WO2012133988A1 - 합성가스의 전환율을 높이기 위한 2단 f-t 반응기 시스템 - Google Patents
합성가스의 전환율을 높이기 위한 2단 f-t 반응기 시스템 Download PDFInfo
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- WO2012133988A1 WO2012133988A1 PCT/KR2011/004992 KR2011004992W WO2012133988A1 WO 2012133988 A1 WO2012133988 A1 WO 2012133988A1 KR 2011004992 W KR2011004992 W KR 2011004992W WO 2012133988 A1 WO2012133988 A1 WO 2012133988A1
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
- B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/005—Separating solid material from the gas/liquid stream
- B01J8/006—Separating solid material from the gas/liquid stream by filtration
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
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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
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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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
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/34—Apparatus, reactors
- C10G2/341—Apparatus, reactors with stationary catalyst bed
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/34—Apparatus, reactors
- C10G2/342—Apparatus, reactors with moving solid catalysts
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00115—Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
- B01J2208/00141—Coils
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
- B01J2208/00256—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles in a heat exchanger for the heat exchange medium separate from the reactor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00027—Process aspects
- B01J2219/0004—Processes in series
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1022—Fischer-Tropsch products
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
- C10J2300/1656—Conversion of synthesis gas to chemicals
- C10J2300/1659—Conversion of synthesis gas to chemicals to liquid hydrocarbons
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention is a two-stage FT reactor system for producing synthetic fuel by Fischer-Tropsch reaction with catalyst contained in slurry (oil, wax) in coal liquefaction (CTL) and natural gas liquefaction (GTL) processes.
- CTL coal liquefaction
- GTL natural gas liquefaction
- it comprises a first reactor consisting of a bubble column reactor and a second reactor consisting of a bubble column reactor or a fixed bed reactor, and two heat exchangers for cooling and heating between the two reactors to provide moisture and low boiling point
- the present invention relates to a two-stage FT reactor system for increasing the conversion rate of syngas to maximize the yield of synthetic fuel and to extend the life of the catalyst used by separating the oil.
- the FT reaction process is a core process of the liquefaction system (CTL), the indirect liquefaction system (CLT), the natural gas liquefaction system (GTL), and the liquefaction system (XTL) for gasifying various raw materials such as biomass and waste such as wood.
- CTL liquefaction system
- CLT indirect liquefaction system
- GTL natural gas liquefaction system
- XTL liquefaction system
- the composition ratio (H 2 / CO ratio) of hydrogen and carbon monoxide generated in the gasification process of the CTL, GTL, XTL process is distributed in various ways depending on the raw material.
- the composition ratio is distributed in the range of 0.6 to 1.2, and in the case of using gas such as natural gas and process waste gas as raw materials, 1.2 to 2.0 Shows the distribution of.
- the FT reaction process induces the synthesis gas (CO + H 2 ) to react with the catalyst in the reactor body to produce a synthetic fuel in the liquid state.
- the catalyst used in the FT reactor mainly uses Fe (iron) catalyst and Co (cobalt) catalyst.
- the type of catalyst used in the FT reactor depends on the composition ratio (H 2 / CO ratio) of the synthesis gas flowing into the reactor.
- the Fe catalyst can be used in a wide range of H 2 / CO ratio of 0.6 to 3.5 because the components contained in the catalyst causes a water gas shift reaction (CO) to convert hydrogen into hydrogen.
- CO water gas shift reaction
- Fe catalysts have lower activity than Co catalysts, resulting in higher reaction temperatures and pressures in order to obtain higher activity, resulting in shorter catalyst lifetimes.
- the cobalt catalyst has high activity, and the reaction temperature and pressure are relatively lower than that of the Fe catalyst, but the catalyst deactivation is accelerated if the H 2 / CO ratio is not maintained at 1.8 to 2.0, thereby shortening the catalyst life. Therefore, when using the Co catalyst in the coal liquefaction process, it is necessary to attach the water gas reactor in front of the FT reactor to maintain the H 2 / CO ratio of the synthesis gas flowing into the FT reactor to 1.8 ⁇ 2.0. In addition, Co catalysts are difficult to apply to syngas generated from coal because they have a disadvantage that the reaction activity is rapidly reduced even if a small amount of impurities such as H 2 S in the synthesis gas.
- the present invention has been made in view of the above problems, and a first object of the present invention is to interconnect one or more first reactors mainly using Fe catalysts and a second reactor mainly using Fe ⁇ Co or Co catalysts.
- a first object of the present invention is to interconnect one or more first reactors mainly using Fe catalysts and a second reactor mainly using Fe ⁇ Co or Co catalysts.
- the second purpose is to adjust the H 2 / CO ratio of the gas injected into the second reactor to 1.8 ⁇ 2.0 by adjusting the conversion rate of CO by adjusting the temperature, pressure and flow rate of the synthesis gas supplied to the first reactor. It is to provide a two-stage FT reactor system for increasing the conversion rate of the syngas that can provide a suitable reaction conditions for the second reactor.
- the third object is to minimize the inflow of impurities into the second reactor by removing moisture and non-point oil in the synthesis gas discharged from the first reactor by using the first heat exchanger, and furthermore, It is to provide a two-stage FT reactor system for heating the temperature of the synthesis gas flowing into the second reactor using heat to increase the conversion efficiency of the synthesis gas of the structure that can increase the efficiency of the reaction while maximizing the energy efficiency.
- the first invention in the FT reactor system, using a Fe catalyst, the first synthesis gas extracted from coal or biomass or natural gas At least one or more first reactors 10 which are supplied with and react with Fe catalyst to obtain synthetic fuel; And a second reactor using a Fe ⁇ Co catalyst or a Co catalyst and receiving a second synthesis gas flowing out after the reaction from the first reactor 10 to react with the Fe ⁇ Co catalyst or Co catalyst to obtain a synthetic fuel.
- the first reactor 10 is supplied with a composition ratio of H 2 / CO included in the first synthesis gas in a range of 0.6 to 1.2, and includes an internal temperature and a pressure of the first synthesis gas.
- the second reactor 20 is the ratio of the composition of H 2 / CO of the second synthesis gas flowing out after the reaction in the first reactor (10) It is preferably configured to have a CO conversion rate in the range of 90 to 95% during the reaction by controlling the internal temperature and pressure and the flow rate of the second synthesis gas when supplied in the range of 1.8 to 2.0.
- the first reactor 10 and the second reactor 20 are preferably bubble column reactors.
- the first reactor 10 is a bubble column reactor
- the second reactor 20 is a fixed bed reactor having a catalyst pipe filled with a catalyst therein.
- the first reactor 10 is provided with a first cooling tube 13 therein to prevent a sudden temperature rise due to the reaction heat generated when reacting with the Fe catalyst
- the second reactor 20 is provided with a second cooling tube 23 therein to prevent a sudden temperature rise due to the reaction heat generated when reacting with the Fe ⁇ Co catalyst or the Co catalyst, and the first reactor 10
- the outflow pipe 12 of the first reactor 10 and the second reactor so as to receive the second synthesis gas flowing out after the reaction from the reaction, and react with the Fe ⁇ Co catalyst or Co catalyst stored in the second reactor 20.
- the fifth invention in the fourth invention, further comprises a first line 40 connecting the inlet side of the first heat exchanger 31 and the first cooling tube 13, the first line 40 is Cooling water supplied to the first heat exchanger (31) cools the second synthesis gas flowing out after the reaction from the first reactor (10), and is continuously transferred to the first cooling tube (13) to the first reactor by the heat of reaction It is configured to cool the inside of (10) to prevent a sudden temperature rise due to the internal reaction heat,
- the second line 41 is the outlet of the first cooling tube 13
- the high temperature cooling water discharged through the side is supplied to the second heat exchanger 32 to heat the second synthesis gas cooled through the first heat exchanger 31, and then discharged as water or steam to be used as another heat source.
- a third line 42 connecting the outlet side of the second cooling tube 23 to the second line 41, wherein the third line 42 is an outlet side of the second cooling tube 23. It is configured to supply the high temperature coolant discharged through the second line 41 to increase the temperature of the coolant flowing into the second heat exchanger 32 along the second line 41. It is desirable to be.
- the sixth invention in the fifth invention, by cooling the third synthesis gas flowing out after the reaction from the second reactor 20 to collect the water / low boiling oil contained in the synthesis gas through the second recovery tank 52 Further comprising a three heat exchanger to be stored, the third heat exchanger 51 is preferably installed in the discharge line 50 is connected to the second reactor (20).
- the seventh invention further includes a fourth line 43 connecting the inlet side of the third heat exchanger 51 and the second cooling tube 23 in the sixth invention, wherein the fourth line 43 is Cooling water supplied to the third heat exchanger 51 cools the third synthesis gas flowing out from the second reactor 20, and is continuously transferred to the second cooling tube 23 to provide a second reactor by internal heat of reaction ( 20) is preferably configured to prevent a sudden temperature rise inside.
- the reaction conditions of the first reactor 10 is the internal temperature 240 °C ⁇ 280 °C, the internal pressure is 15 atm ⁇ 40 atm, the flow rate of the first synthesis gas is 5 It is preferable that it is-20 cm / sec.
- the reaction conditions of the second reactor 20 is a temperature of 150 °C to 230 °C, the pressure is 10 at 30 to 30 atm, the flow rate of the first synthetic gas is 5 to 20 cm / sec is preferred.
- two independent reactors are installed to select a catalyst suitable for the composition ratio of H 2 / CO of the synthesis gas, and maintain process conditions suitable for each characteristic.
- the first heat exchanger is used to remove moisture and non-point oil in the synthesis gas discharged from the first reactor, thereby minimizing the inflow of impurities into the second reactor, and further, the second heat exchanger is used to Heating the temperature has the effect of increasing the efficiency of the reaction while increasing the efficiency of energy to the maximum.
- FIG. 1 is a block diagram of a two-stage F-T reactor system for increasing the conversion rate of the synthesis gas according to the first embodiment of the present invention
- FIG. 2 is a block diagram of a two-stage F-T reactor system for increasing the conversion rate of the synthesis gas according to a second embodiment of the present invention.
- FIG. 1 is a block diagram of a two-stage F-T reactor system for increasing the conversion rate of the synthesis gas according to the first embodiment of the present invention.
- the present invention interconnects the first reactor 10 mainly using the Fe catalyst and the second reactor 20 mainly using the Fe ⁇ Co or Co catalyst to form two reaction zones.
- Two-stage FT to increase the conversion rate of syngas to increase the total conversion rate of syngas, maximize the yield of synthesis fuel, and extend the life of the catalyst by having different catalyst and reaction conditions in each reaction zone. It relates to a reactor system.
- the two-stage FT reactor system for improving the conversion rate of the synthesis gas according to the present invention consists of two parts, which is the first reactor 10, the second reactor 20 interconnected with the first reactor (10) It is composed of
- the first reactor is composed of a bubble column reactor in which a slurry containing Fe catalyst is stored.
- a dispersion plate 14 for dispersing bubble particles of the first synthesis gas extracted from coal, and Fischer- of the first synthesis gas and the Fe catalyst in the inner central region.
- Filtering means 15 for releasing the synthetic fuel produced by the Tropsch reaction and filtering the catalyst, and a first cooling tube for cooling the reaction heat by the Fischer-Tropsch reaction of the synthesis gas and the Fe catalyst. 13) is provided.
- the first reactor 10 is supplied with the first synthesis gas through the inlet pipe 11, at which time the composition ratio of H 2 / CO contained in the first synthesis gas is supplied in the range of 0.6 ⁇ 1.2 Temperature and pressure, and the flow rate of the first synthesis gas is adjusted to have a CO conversion in the range of 50 to 80% when reacted with the Fe catalyst.
- the total composition ratio of the first synthesis gas is in the range of H 2 : 35% ⁇ 40%, CO: 40% ⁇ 45%, CO 2 : 10% ⁇ 20%, CH 4 : 1% ⁇ 5%, and the internal temperature is It is required to be in the range of 240 ° C. to 280 ° C., an internal pressure of 15 atm to 40 atm, and a flow rate of 5 to 20 cm / sec.
- the reaction temperature of the first reactor (10) is maintained in the range of 240 °C ⁇ 280 °C, the internal pressure is maintained at 15 atmospheres to 40 atmospheres, the flow rate is adjusted to 5 ⁇ 20cm / sec to change the CO conversion rate 50 ⁇ 80 You can set it to the% range.
- the Fischer-Tropsch reaction equation of the present invention is defined as in [Formula 1], and is a main reaction equation of the first reactor 10 and the second reactor 20.
- the conversion rate of CO is 50 depending on the composition ratio of the first synthesis gas, the flow rate, the internal temperature, and the internal pressure.
- the ratio of H 2 / CO of the second synthesis gas supplied to the second reactor 20 is maintained in the range of 80% to 80%, thereby providing a structure that can be supplied in the range of 1.8 to 2.0.
- a wax-type synthetic fuel produced in a state in which a conversion rate of CO is 50 to 80% by reacting with a Fe catalyst through [Formula 1] may be first obtained through the filtering means 15. Can be.
- the H 2 / CO ratio of the second synthesis gas is introduced into the second reactor 20 using the Fe ⁇ Co catalyst or the Co catalyst at 1.8 or lower, or the temperature is too high.
- the following subreaction formula [Formula 4] may be generated.
- Such a reaction is not preferable because it generates carbon, carbon covers the surface of the catalyst, promotes deactivation of the catalyst, weakens the conversion of CO, and consequently, obtains synthetic fuel in the second synthesis gas.
- the second reactor 20 uses a Fe ⁇ Co catalyst or a Co catalyst, and has a structure in which a second cooling tube 23 is installed to remove reaction heat generated when the second synthesis gas reacts with the catalyst.
- the second reactor 20 may be composed of a bubble column reactor or a fixed bed reactor having a catalyst pipe filled with a catalyst therein.
- a bubble column reactor or a fixed bed reactor having a catalyst pipe filled with a catalyst therein.
- the second reactor 20 may be supplied with a second synthesis gas having a phase of H 2 / CO of 1.8 to 2.0 by maintaining a conversion ratio of 50 to 80% as described above in the first reactor 10.
- the total composition ratio of the second synthesis gas is H 2 : 40% to 50%, CO: 20 to 30%, CO 2 : 20% to 40%, CH 4 : 2% to 7% range.
- the reaction conditions of the second reactor 20 is a temperature 150 °C ⁇ 230 °C
- the pressure is 10 at 30 ⁇ 30 atm
- the flow rate of the first synthetic gas is preferably 5 ⁇ 20cm / sec.
- the second reactor 20 is connected to the first reactor 10 to receive the second synthesis gas from the first reactor 10, and the trace amount of impurities contained in the first synthesis gas is the first reactor 10.
- the trace amount of impurities contained in the first synthesis gas is the first reactor 10.
- the Fe catalyst in or is absorbed in the slurry it is also included in the oil and water condensed in the first heat exchanger 31 is removed because it can be prevented from entering the second reactor (20)
- a substance that suppresses the activity of the Co catalyst is hardly supplied, thereby extending the life of the Co catalyst.
- the second synthesis gas H 2 / CO composition ratio supplied to the second reactor 20 is supplied in the range of 1. 8 ⁇ 2.0 to the CO conversion rate of the second synthesis gas to 90% ⁇ 95% or more by the reaction conditions described above Because of the reaction, the overall process yield is higher than 95%, which can improve the economics of the process.
- the present invention further provides a first heat exchanger 31 for cooling the syngas discharged through the inside of the first reactor 10 and the outlet pipe 12 of the first reactor 10, and the first heat exchange. It consists of a second heat exchanger (32) which is heated by the reaction heat of the first reactor (10) for heating the synthesis gas cooled through the group (31).
- connection line 30 connects the inlet pipes 21 of the second reactor 20 to each other.
- connection line 30 the second synthesis gas is cooled from the first reactor 10 so that the water and the low boiling oil contained in the second synthesis gas are collected and stored through the first recovery tank 33.
- the first heat exchanger 31 is installed.
- the first heat exchanger 31 cools the second high temperature synthesis gas transported along the connection line 30 to supply moisture and low boiling oil included in the second synthesis gas through the first recovery tank 33. It can be collected, which is a structure that can prevent the supply of water to suppress the Co catalyst activity of the second reactor (20).
- connection line 30 has a second heat exchange to heat the second synthesis gas cooled through the first heat exchanger 31 to the reaction temperature of the Fe ⁇ Co catalyst or Co catalyst of the second reactor 20.
- the machine 32 is installed.
- the first line 40 is connected to the inflow side of the first heat exchanger 31 and the first cooling tube 13.
- the first line 40 cools the second synthesis gas flowing out after the coolant supplied to the first heat exchanger 31 is reacted from the first reactor 10, and continuously the first cooling tube 13 And cooled to the inside of the first reactor 10 by the heat of reaction to prevent rapid temperature rise by the heat of internal reaction.
- the outlet side of the second heat exchanger 32 and the first cooling tube 13 has a structure in which the second line 41 is connected.
- the second line 41 is cooled by the first heat exchanger 31 by allowing the high temperature cooling water discharged through the outlet side of the first cooling tube 13 to be supplied to the second heat exchanger 32.
- the second synthesis gas is heated and then discharged in the form of water or steam to be used as another heat source.
- the structure further includes a third line 42 connecting the outlet side of the second cooling tube 23 and the second line 41.
- the third line 42 is configured such that the high temperature cooling water discharged through the outlet side of the second cooling tube 23 can be supplied to the second line 41 so that the second line 42 is along the second line 41. It is comprised so that the temperature of the cooling water which flows into the heat exchanger 32 can be raised.
- the first synthesis gas is introduced through the inlet pipe 11 of the first reactor 10.
- the first synthetic gas introduced is made to uniformize the bubble particles through the dispersion plate 14, and then react with the Fe catalyst to generate synthetic fuel.
- the generated synthetic fuel is collected through the filtering means 15, and the high temperature second synthesis gas flowing out to the connection line 30 after the reaction is cooled by the first heat exchanger 31 to be included in the second synthesis gas.
- Moisture and low boiling oil can be collected through the first recovery tank 33. This is to prevent moisture from flowing into the second reactor 20 to suppress Co catalyst activity.
- the low temperature second synthesis gas from which the water and the low boiling oil are removed is heated again through the second heat exchanger 32 to be introduced into the second reactor 20.
- the second synthesis gas flowing into the second reactor 20 is reacted with the Fe Co catalyst or Co catalyst to obtain the synthetic fuel through the filtering means 24 provided in the second reactor 20, and generated during the reaction. And unreacted gas are discharged to the outside.
- the movement path of the cooling water is as follows.
- the first low temperature cooling water is supplied to the first heat exchanger 31 to cool the second synthetic fuel and flow out to the first line 40.
- the coolant cooling the second synthetic fuel flows into the first cooling tube 13 through the first line 40 to cool the reaction heat of the first reactor 10 and is converted into a high temperature cooling water so that the second line ( 41).
- the separate cooling water that cools the reaction heat of the second reactor 20 and is converted into high temperature cooling water flows out through the third line 42 and joins the cooling water of the second line 41.
- the joined high temperature coolant is supplied to the second heat exchanger 32 through the second line 41 to heat the second synthetic fuel and to be steamed to be used as another heat source.
- FIG. 2 is a block diagram of a two-stage F-T reactor system for increasing the conversion rate of the synthesis gas according to a second embodiment of the present invention.
- the second embodiment includes the first embodiment and cools the third synthesis gas flowing out after the reaction from the second reactor 20 to remove the water and the low boiling oil included in the third synthesis gas.
- the structure further includes a three heat exchanger to be collected and stored through the two recovery tanks (52).
- the second reactor 20 is configured as a bubble column reactor in an embodiment, the third heat exchanger 51 is installed in the discharge line 50 is connected to the outlet pipe 22 of the second reactor (20) Structure.
- a fourth line 43 which connects the inlet side of the third heat exchanger 51 and the second cooling tube 23 to the third heat exchanger 51. Cooling water supplied to the C) cools the third synthesis gas flowing out from the second reactor 20, and is continuously transferred to the second cooling tube 23, so that the inside of the second reactor 20 by the internal heat of reaction is abrupt. It is configured to prevent the temperature rise.
- This structure is to supply the low-temperature cooling water of the third synthesis gas or the low boiling point oil flowing through the discharge line 50 by supplying the cooling water of the low temperature to the third heat exchanger 51, the unreacted Gas is a structure that can be discharged to the outside.
- the high temperature cooling water flowing out through the second cooling tube 23 is merged into the second line 41 through the third line 42 to heat the second synthesis gas through the second heat exchanger 32. It is a constitution.
- the volume of the second reactor 20 according to the present invention is proportional to the number of first reactors 10 and the CO conversion rate in the first reactors.
- the number of first reactors 10 is the same as in the embodiment.
- the volume of the second reactor 20 is 30 to 60% of the volume of the first reactor 10. Therefore, when there are two first reactors 10, the volume of the second reactor 20 may be configured as 60% to 120% of the first reactor 10, of course.
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Abstract
Description
Claims (9)
- F-T 반응기 시스템에 있어서,Fe 촉매를 사용하고, 석탄 또는 바이오매스 또는 천연가스에서 추출된 제 1합성가스를 공급받아 Fe 촉매와 반응시켜 합성연료를 획득하는 적어도 1개 이상의 제 1반응기(10); 및Fe·Co 촉매 또는 Co 촉매를 사용하고, 상기 제 1반응기(10)로부터 반응 후 유출되는 제 2합성가스를 공급받아 Fe·Co 촉매 또는 Co 촉매와의 반응시켜 합성연료를 획득하는 제 2반응기(20);를 포함하여 이루어지되,상기 제 1반응기(10)는 제 1합성가스에 포함된 H2/CO의 조성비를 0.6 ~ 1.2 범위로 공급받아 내부온도 및 압력과, 제 1합성가스의 유속을 조절하여 반응시 50 ~ 80%범위의 CO 전환율을 갖도록 구성하고,상기 제 2반응기(20)는 제 1반응기(10)에서 반응 후 유출되는 제 2합성가스의 H2/CO의 조성비를 1.8 ~ 2.0 범위로 공급받아 내부온도 및 압력과, 제 2합성가스의 유속을 조절하여 반응시 90 ~ 95% 범위의 CO 전환율을 갖도록 구성되는 것을 특징으로 하는 합성가스의 전환율을 높이기 위한 2단 F-T 반응기 시스템
- 제 1항에 있어서,상기 제 1반응기(10) 및 제 2반응기(20)는 기포탑 반응기인 것을 특징으로 하는 합성가스의 전환율을 높이기 위한 2단 F-T 반응기 시스템.
- 제 1항에 있어서,상기 제 1반응기(10)는 기포탑 반응기이고, 제 2반응기(20)는 내부에 촉매가 충진된 촉매파이프를 갖는 고정층 반응기인 것을 특징으로 하는 합성가스의 전환율을 높이기 위한 2단 F-T 반응기 시스템.
- 제 1항 내지 제 3항 중 어느 한 항에 있어서,상기 제 1반응기(10)는 내부에 제 1냉각관(13)을 구비하여 Fe 촉매와 반응시 발생되는 반응열에 의한 급격한 온도상승을 방지하고,상기 제 2반응기(20)는 내부에 제 2냉각관(23)을 구비하여 Fe·Co 촉매 또는 Co 촉매와 반응시 발생되는 반응열에 의한 급격한 온도상승을 방지하며,상기 제 1반응기(10)로부터 반응 후 유출되는 제 2합성가스를 공급받아 제 2반응기(20)에 저장된 Fe·Co 촉매 또는 Co 촉매와 반응시킬 수 있도록 상기 제 1반응기(10)의 유출관(12)과, 제 2반응기(20)의 유입관(21)을 상호 연결하는 연결라인(30)과,상기 제 1반응기(10)로부터 반응 후 유출되는 제 2합성가스를 냉각하여 제 2합성가스에 포함된 수분 및 저비점 오일을 제 1회수탱크(33)를 통해 수거하여 저장될 수 있도록 상기 연결라인(30)에 설치되는 제 1열교환기(31)와,상기 제 1열교환기(31)를 통해 냉각된 제 2합성가스를 제 2반응기(20)의 Fe·Co 촉매 또는 Co 촉매의 반응온도까지 가열할 수 있도록 상기 연결관에 설치되는 제 2열교환기(32)를 더 포함하여 이루어지는 것을 특징으로 하는 합성가스의 전환율을 높이기 위한 2단 F-T 반응기 시스템.
- 제 4항에 있어서,상기 제 1열교환기(31)와 제 1냉각관(13)의 유입측을 연결하는 제 1라인(40)을 더 포함하되, 상기 1라인(40)은 제 1열교환기(31)로 공급된 냉각수가 상기 제 1반응기(10)로부터 반응 후 유출되는 제 2합성가스를 냉각하고, 연속적으로 제 1냉각관(13)으로 이송되어 반응열에 의한 제 1반응기(10)의 내부를 냉각하여 내부 반응열에 의한 급격한 온도 상승을 방지하도록 구성되고,상기 제 1냉각관(13)의 유출측과 제 2열교환기(32)를 연결하는 제 2라인(41)을 더 포함하되, 상기 제 2라인(41)은 제 1냉각관(13)의 유출측을 통해 배출되는 고온의 냉각수가 제 2열교환기(32)로 공급되도록 하여 제 1열교환기(31)를 통해 냉각된 제 2합성가스를 가열한 후 물 또는 스팀형태로 배출되어 다른 열원으로 사용될 수 있도록 구성되며,상기 제 2냉각관(23)의 유출측과 제 2라인(41)을 연결하는 제 3라인(42)을 더 포함하되, 상기 제 3라인(42)은 제 2냉각관(23)의 유출측을 통해 배출되는 고온의 냉각수가 제 2라인(41)으로 공급될 수 있도록 구성하여 제 2라인(41)을 따라 제 2열교환기(32)로 유입되는 냉각수의 온도를 상승을 도모할 수 있도록 구성되는 것을 특징으로 하는 합성가스의 전환율을 높이기 위한 2단 F-T 반응기 시스템.
- 제 5항에 있어서,상기 제 2반응기(20)로부터 반응 후 유출되는 제 3합성가스를 냉각하여 합성가스에 포함된 물/저비점오일을 제 2회수탱크(52)를 통해 수거하여 저장될 수 있도록 3열교환기를 더 포함하되, 상기 제 3열교환기(51)는 제 2반응기(20)와 연결되는 배출라인(50)에 설치되는 것을 특징으로 하는 합성가스의 전환율을 높이기 위한 2단 F-T 반응기 시스템.
- 제 6항에 있어서,상기 제 3열교환기(51)와 제 2냉각관(23)의 유입측을 연결하는 제 4라인(43)을 더 포함하되, 상기 제 4라인(43)은 제 3열교환기(51)로 공급된 냉각수가 상기 제 2반응기(20)로부터 유출되는 제 3합성가스를 냉각하고, 연속적으로 제 2냉각관(23)으로 이송되어 내부 반응열에 의한 제 2반응기(20)에 내부의 급격한 온도 상승을 방지할 수 있도록 구성되는 것을 특징으로 하는 합성가스의 전환율을 높이기 위한 2단 F-T 반응기 시스템.
- 제 1항에 있어서,상기 제 1반응기(10)의 반응조건은 내부온도 240℃ ~ 280℃이고, 내부압력은 15기압 ~ 40기압이며, 유입되는 제 1합성가스의 유속은 5 ~ 20cm/sec인 것을 특징으로 하는 합성가스의 전환율을 높이기 위한 2단 F-T 반응기 시스템.
- 제 8항에 있어서,상기 제 2반응기(20)의 반응조건은 온도 150℃ ~ 230℃이고, 압력은 10기압 ~ 30기압이며, 유입되는 제 1합성가스의 유속은 5 ~ 20cm/sec인 것을 특징으로 하는 합성가스의 전환율을 높이기 위한 2단 F-T 반응기 시스템.
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FI127086B (en) | 2013-10-10 | 2017-11-15 | Teknologian Tutkimuskeskus Vtt Oy | Process and apparatus for producing a hydrocarbon fraction and hydrocarbon fraction and its use |
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US5763716A (en) * | 1986-05-08 | 1998-06-09 | Rentech, Inc. | Process for the production of hydrocarbons |
US6642281B1 (en) * | 2000-09-01 | 2003-11-04 | Exxonmobil Research And Engineering Company | Fischer-tropsch process |
WO2007069317A1 (ja) * | 2005-12-14 | 2007-06-21 | Nippon Steel Engineering Co., Ltd. | 気泡塔型フィッシャー・トロプシュ合成スラリー床反応システム |
KR100986751B1 (ko) * | 2009-09-17 | 2010-10-08 | 한국에너지기술연구원 | Ft 슬러리 기포탑 반응기의 반응열 제거용 다단분리형 냉각장치 |
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