WO2015129970A1 - Appareil et procédé gaz-à-liquide de fischer-tropsch pour produire du pétrole brut synthétique unique - Google Patents

Appareil et procédé gaz-à-liquide de fischer-tropsch pour produire du pétrole brut synthétique unique Download PDF

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WO2015129970A1
WO2015129970A1 PCT/KR2014/007012 KR2014007012W WO2015129970A1 WO 2015129970 A1 WO2015129970 A1 WO 2015129970A1 KR 2014007012 W KR2014007012 W KR 2014007012W WO 2015129970 A1 WO2015129970 A1 WO 2015129970A1
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Prior art keywords
crude oil
synthetic crude
gtl
producing
unit
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PCT/KR2014/007012
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English (en)
Korean (ko)
Inventor
권혁
문영식
최정호
김원석
박태신
고글랜
덴흠더글라스
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대우조선해양 주식회사
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Priority claimed from KR1020140024695A external-priority patent/KR101562823B1/ko
Priority claimed from KR1020140059689A external-priority patent/KR101597557B1/ko
Application filed by 대우조선해양 주식회사 filed Critical 대우조선해양 주식회사
Priority to JP2016552950A priority Critical patent/JP2017512225A/ja
Priority to US15/122,140 priority patent/US20160369173A1/en
Priority to EP14883641.4A priority patent/EP3112250A4/fr
Publication of WO2015129970A1 publication Critical patent/WO2015129970A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G5/00—Recovery of liquid hydrocarbon mixtures from gases, e.g. natural gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/31—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen thermal, non catalytic conversion
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1025—Natural gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4037—In-situ processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4062—Geographical aspects, e.g. different process units form a combination process at different geographical locations

Definitions

  • the present invention relates to a Fischer-Tropsch (FT) Gas-to-Liquid (FT) device and method for producing a single synthetic crude oil, and in particular, to GTL FPSO (Floated Production, Storage, and Off-loading) ),
  • FT wax is a low-level, general grade to fluidize FT wax, which is difficult to transport due to its solid state in the syncrude products (FT naphtha, FT heavy oil, FT wax) as intermediate products of the chemical process.
  • the FT GTL process involves the use of a high pressure catalytic reactor to convert syngas, a mixture of hydrogen and carbon monoxide, including small amounts of methane and carbon dioxide, into large hydrocarbon molecules.
  • the FT synthesis reaction in the Fischer-Tropsch synthesis reactor is as follows.
  • the catalyst iron oxide-based and cobalt-based materials are used, the temperature is 200 to 350 ° C., and the pressure is 10 to 30 bar. This reaction is a moderate exothermic reaction, and the exothermic control through heat exchange is important for improving the catalytic reaction rate, which is a key element of the reactor design.
  • the FT product produced from the catalytic reactor consists of unreacted syngas, methane, ethane, LPG (C3 to C4), naphtha (C5 to C10), heavy oil (C11 to C22) and wax (> C22).
  • FT essentially produces hundreds of components in the carbon numbers 1 to 40 and above.
  • the relative amount of such material in the raw product depends mainly on the reactor reaction temperature and the catalyst used.
  • the catalyst used there are three basic FT operating systems. That is, high temperature FT reaction using iron catalyst (HTFT-Fe), low temperature FT reaction using iron catalyst (LTFT-Fe), low temperature FT reaction using cobalt catalyst (LTFT-Co).
  • FPSO is a floating crude oil production storage and unloading facility, produces and stores the crude oil floating on the sea and serves to unload crude oil transportation means such as tankers.
  • the FPSO includes drilling equipment for drilling crude oil and an oil / gas separation device for separating crude oil and associated gas in a glass oil state.
  • the FPSO also includes storage facilities for storing crude oil and unloading means for transferring crude oil to crude oil transportation means.
  • FPSO-GTL and FPSO-DME which is used as a raw material of the GTL process, are manufactured as a synthesis gas on the ship, and the accompanying gas of the oil field is applied.
  • natural gas extracted directly from the marginal gas field can be used in the FPSO-GTL process for producing synthetic fuel, or in the FPSO-LNG process for direct liquefaction.
  • Patent Document 1 discloses an FPSO facility including a separator for glacier oil and an oil / gas separation unit, and a direct method including a reforming reactor, a dimethylether reactor, a CO2 subsea storage device, and a power generation system for internal power generation.
  • An FPSODME apparatus for manufacturing an offshore DME comprising a hydrogen separator and a carbon dioxide separation unit between the reforming reactor and the dimethyl ether reactor, wherein the dimethyl ether reactor is combined with a carbon dioxide separator to generate the separated carbon dioxide and the internal power generation system.
  • an offshore oilfield FPSO-DME device configured to recycle water and carbon dioxide back to the reforming reactor and to store excess carbon dioxide on the seabed.
  • Patent Document 2 the FPSO facility comprising a glass oil separator for separating the oil from the oil and the accompanying gas and crude oil, oil / gas separation unit for separating the separated crude oil and oil; A reforming reactor for receiving a gas from which the carbon compound having 1 to 4 carbon atoms separated from the gas supplied from the FPSO facility is removed from the H 2 S component as a sulfur compound through a desulfurizer; Liquid carbon compound production apparatus for producing a liquid carbon compound using the synthesis gas passed through the reforming reactor; An upgraded reactor for supplying separated hydrogen by converting the synthesis gas passed through the reforming reactor into a water gas conversion reaction; A CO2 subsea storage device for supplying surplus in carbon dioxide other than hydrogen separated from syngas; An FPSO-GTL apparatus including an internal power generation system for internal power generation of an FPSO-GTL apparatus, wherein a hydrogen separator and a carbon dioxide separation unit are configured between the reforming reactor and the liquid carbon compound producing apparatus, and the liquid carbon compound is produced.
  • a reforming reactor for
  • a water separator is constructed between the apparatus and the upgrading reactor, the offshore oil configured to recycle the separated water and carbon dioxide and the water and carbon dioxide produced in the internal power generation system back to the reforming reactor and to store excess carbon dioxide in the seabed.
  • a dedicated FPSO-GTL device is disclosed.
  • Synthetic crude oil is an artificial fuel made from natural gas, coal, and bio raw materials in addition to petroleum. In Korea, it is being developed as a next-generation clean fuel compound technology at major large corporations and research institutes under the government's initiative. As the high oil price trend is intensifying in the future, demand for GTL clean fuel is expected to soar.
  • GTL FPSO In the same vein, the development of GTL FPSO to implement land technologies at sea is being promoted, but there are still many problems to be solved before commercialization.
  • One of the problems inherent in the GTL FPSO includes the issue of "guaranteed liquidity for the storage and transportation of GTL synthetic crude oil". This is due to the high viscosity of the synthetic oil produced in GTL FPSO containing a large amount of wax. Therefore, the liquidity of synthetic crude oil is recognized as one of the key factors to secure efficient operation and economic feasibility of GTL FPSO.
  • Korean Patent Publication No. 0339993 includes contacting tar / sludge with an effective amount of a surfactant and an effective amount of an inorganic acid and / or a carrier, wherein the inorganic acid Provides a method of washing or fluidizing tar / sludge from vessels / tubes which are sulfuric acid, phosphoric acid or mixtures thereof. Accordingly, the effect of removing tar / sludge in a form that can be easily transported, handled and pumped is expected.
  • an object of the present invention is to improve the economics of a series of processes from production / storage / unloading / transport / separation by securing the fluidity by producing and mixing while controlling the wax components of the synthetic crude oil produced in GTL FPSO It is to provide a wax component control device for GTL FPSO synthetic crude oil.
  • FT Fischer-Tropsch
  • FPSO Floated Production, Storage, and Off-loading
  • a gas injection stabilization unit that performs stabilization on the produced natural gas to generate natural gas condensate
  • a single FT GTL apparatus for producing crude oil comprising a reforming unit for reforming natural gas processed in the gas injection stabilization unit to produce a synthetic crude oil product.
  • a product processing unit for mixing the natural gas condensate and the synthetic crude product, it is possible to produce a single synthetic crude oil.
  • the gas injection stabilization unit may include a first three-phase separator injecting CH 1 to 40 and H 2 O to separate CH 1 to 4 and the natural gas condensate (CH 5 to 40) and water (H 2 O). .
  • the synthetic crude oil product is FT naphtha, FT heavy oil, FT wax
  • the reforming unit is a FT reactor for producing the FT wax and a second mixture for producing a first mixture of the FT naphtha and FT heavy oil mixed.
  • Three-phase separators are preferred.
  • the second three-phase separator may separate the residual gas, H 2 O, and the first mixture by heat-exchanging the synthesis gas treated in the FT reactor in a first heat exchanger.
  • the product processing unit stores the first mixture, FT naphtha, a second mixture of FT heavy oil and FT wax, a product mixing tank for mixing natural gas condensate, and a GTL liquid mixed in the product mixing tank. It may include a storage tank.
  • the product processing unit is a second heat exchanger that heat exchanges for the FT wax produced in the FT reactor, a hydrocracking reaction or mild hydroisomerization reaction for the FT wax heat exchanged in the second heat exchanger.
  • a reactor for producing the second mixture through may further include a separator for separating the unreacted residual gas in the second mixture.
  • the product processing unit further comprises a first compressor for compressing residual gas and a second compressor for adding hydrogen, wherein the unreacted residual gas separated in the separator is separated from the first compressor and the second compressor. It may be supplied to the second heat exchanger via a compressor.
  • a residual gas separation unit for separating the residual gas and the first mixture of FT naphtha and FT heavy oil mixed in the synthetic crude oil
  • the first mixture separated in the residual gas separation unit may be supplied to the product processing unit.
  • the reforming unit F-T synthesis unit for producing a synthesis gas generated from natural gas as a synthetic oil; And a control unit for controlling the F-T synthesis unit to maintain the wax component of the synthetic crude oil modified with the synthetic oil at a set value.
  • the FT synthesis unit comprises an LT-FT reactor and a HT-FT reactor in series or in parallel, and the flow rate of the LT-FT reactor and the HT-FT reactor in response to the composition of the synthetic crude oil generated downstream I can regulate it.
  • control unit may include a wax detection unit for detecting the wax content of the synthetic crude oil, and an unreacted gas detection unit for detecting the content of the unreacted gas.
  • control unit may be controlled to keep the wax component to a minimum within the limit of keeping the unreacted gas within the set value.
  • FT Fischer-Tropsch
  • FT Gas-to-Liquid
  • step (c) may be carried out by wax hydrocracking or mild hydrogenation isomerization.
  • the single synthetic crude oil produced in step (d) can be stored and transported without heat treatment.
  • the method may further comprise (e) refining the single synthetic crude oil in a land refining plant.
  • the FT GTL apparatus and method for producing a single synthetic crude oil according to the present invention through simple installation of equipment upgrading equipment, it is possible to save the deck space in the FPSO, to reduce the production cost, and to store the product in the FPSO Only one tank is needed, and there is no need for additional heat supply to move it to storage and pumps, resulting in lower transportation costs.
  • FT GTL apparatus and method for producing a single synthetic crude oil after mixing FT naphtha and FT heavy oil, a portion of the FT wax can be transported at a low level so that the synthetic crude oil can be transported without heating.
  • a general hydrocracking reaction or weak hydroisomerization reaction the complexity, space and cost can be reduced when compared with the entire refinery having high pressure hydrocracking, and the amount of hydrogen used compared with the entire refinery. You can also achieve the effect.
  • the present invention has the effect of accumulating the commercialization technology of the related field by improving the economics for a series of processes ranging from production / storage / unloading / transport / separation by securing the fluidity of the synthetic crude oil produced in GTL FPSO.
  • FIG. 1 is an overall configuration diagram of an FT GTL apparatus for producing a single synthetic crude oil according to a first embodiment of the present invention.
  • FIG. 2 is a diagram illustrating a coupling relationship between main units of FIG. 1.
  • FIG. 3 is a flowchart illustrating a FT GTL method for producing a single synthetic crude oil according to the first embodiment of the present invention.
  • FIG. 5 is a view for explaining the production / storage / unloading / transport / separation of a single synthetic crude oil according to a first embodiment of the present invention.
  • FIG. 6 is a flowchart illustrating the main process of the GTL FPSO according to the second embodiment of the present invention.
  • FIG. 7 is a configuration diagram showing main parts of the F-T synthesis unit of FIG. 6.
  • FIG. 7 is a configuration diagram showing main parts of the F-T synthesis unit of FIG. 6.
  • GTL FPSO is an offshore structure that can produce clean energy at sea by fusing GTL with floating oil production storage and unloading facilities (FPSO).
  • the GTL process is a reforming process that generates syngas (H2, CO) from natural gas (NG), a FT (Fischer-Tropsch) process that generates synthetic oil from syngas, and synthetic crude oil as the desired carbon number fuel. Conversion to an upgrading process.
  • the first embodiment of the present invention is for producing a synthetic crude oil product that can be transported in a single FT GTL FPSO for this purpose. That is, it is a new concept to produce a single mixed FT synthetic crude that can be stored and transported without heat treatment with a mixture of FT naphtha, FT heavy oil and treated FT wax.
  • the single mixed FT synthetic crude oil concept requires the use of suitable catalysts, reactor designs, and operating systems for wax hydrocracking or mild hydroisomerization.
  • This single mixed FT synthetic crude oil concept can reduce the cost and space for FT product processing and simplify the storage and transportation conditions for FT GTL FPSO products.
  • synthetic crude oil produced from multiple FT GTL FPSOs is transported and processed in a single coastal refining plant. It can also be produced as a commercially available vehicle fuel by mixing and / or further refinement with common crude oil products. This concept is useful because it allows the entire system to benefit from economies of scale in coastal refining plants, while operating carrier fleets more efficiently and minimizing space and capital requirements for FPSOs.
  • a part of the FT wax is mixed with a low level of general hydrocracking reaction or weak hydroisomerization reaction so that the synthetic crude oil can be transported without heating.
  • the concept involves the use of catalysts and operating systems that do not produce the final FT product, but transforms the blended crude oil into sufficient storage and transport without heat treatment. It also does not involve diluting (or mixing) naphtha and heavy oil with the treated wax, but involves the use of different catalysts for the purpose of producing multiple products.
  • This concept involves hydrocracking FT wax to raise the pour point freezing point without intentionally modifying other properties, only without hydrogenation or intentionally attempting to modify other properties.
  • the size, space and cost of processing FPSO onboard FT products will be reduced while simplifying product storage and transportation.
  • FIG. 1 is an overall configuration diagram of an FT GTL apparatus for producing a single synthetic crude oil according to a first embodiment of the present invention.
  • the FT GTL apparatus for producing a single synthetic crude oil according to the first embodiment of the present invention is an FT GTL apparatus for producing a single synthetic crude oil in FPSO, as shown in FIG. 10), desulfurization unit 20, natural gas saturation and pre-reforming unit 30, small reforming unit 40, syngas conditioning unit 50, FT synthesis unit 60, a tail gas separation unit 70, and a production treatment unit 80.
  • the gas injection stabilization unit 10 performs stabilization on the produced crude natural gas (RAW NG) to generate natural gas, natural gas condensate and water (H 2 O), and the natural gas condensate is processed into a product. Supplied to the unit 80.
  • the desulfurization unit 20 removes sulfur contained in natural gas and supplies crude natural gas to the natural gas saturation and preliminary reforming unit 30.
  • a portion of the crude natural gas pretreated in the natural gas saturation and preliminary reforming unit 30 is used as a gas for fuel, and the remaining natural gas is heated by steam and supplied to the reforming unit 40 and discharged to the saturator.
  • the reforming unit 40 reforms the natural gas supplied through steam in the natural gas saturation and preliminary reforming unit 30 to crude syngas (RAW SYNGAS) to produce a synthetic crude product.
  • the gas not processed in the reforming unit 40 is supplied to the natural gas saturation and preliminary reforming unit 30 as fuel gas.
  • the crude syngas treated in the reforming unit 40 is generated as syngas SYNGAS in the syngas adjusting unit 50, and hydrogen (H2) generated in this process is fuel gas, and the reforming unit 40 and product processing. Supplied to the unit 80.
  • the syngas condensate produced in the syngas adjusting unit 50 is supplied or discharged to the natural gas saturation and preliminary reforming unit 30.
  • the syngas supplied from the syngas adjusting unit 50 is separated into a first mixture of FT naphtha and FT heavy oil and FT wax through the FT synthesis unit 60 and supplied to the product processing unit 80.
  • the residual gas separation unit 70 separates a residual gas and a first mixture of FT naphtha and FT heavy oil from the syngas supplied from the FT synthesis unit 60, and the first mixture is a product processing unit 80.
  • the remaining gas is partially discharged or supplied to the natural gas saturation and preliminary reforming unit 30 for recycling.
  • the product processing unit 80 is supplied from the natural gas condensate supplied from the gas injection stabilization unit 10, the first mixture and FT wax supplied from the FT synthesis unit 60, and the residual gas separation unit 70.
  • the first mixture is mixed to produce a single synthetic crude oil according to the invention.
  • the boiler feed water (BFW) for forming steam is supplied to the reforming unit 40 and the syngas adjusting unit 50.
  • FIG. 2 is a diagram illustrating a coupling relationship between main units of FIG. 1.
  • the gas injection stabilization unit 10 injects CH 1 to 40 and H 2 O to separate CH 1 to 4 and the natural gas condensate (CH 5 to 40) and water (H 2 O).
  • a phase separator 41 The natural gas condensate (CH5 ⁇ 40) is supplied to the product processing unit 80, the water (H2O) is supplied to the natural gas saturation and preliminary reforming unit (30).
  • the reforming unit 40 includes an FT reactor 41 for producing FT wax in natural gas and a second three-phase separator 42 for producing a first mixture of the FT naphtha and FT heavy oil.
  • the second three-phase separator 42 heats the syngas treated in the FT reactor 41 in a first heat exchanger 43 to separate residual gas, H 2 O, and the first mixture.
  • the mixture is fed to the product processing unit 80.
  • the product processing unit 80 is supplied from the first mixture supplied from the second three-phase separator 42, the second mixture of FT naphtha, the FT heavy oil and the FT wax, and the gas injection stabilization unit 10.
  • the product mixing tank 81 for mixing the natural gas condensate, the storage tank 82 for storing the GTL liquid mixed in the product mixing tank 81, the heat exchanger for the FT wax produced in the FT reactor 41
  • a reactor 84 for producing the second mixture through a hydrocracking reaction or a mild hydroisomerization reaction with respect to the FT wax heat exchanged in the second heat exchanger 83 and the second heat exchanger 83;
  • a separator 85 for separating unreacted residual gas from the second mixture.
  • the single synthetic crude oil product according to the invention is a mixture of FT naphtha, FT heavy oil and FT wax.
  • the first mixture of FT naphtha and FT heavy oil, the second mixture of FT naphtha, FT heavy oil and FT wax, and natural gas condensate are mixed and stored in the product mixing tank 81 as described above. It is a product stored in the tank 82.
  • a single synthetic crude oil product manufactured as described above requires only one tank, storage tank 82, for storage of the product in the FPSO, and requires no additional heat supply to move to storage and pumps, thereby reducing transportation costs. can do.
  • the product processing unit 80 further includes a first compressor 86 for compressing the residual gas separated in the separator 85 and a second compressor 87 for adding hydrogen, the separator 85
  • the unreacted residual gas separated in is supplied to the second heat exchanger 83 via the first compressor 86 and the second compressor 87.
  • FIG 3 is a process chart for explaining a single synthetic crude oil production FT GTL method according to a first embodiment of the present invention
  • Figure 4 is a production / storage / unloading / transport of a single synthetic crude oil according to a first embodiment of the present invention It is a figure for demonstrating / separation.
  • the FT GTL method for producing a single synthetic crude oil according to the first embodiment of the present invention is a FT GTL method for producing a single synthetic crude oil in FPSO.
  • natural gas is stabilized in the gas injection stabilization unit 10 to generate natural gas condensate. (S10).
  • the sulfur contained in the natural gas is then removed in the desulfurization unit 20 and syngas is produced through the natural gas saturation and preliminary reforming unit 30 and the small reforming unit 40.
  • the reforming unit 40 generates a first mixture and FT wax in which FT naphtha and FT heavy oil are mixed through the synthesis gas (S20).
  • the product processing unit 80 performs a wax hydrocracking reaction or a mild hydroisomerization reaction on the FT wax to generate a second mixture of FT naphtha, FT heavy oil, and FT wax (S30).
  • the product processing unit 80 mixes the natural gas condensate produced in step S10, the first mixture generated in step S20, and the second mixture generated in step S30 to produce a single synthetic crude oil ( S40).
  • the single synthetic crude oil produced in step S40 is stored and transported without heat treatment, as shown in FIG. 4 (S50).
  • the single synthetic crude oil transported in the step S50 is purified in a land refining plant (S60).
  • the FT synthesis unit 600 is installed to generate syngas generated from natural gas as synthetic oil.
  • the GTL main processes include a natural gas saturation and pre-reforming unit 300, a reforming unit 400, a syngas control unit 500, a syngas control unit 500, and an FT synthesis unit 600.
  • the FT synthesis unit 600 serves to convert syngas into synthetic oil, and the product processing unit 800 plays a role of generating synthetic crude oil by upgrading the synthetic oil.
  • Syngas generated in excess in the FT synthesis unit 600 is classified in the residual gas separation unit 700 and partly recycled to the preforming unit 20.
  • Synthetic crude oil produced via the product processing unit 800 is stored in a tank.
  • the synthetic crude oil produced by GTL FPSO has a high viscosity containing a large amount of wax (Wax), so it must secure the fluidity for storage, unloading, transport. As the wax approaches 100%, it solidifies at room temperature / atmospheric pressure, making storage and unloading impossible.
  • Wax wax
  • control unit 900 controls the FT synthesis unit 600 to maintain the wax component of the synthetic crude oil modified with the synthetic oil at the set value.
  • the control unit 900 determines the state of the synthetic crude oil stored in the tank and performs an algorithm for optimally maintaining the wax component.
  • the FT synthesis unit 600 includes the LT-FT reactor 620 and the HT-FT reactor 640 in series or in parallel, and the The flow rate of the LT-FT reactor 620 and the HT-FT reactor 640 is controlled according to the composition.
  • the FT synthesis unit 600 includes an HT-FT reactor 640 downstream of the LT-FT reactor 620.
  • LT-FT reactor 620 is operating temperature range of 220 ⁇ 250 °C mainly synthesized in a liquid phase such as heavy oil or wax
  • HT-FT reactor 640 is operating temperature range of 330 ⁇ 350 °C mainly gasoline, naphtha Synthesize in the same vapor phase as
  • reference numeral 48 is a separator for removing water and the like after the synthesis reaction.
  • the mark on the right side shows that about 50% of the wax is included in the one-step reaction through the LT-FT reactor 620, but the mark on the left shows the two-step reaction through the HT-FT reactor 640.
  • the wax was later reduced to about 10% and the naphtha content appeared to increase.
  • the LT-FT reactor 620 may be disposed downstream of the HT-FT reactor 640 according to the characteristics of the synthetic crude oil to be produced. For example, if you want to produce a lot of light synthetic crude oil such as gasoline, naphtha, diesel.
  • the control unit 900 includes a wax detector 920 for detecting wax content of synthetic crude oil, an unreacted gas detector 940 and a driver for detecting the content of unreacted gas. 960 is provided.
  • the wax detector 920 and the unreacted gas detector 940 are not necessarily limited to hardware such as a specific sensor, and may include a database and software of content changes previously accumulated corresponding to the components of synthetic crude oil.
  • the control unit 900 is characterized in that the control to keep the wax component to a minimum within the limit to keep the unreacted gas within the set value.
  • Minimizing the wax component of the synthetic crude oil, as shown in Figure 3 causes an increase in the component of the unreacted gas, such as LPG, resulting in a decrease in transport efficiency.
  • the unreacted gas is controlled to maintain the optimum wax component within the range not exceeding the set value.
  • the wax component should be maintained within the range to ensure the fluidity of the synthetic crude oil.
  • the LT-FT reactor 620 and the HT-FT reactor 640 of the second embodiment of the present invention are both commercially available on land and have low risk when applied to the sea. As a result, there is no need to secure liquidity through an upgrading process that has not been verified at sea, and CAPEX and OPEX in the upgrading system can be reduced.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un appareil de gaz-à-liquide (GTL) de Fischer-Tropsch (FT) pour produire du pétrole brut synthétique unique, et un procédé GTL FT pour produire du pétrole brut synthétique unique. L'appareil GTL FT de production de pétrole brut synthétique unique de la présente invention est un appareil GTL FT pour produire du pétrole brut synthétique unique à partir d'une production, un stockage et un déchargement flottants, (FPSO), et est caractérisé en ce qu'il comprend : une unité de stabilisation d'injection de gaz pour réaliser une stabilisation sur le gaz naturel produit pour générer un condensat de gaz naturel; et une unité de modification pour modifier le gaz naturel, qui a été traité dans l'unité de stabilisation d'injection de gaz, pour produire un produit de pétrole brut synthétique.
PCT/KR2014/007012 2014-02-28 2014-07-30 Appareil et procédé gaz-à-liquide de fischer-tropsch pour produire du pétrole brut synthétique unique WO2015129970A1 (fr)

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JP2016552950A JP2017512225A (ja) 2014-02-28 2014-07-30 単一合成原油生産用のｆｔ−ｇｔｌ装置及び方法
US15/122,140 US20160369173A1 (en) 2014-02-28 2014-07-30 Ft gtl apparatus and method for producing single synthetic crude oil
EP14883641.4A EP3112250A4 (fr) 2014-02-28 2014-07-30 Appareil et procédé gaz-à-liquide de fischer-tropsch pour produire du pétrole brut synthétique unique

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KR10-2014-0024695 2014-02-28
KR1020140024695A KR101562823B1 (ko) 2014-02-28 2014-02-28 Gtl fpso 합성원유의 왁스성분 조절장치
KR10-2014-0059689 2014-05-19
KR1020140059689A KR101597557B1 (ko) 2014-05-19 2014-05-19 단일 합성원유 생산용 ft gtl 장치 및 방법

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US20160369173A1 (en) 2016-12-22
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EP3112250A1 (fr) 2017-01-04

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