1 are illustrated, and some of the components are not illustrated.

  As described above, the off-gas discharged from the top of the naphtha stabilizer contains hydrocarbons having 4 or less carbon atoms. These hydrocarbons having 4 or less carbon atoms are hydrocarbons that are not products, but can be used as hydrocarbon raw materials introduced into the first reformer 12.

  As shown in FIG. 2, in the configuration example according to the present embodiment, the end of the off-gas recovery / supply path 100 is connected to the top of the naphtha stabilizer 72 and the other end of the off-gas recovery / supply path 100 is connected. Is connected to the further upstream side of the reformer 12. By providing such a path 100, the hydrocarbon gas having 4 or less carbon atoms contained in the off gas can be reused as part of the hydrocarbon raw material introduced into the reformer 12.

  By providing the off gas recovery / supply path 100 as described above, the amount of natural gas supplied from a natural gas supply source (not shown) provided further upstream of the reformer 12 can be reduced. Therefore, the utilization efficiency of the hydrocarbon raw material as the whole liquid fuel synthesis system can be improved.

  Note that at the connection point between the off-gas recovery / supply path 100 and the main path for supplying natural gas, both paths are connected via a regulating valve (not shown) and the pressure of the off-gas existing in the path 100. The supply amount of natural gas may be adjusted according to the flow rate or the like.

  FIG. 3 is a diagram illustrating another configuration example of supplying off-gas discharged from the top of the naphtha stabilizer 72 to a device upstream of the naphtha stabilizer 72 in the liquid fuel synthesis system according to the present embodiment. FIG. Also in FIG. 3, for convenience of explanation, the main components of the liquid fuel synthesizing system 1 of FIG. 1 are shown, and some of the components are not shown.

  In this configuration example, off-gas discharged from the top of the naphtha stabilizer 72 is introduced into a second reformer 102 (hereinafter referred to as “reformer 102”) provided separately from the reformer 12. Then, the gas is reformed to produce a synthesis gas mainly composed of carbon monoxide gas and hydrogen gas. Carbon dioxide required for reforming off-gas may be supplied from a separately provided carbon dioxide supply source (not shown), or a carbon dioxide supply source for supplying carbon dioxide to the reformer 12 ( (Not shown) may be supplied, or may be reformed only with steam.

  The synthesis gas synthesized by the reformer 102 is supplied to the upstream side of the bubble column reactor 30 via the synthesis gas supply path 104 connected to the reformer 102, and is used as a raw material for the FT synthesis reaction or the like. Use as As described above, the off gas discharged from the top of the tower is reformed and used as a synthesis gas, whereby the utilization efficiency of natural gas as the whole liquid fuel synthesis system can be improved.

  It should be noted that the amount of synthesis gas produced by the reformer 12 and the reformer 102 can be monitored, respectively. It is also possible to reduce the amount of natural gas supplied from a natural gas supply source (not shown) by suppressing the amount of synthesis gas produced in the mass device 12.

  FIG. 4 illustrates still another configuration example in which the off-gas discharged from the top of the naphtha stabilizer 72 is supplied to a device upstream of the naphtha stabilizer 72 in the liquid fuel synthesis system according to the present embodiment. It is a block diagram for. In FIG. 4 as well, for convenience of explanation, major components of the liquid fuel synthesizing system 1 of FIG. 1 are shown, and some components are not shown.

  The configuration example shown in FIG. 4 includes a reformer 102 for reforming off-gas discharged from the top of the naphtha stabilizer 72, and carbon monoxide gas and hydrogen gas synthesized by the reformer 102 as main components. The hydrogen separation device 106 that separates the synthesis gas into carbon monoxide gas and hydrogen gas, and the hydrogen storage device 110 that stores the hydrogen gas separated by the hydrogen separation device 106 are mainly provided.

  Since the reformer 102 has the same function as that shown in FIG. 3 and exhibits the same effect, a detailed description thereof will be omitted. The hydrogen separation device 106 is a device that separates the synthesis gas synthesized by the reformer 102 into carbon monoxide gas and hydrogen gas. The hydrogen separator 106 includes a carbon monoxide gas supply path 108 for supplying the separated carbon monoxide gas further upstream of the bubble column reactor 30, and a hydrogen storage capable of storing the separated hydrogen gas. The device 110 is connected. The hydrogen separation device 106 described above has the same function as the hydrogen separation device 26 provided in the synthesis gas generation unit 3 and can exhibit the same effect.

  A separate supply path may be provided in the reformer 102 so that the synthesized gas synthesized can be directly supplied to the upstream side of the reformer 12.

  The carbon monoxide gas supply path 108 supplies the carbon monoxide gas separated by the hydrogen separator 106 in order to adjust the carbon monoxide gas concentration of the synthesis gas supplied to the bubble column reactor 30, for example. In other words, the carbon monoxide concentration of the synthesis gas generated in the reformer 12 is monitored, and when the amount of carbon monoxide supplied from the reformer 12 is small, the carbon monoxide gas supply path 108 is provided. Alternatively, carbon monoxide gas may be supplied to the reformer 12 from the carbon monoxide gas supply path 108 via a carbon monoxide storage device and a carbon monoxide compressor (not shown).

  The hydrogen storage device 110 is configured by a storage tank configured by a pressure vessel such as a spherical storage tank, for example, and can store the hydrogen gas separated by the hydrogen separation device 106, for example, by liquefying. A hydrogen gas supply path 112 is connected to the hydrogen storage device 110.

  The hydrogen gas supply path 112 can appropriately adjust the hydrogen gas concentration by supplying the hydrogen gas to any location that requires the hydrogen gas in the liquid fuel synthesis system 1 according to the present embodiment. The locations requiring hydrogen gas include, for example, a desulfurization reactor 10 for hydrodesulfurizing natural gas that is a hydrocarbon raw material, and a plurality of different boiling points from synthesis gas mainly composed of carbon monoxide gas and hydrogen gas. A bubble column reactor 30 for synthesizing a liquid fuel, and hydrogenation reactors 50 for hydrogenating a liquid fuel having an unsaturated carbon-carbon bond such as a C═C double bond or a C≡C triple bond, 52, 54 and so on.

  In the liquid fuel synthesizing system 1 according to this embodiment, by providing the supply means as described above, the amount of natural gas used as a raw material is about 10 to 15 in the entire system as compared with the conventional liquid fuel synthesizing system. % Or more can be reduced.

  By providing the hydrogen storage device 110, the hydrogen gas can be instantaneously supplied from the hydrogen storage device 110 when hydrogen gas is needed. Therefore, when the liquid fuel synthesizing system 1 is restarted, the hydrogen gas stored in the hydrogen storage device 110 is immediately supplied to the hydrogen utilization reactors such as the hydrogenation reactors 50, 52, 54 and the desulfurization reactor 10. Therefore, the time required for starting up these hydrogen utilization reactors to operate stably can be reduced to the 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, light oil, and wax can be improved.

  As mentioned above, although preferred embodiment of this invention was described referring an accompanying drawing, it cannot be overemphasized that this invention is not limited to this example. 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.

  For example, in the above embodiment, natural gas is used as the hydrocarbon raw material supplied to the liquid fuel synthesizing system 1. However, the present invention is not limited to this example, and other hydrocarbon raw materials such as asphalt and residual oil are used. May be.

  Moreover, although the said embodiment demonstrated the case where the decarbonation apparatus 20 was provided in the liquid fuel synthesis system 1, depending on the case, the decarboxylation apparatus 20 does not need to be provided.

Moreover, in the said embodiment, although the liquid hydrocarbon was synthesize | combined by FT synthesis reaction as a synthesis reaction in the bubble column reactor 30, this invention is not limited to this example. As the synthesis reaction in the bubble column reactor, for example, oxo synthesis (hydroformylation reaction) “RCH═CH ₂ + CO + H ₂ → RCH ₂ CH ₂ CHO”, methanol synthesis “CO + 2H ₂ → CH ₃ OH”, dimethyl ether (DME) The present invention can also be applied to synthesis “3CO + 3H ₂ → CH ₃ OCH ₃ + CO ₂ ” and the like.

  In the above embodiment, examples of the desulfurization reactor 10, the WAX fraction hydrocracking reactor 50, the kerosene / light oil fraction hydrotreating reactor 52, and the naphtha fraction hydrotreating reactor 54 are used as the hydrogen utilization reactor. However, the present invention is not limited to this example, and any apparatus other than those described above may be used as long as the apparatus performs a predetermined reaction using hydrogen gas in the liquid fuel synthesis system. Specifically, the hydrogen utilization reaction apparatus is, for example, a fuel cell, an apparatus for performing a hydrogenation reaction of naphthalene (naphthalene → decalin), an apparatus for performing an aromatic hydrocarbon (benzene) hydrogenation reaction (benzene → cyclohexane, etc.) Alternatively, an apparatus for performing a hydrogenation reaction on an unsaturated fatty acid may be used.

  In the above embodiment, the bubble column type slurry bed type reactor is used as the reactor for synthesizing the synthesis gas into the liquid hydrocarbon. However, the present invention is not limited to this example, and for example, a fixed bed type reactor. The FT synthesis reaction may be performed using such as.

  In the above embodiment, the off gas discharged from the top of the naphtha stabilizer has been described as an example. However, the present invention is not limited to the exhaust gas from the top of the naphtha stabilizer. It is also possible to perform the above-described treatment on the exhaust gas from the top of the distillation column and the exhaust gas from the gas-liquid separator.

The present invention includes a first reformer for reforming a hydrocarbon raw material to produce a synthesis gas mainly composed of carbon monoxide gas and hydrogen gas; and from the carbon monoxide gas and hydrogen gas contained in the synthesis gas. A reactor for synthesizing liquid hydrocarbons; a first rectifying tower for fractionating a plurality of types of liquid fuels having different boiling points by heating the liquid hydrocarbons synthesized in the reactor; and included in the synthesis gas A hydrogen-using reaction device that performs a predetermined reaction on the hydrocarbon raw material or the liquid fuel using the hydrogen gas; and a second refiner that purifies the liquid separated and recovered from the hydrogen-using reaction device. A distillation column; and supply means for supplying a gas discharged from the second rectification column to at least one of the first reformer, the hydrogen-utilization reactor, and the reactor as a part of a raw material. A liquid fuel synthesis system comprising: To.
According to the liquid fuel synthesizing system of the present invention, the utilization efficiency of raw materials can be improved, and the amount of carbon dioxide emissions can be reduced.

Claims (7)

A first reformer for reforming a hydrocarbon raw material to produce a synthesis gas mainly composed of carbon monoxide gas and hydrogen gas;
A reactor for synthesizing liquid hydrocarbons from carbon monoxide gas and hydrogen gas contained in the synthesis gas;
A first rectifying column for heating the liquid hydrocarbon synthesized in the reactor to fractionate a plurality of types of liquid fuels having different boiling points;
A hydrogen-based reaction apparatus that performs a predetermined reaction on the hydrocarbon raw material or the liquid fuel using the hydrogen gas contained in the synthesis gas;
A second rectifying column for purifying the liquid separated and recovered from the hydrogen-utilizing reactor;
A supply means for supplying a gas discharged from the second rectification column to at least one of the first reformer, the hydrogen-utilizing reactor, and the reactor as a part of a raw material. Fuel synthesis system.   The hydrogen-utilizing reaction apparatus includes a hydrogenation reactor that hydrogenates at least one of the plurality of types of liquid fuels, or a desulfurization reaction that hydrodesulfurizes the hydrocarbon raw material supplied to the first reformer. The liquid fuel synthesis system according to claim 1, comprising at least one of the vessels. A naphtha stabilizer provided downstream of the second rectifying column;
2. The liquid according to claim 1, wherein the gas is discharged from the naphtha stabilizer and is supplied as a part of a raw material to at least one of the first reformer, the hydrogen-utilizing reactor, and the reactor. Fuel synthesis system.   The liquid fuel synthesis system according to claim 3, further comprising a second reformer that reforms the gas discharged from the naphtha stabilizer. A hydrogen separation device for separating hydrogen gas from the synthesis gas obtained by the second reformer;
The liquid fuel synthesizing system according to claim 4, wherein the supply means supplies the hydrogen gas separated by the hydrogen separator to the reactor or the hydrogen utilizing reactor.   The liquid fuel synthesis system according to claim 5, further comprising a hydrogen storage device that stores hydrogen gas separated by the hydrogen separation device.   The liquid fuel synthesizing system according to claim 6, wherein the supply unit supplies the hydrogen gas stored in the hydrogen storage device to the hydrogen utilization reaction device when the liquid fuel synthesizing system is activated.

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