WO2009113714A1 - 天然ガスから液状炭化水素を製造する方法 - Google Patents
天然ガスから液状炭化水素を製造する方法 Download PDFInfo
- Publication number
- WO2009113714A1 WO2009113714A1 PCT/JP2009/055217 JP2009055217W WO2009113714A1 WO 2009113714 A1 WO2009113714 A1 WO 2009113714A1 JP 2009055217 W JP2009055217 W JP 2009055217W WO 2009113714 A1 WO2009113714 A1 WO 2009113714A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gas
- synthesis gas
- hydrogen
- reaction
- fischer
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
-
- 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
- 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
- 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
- C01B2203/02—Processes for making hydrogen or synthesis gas
-
- 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
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- 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
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
-
- 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
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
-
- 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
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0415—Purification by absorption in liquids
-
- 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
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/042—Purification by adsorption on solids
- C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
-
- 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
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
-
- 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
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/048—Composition of the impurity the impurity being an organic compound
-
- 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
-
- 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
-
- 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
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
-
- 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
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1258—Pre-treatment of the feed
-
- 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
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1258—Pre-treatment of the feed
- C01B2203/1264—Catalytic pre-treatment of the feed
- C01B2203/127—Catalytic desulfurisation
-
- 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
- C01B2203/14—Details of the flowsheet
- C01B2203/146—At least two purification steps in series
-
- 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
- C01B2203/14—Details of the flowsheet
- C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis 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
- C10G2300/10—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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2300/80—Additives
- C10G2300/805—Water
- C10G2300/807—Steam
Definitions
- the present invention relates to a so-called GTL process for producing liquid hydrocarbons containing fuel oil from natural gas.
- the GTL process shown in Fig. 2 is a hydrodesulfurization process in which sulfur compounds in natural gas are hydrodesulfurized from the natural gas feed side (ie upstream side) located on the left side of the drawing 120, natural gas and steam, and / or Syngas production process 1 30 to produce synthesis gas by reforming reaction with carbon dioxide, Decarbonation process 140 provided if necessary, Fischer 'Tropsch (FT) synthesis from synthesis gas to produce Fischer' Tropsch oil Fischer Tropsch oil production process 1 50, hydrotreating the produced Fischer-Tropsch oil, upgrading reaction process 1 60, hydrotreated material obtained by the upgrading reaction process It has an upgrading gas-liquid separation step 170 for obtaining liquid hydrocarbons.
- FT Fischer 'Tropsch
- the synthesis gas produced in the synthesis gas production process 1 30 is partially branched at the stage before entering the Fischer's Tropsch oil production process 1 50 to form a branch line 145, and then branched.
- Syngas in line 145 is water Hydrogen is separated into high-purity hydrogen (line 1 9 2) and off-gas (line 1 9 1) in the hydrogen separation process 1 90 by the elemental PSA (Pressure Swing Adsorption) method.
- the separated high-purity hydrogen passes through line 1 9 2 and line 1 9 7 to hydrogen circulation line 1 7 7 which is circulated from upgrading gas-liquid separation process 1 70 to upgrading reaction process 1 6 0.
- off-gas purged from line 1 9 1 is usually used as fuel.
- the present invention was devised in view of the above-described current situation, and its purpose is to recycle off-gas discharged from the hydrogen separation step in the so-called GTL process for producing liquid hydrocarbons from natural gas.
- the purpose is to provide a method that can be taken in and reused as raw material, thereby increasing the raw material intensity.
- the present invention provides a hydrodesulfurization process for removing sulfur compounds in natural gas by hydrodesulfurization, and a modification of natural gas, steam, and Z or carbon dioxide that has undergone the hydrodesulfurization process.
- a synthetic gas production process for producing synthesis gas by a quality reaction a Fischer Tropsch oil production process for producing a Fischer Tropsch oil by reacting the synthesis gas produced in the synthesis gas production process with a Fischer Tropsch reaction, An upgrade reaction step for hydrotreating the Fischer-Tropsch oil produced in the Fischer Tropsch oil production process, and a hydrogenation obtained in the upgrade reaction step.
- a part of the upgrading gas-liquid separation process for gas-liquid separation of the treated product to obtain liquid hydrocarbons and the synthesis gas produced in the synthesis gas production process before entering the Fisher-to-mouth push oil production process A branch line is formed by branching, and the syngas entering the branch line is subjected to a water gas shift reaction to increase the hydrogen concentration, and high purity hydrogen is separated from the outlet gas of the shift process, resulting in A hydrogen separation step for separating the residual gas; and a liquid hydrocarbon production process from natural gas having: a residual gas (off-gas) separated in the hydrogen separation step is circulated to the synthesis gas production step, Is used as a raw material for synthetic gas production.
- the residual gas (off-gas) separated in the hydrogen separation step is configured to contain methane and carbon dioxide as main components.
- the high purity hydrogen gas separated in the hydrogen separation step is supplied to the hydrodesulfurization step and the upgrade reaction step, respectively.
- the synthesis gas production step includes a catalyst layer outlet temperature of 80 to 95 ° C., a catalyst layer outlet pressure of 1.5 to 3.0 MPa, and GHSV ( gas hourly space velocity) force S 5 0 0 ⁇ . . . ! ! ! : — Configured to be 1 .
- the synthesis gas production step is configured such that the natural gas supplied as a raw material contains a hydrocarbon having 1 to 6 carbon atoms mainly composed of methane.
- the synthesis gas produced in the synthesis gas production process is partially branched at the stage before entering the fish-mouth push oil production process to form a branch line, and before the branch line reaches the hydrogen separation process.
- a shift process is provided to increase the hydrogen concentration by subjecting the synthesis gas entering the branch line to a water gas shift reaction.
- the residual gas (off-gas) separated in the hydrogen separation step provided as a subsequent step of the shift step is circulated to the synthesis gas production step, and this is used as a raw material for synthesis gas production. Therefore, the raw material intensity can be improved by taking the off-gas from the hydrogen separation process, which has been used as fuel, into the process again and reusing it as a raw material.
- FIG. 1 is a scheme showing a process for producing liquid hydrocarbons from natural gas according to the present invention.
- Figure 2 is a scheme showing the process for producing liquid hydrocarbons from natural gas using the prior art.
- FIG. 1 is a scheme showing a process for producing liquid hydrocarbons from natural gas according to the present invention.
- sulfurization in natural gas is sequentially performed from the natural gas feed (line 19) side shown on the left side of the drawing in FIG.
- Hydrodesulfurization step 20 for removing the compound by hydrodesulfurization
- synthesis gas production step 30 for producing synthesis gas by reforming reaction of natural gas and steam and / or carbon dioxide, desulfurization provided as necessary
- Carbon dioxide process 40 Fischer's Tropsch reaction with synthesis gas
- Fischer's Tropsch oil production process Fischer's Tropsch oil production process
- Tropsch oil production process 50 and the resulting Fischer's Tropsch oil hydrotreating upgrade process 6
- an upgrading gas-liquid separation step 70 for obtaining liquid hydrocarbons by gas-liquid separation of the obtained hydrogenated product.
- the upgrading reaction step 60 and the upgrading gas-liquid separation step 70 are described separately. It can be handled as one process without any problem, in which case it is simply called the “upgrading process”.
- the synthesis gas produced in the synthesis gas production process 30 is subjected to a decarboxylation process 40 as necessary and before entering the Fischer's Tropsch oil production process 50.
- a part is branched to the branch line 45, and the synthesis gas branched to the branch line 45 is introduced into the hydrogen separation process 90 through the shift process 80.
- the shift step 80 an operation of increasing the hydrogen concentration by performing a water gas shift reaction of the synthesis gas is performed.
- the hydrogen separation step 90 high-purity hydrogen is separated, and the residual gas generated at the same time is separated.
- the high-purity hydrogen produced in the hydrogen separation process 90 is supplied to the upgrading reaction process 60 from the line 9 2 through the lines 9 7 and 8 7 and from the line 9 2 to the line 96.
- the residual gas (off-gas) separated in the hydrogen separation step 90 is circulated to the synthesis gas production step 30 through the line 95 and used again as a raw material.
- a shift process 80 is provided to increase the hydrogen concentration by a water gas shift reaction, and the synthesis gas that has undergone the shift process is introduced into the hydrogen separation process 90 to achieve high purity. Hydrogen and residual gas are separated, and the separated residual gas (off gas) is circulated (recycled) through the line 95 to the synthesis gas production process 30 to be reused as a raw material for synthesis gas production. It is in the point.
- the hydrodesulfurization process indicated by reference numeral 20 in FIG. 1 is a process for hydrodesulfurizing sulfur compounds in natural gas fed from a line 19 as a raw material.
- high-purity hydrogen produced in the hydrogen separation step 90 is supplied as hydrogen for hydrodesulfurization through lines 92 and 96.
- the synthesis gas production process 30 is a process for producing synthesis gas (CO and H 2 ) by a reforming reaction (reforming reaction) of natural gas supplied as a raw material with steam and nitrogen or carbon dioxide.
- a reforming reaction reforming reaction
- hydrocarbon feed gas containing methane as the main component as raw material CO and H by steam (H 2 O) and Z or carbon dioxide (CO 2 ) reforming in the presence of a catalyst for synthesis gas production 2 is a process for producing a synthesis gas containing 2 as a main component.
- the residual gas separated in the hydrogen separation process 90 is fed through the line 95 as a synthesis gas production raw material. Circulation (recycling) is to be used.
- a preferable range of H 2 OZC is 0.3 to 1.7, and a more preferable range is 0.7 to 1.3.
- the preferable range of CO 2 / C is 0.2 to 0.8, and the more preferable range is 0.4 to 0.6.
- the outlet temperature of the catalyst layer is usually 800 to 950 ° C, preferably 850 to 920 ° C, and the outlet pressure of the catalyst layer is 1.5 to 3.
- GH SV gas hourly space velocity
- a catalyst for syngas production has a carrier (carrier) as a base material and a catalytic metal carried on the carrier.
- a calcined magnesium oxide molded body is preferably used as the carrier.
- a molded body is formed by pressure-molding magnesium oxide powder into a predetermined shape with a mold and then firing.
- the specific shape of the molded body is not particularly limited, but it is generally desirable to use industrial catalyst forms such as rings, saddles, multiholes, and pellets. It may be an irregular shape such as crushed material.
- Magnesium oxide molded bodies used as carrier, BET method in the measured specific surface area is 0. 1: 1. is preferably Om 2 / g, more that 0.2 to 0 is 5111 2 Bruno 8. preferable. Inconvenience that a specific surface area of 1.
- the rate of formation of the force one carbon on the catalyst exceeds Om 2 Zg increases, whereas, insufficient activity per catalyst unit weight and which is less than 0. lm 2 / g As a result, there is a tendency that a large amount of catalyst is required.
- the specific surface area of the obtained carrier can be controlled by adjusting the firing temperature and firing time.
- magnesium oxide MgO
- the purity of magnesium oxide (Mg 2 O) is required to be 98% by weight or more, preferably 99% by weight or more.
- the component that enhances the carbon deposition activity, the component that decomposes in a high-temperature reducing gas atmosphere, Mixing of metals such as iron and nickel and silicon dioxide (S i O 2 ) is not preferable.
- ruthenium (Ru) as a catalyst metal is supported in a metal conversion amount (weight ratio with respect to the catalyst support) in the range of 10 to 5000 wt-pm, preferably 100 to 200 00 wt-pm. If the supported amount exceeds 5000 w tp pm, the catalyst cost increases and the amount of carbon deposited during the reaction increases. On the other hand, if the supported amount is less than 10 w t_p pm, sufficient catalytic activity cannot be obtained. Inconvenience tends to occur.
- Rh rhodium
- carbon as a lubricant is mixed with magnesium oxide (MgO) powder and then pressure-molded into a predetermined shape. Thereafter, the molded product is calcined at a calcining temperature of 100 ° C. or higher, preferably 1 150 ° to I 300 ° C., and more preferably 1 15 50 to 1250 ° C. for 1 to 4 hours. . Baking is usually performed in air Is called.
- MgO magnesium oxide
- the formed carrier is impregnated with a ruthenium salt-containing aqueous solution, and then dried and fired, whereby ruthenium (R u) can be supported on the outer surface of the magnesium oxide molded body.
- Suitable methods for impregnating the ruthenium salt-containing aqueous solution include a dipping method and a spray method. Among these, it is particularly preferable to use a spray method in which a ruthenium salt-containing aqueous solution is sprayed toward a carrier.
- ruthenium salt ruthenium chloride, ruthenium nitrate, etc. are preferably used.
- the carrier on which Ru has been adsorbed is dried at a temperature of 50 to 1550 ° C. for about 1 to 4 hours, and then 3 0 to 5 0 0 ° C., preferably 3 5 0 to 4 5 0. At the temperature of C :! Bake for 4 hours.
- the atmosphere for drying and firing may be in the air.
- natural gas containing methane as the main component generally hydrocarbons having 1 to 6 carbon atoms, mainly methane
- line 2 H 2 0 and Z or C 0 2 using a mixed gas of steam and / or carbon dioxide supplied from 5 and residual gas (off-gas) separated in hydrogen separation process 90 and recycled through line 95 Reforming produces syngas containing CO and H 2 as main components.
- the residual gas 95 contains mainly methane and carbon dioxide, and also contains hydrogen that could not be separated.
- the main component of the raw material as methane
- the product gas generally has a composition that causes carbon deposition on the catalyst surface, resulting in catalyst degradation due to carbon deposition.
- the above-mentioned catalyst for producing synthesis gas is used as a catalyst capable of solving such problems.
- the synthesis gas described above is subjected to Fischer-Tropsch reaction, and gaseous products are separated from the reaction products to produce Fischer-Tropsch oil.
- the FT synthesis reaction is a reaction that gives a hydrocarbon mixture from the synthesis gas CO and H 2 according to the following formula.
- the catalyst metal for example, metallic iron (F e :), cobalt (C o), ruthenium (Ru), Eckenole (N i) and the like are used.
- a support such as silica, alumina, silica alumina, titania or the like can be used.
- reaction conditions are generally about reaction temperature: 200 to 350 ° C., reaction pressure: normal pressure to about 4.0 MPaG.
- reaction temperature 250 to 350 ° C.
- reaction pressure 2.0 to 4.
- OMP a G is preferable.
- reaction temperature 220 to 250 ° C
- reaction pressure about 0.5 to 4.0 MPaG is preferable.
- the reaction is a kind of polymerization reaction, and it is generally difficult to keep the degree of polymerization (n) constant, and the products are widely present in the range of ⁇ .
- the carbon number distribution of the produced hydrocarbon can be expressed by the chain growth probability ⁇ in the distribution rule according to the Schulz-Flory distribution rule.
- the value of ⁇ is about 0.85 to 0.95.
- ⁇ -olefin is produced first, and then the produced ⁇ -olefin is produced into linear paraffin by hydrogenation, lower paraffin such as methane by hydrogenolysis, or secondary chain growth. As a result, it becomes a higher-grade hydrocarbon.
- alcohols such as ethanol, ketones such as acetone, and carboxylic acids such as acetic acid are also produced as secondary products.
- FT synthesis reactors examples include fixed bed reactors, fluidized bed reactors, and steam reactors. Rally bed reactors, supercritical reactors, etc. are used.
- the hydrocarbons produced by FT synthesis are mostly composed of linear olefin (1-olefin) and linear paraffin.
- the separation means for separating the gaseous product from the Fischer-Tropsch reaction product to produce Fischer-Tropsch oil is not particularly limited, and various known separation means should be used. Can do. As an example, for example, a flash separator may be used.
- Fischer 'Tropsch oil production process 50 The Fischer' toe push oil obtained from 50 is then subjected to hydrotreating (catalytic hydrotreating).
- the hydrotreatment can be performed using any catalyst bed reactor such as, for example, a fluidized bed, a moving bed, or a fixed bed.
- the hydrotreating conditions are, for example, a reaction temperature of about 175 to 400 ° C, hydrogen partial pressure:! ⁇ 25MPaG (10 ⁇ 2500 pressure)
- product hydrocarbons 71 such as naphtha, kerosene, and light oil are separated into gaseous substances mainly composed of hydrogen.
- the gaseous substance mainly composed of hydrogen is circulated and used in the upgrade reaction process 60 through lines 7 2, 7 7 and 8 7, and a part of the gaseous substance is off-gased from line 73. As discharged.
- the synthesis gas produced in the synthesis gas production process 30 and after the decarboxylation process 40 is separated from the main line at the stage before entering the Fischer 'Tropsch oil production process 50. to go into.
- the main line after branching is indicated by reference numeral 47.
- the branch line 45 is provided with a shift step 80, and by this shift step 80, the synthesis gas in the branch line 45 is increased in hydrogen concentration by a water gas shift reaction. That is, CO, which is one of the synthesis gas components, reacts with water vapor (water gas shift reaction) to generate H 2 and C 0 2 , as shown in the following reaction formula. Will increase.
- the amount of synthesis gas supplied to the branch line 45 is set based on the amount of hydrogen required in the upgrading reaction step 60 and the hydrodesulfurization step 20.
- the hydrogen separation step 90 high-purity hydrogen 92 is produced from the outlet gas supplied from the shift step 80, which is the previous step, through the line 81, and the resulting residual gas 95 is separated.
- the residual gas 95 includes methane and carbon dioxide as main components, and further includes hydrogen that could not be separated.
- the remaining gas 95 is recycled to the synthesis gas production process 30 through the line 95. Further, high-purity hydrogen is taken out through line 92 and supplied to upgrading reaction step 60 and hydrodesulfurization step 20. It is preferable to use a hydrogen PSA (Pressure Swing Adsorption) apparatus for the hydrogen separation step 90.
- Hydrogen PSA equipment has adsorbents (zeolite adsorbent, activated carbon, alumina, silica gel, etc.) in multiple adsorption towers arranged in parallel. Pressurization, adsorption and desorption of hydrogen in each adsorption tower ( High-purity hydrogen gas (eg, 98% or more) can be separated from the synthesis gas by repeating each step of pressure reduction and purging in order.
- the hydrogen separation step 90 is not limited to the hydrogen PSA method, and a hydrogen storage alloy adsorption method, a membrane separation method, or a combination thereof can also be used.
- catalyst layer outlet temperature 900 ° C
- catalyst layer outlet pressure 2. OMP aG
- GH SV 2000 hr H 2 O / C 0. 92
- the material balance from the synthesis gas production section entrance to the upgrade exit shown in Fig. 1 was taken, and based on the material balance, the synthesis gas production process in the liquid hydrocarbon production process from natural gas was evaluated.
- the material balance was calculated based on the composition at the locations indicated by symbols (1) to (1 3) shown in FIG.
- the proportion of carbon atoms that constitute hydrocarbons in the raw natural gas becomes liquid hydrocarbon products (kerosene, light oil, naphtha).
- the ratio is 60.8%, but in the present invention including the process system for recycling the residual gas, the number is increased to 64.8%.
- the amount of raw natural gas was reduced by 6.2% compared to the case where residual gas was not recycled (conventional example shown in Fig. 2).
- Residual gas mainly consists of methane and carbon dioxide, of which the contribution to the improvement of raw material consumption by recycling of methane is 0.9% (contribution rate of 13%), and the basic unit of raw material by recycling of carbon dioxide The contribution to improvement was 5.7% (contribution rate 87%).
- the synthesis gas produced in the synthesis gas production process is partially branched at the stage before entering the Fischer-Tropsch oil production process to form a branch line, and the branch line becomes a hydrogen separation process.
- a shift process is carried out to increase the hydrogen concentration of the synthesis gas entering the branch line by a water-gas shift reaction, and the remaining gas (off-gas) separated in the hydrogen separation process provided as a subsequent process of the shift process is converted into synthesis gas.
- a raw material for production it is configured to be recycled in the synthesis gas production process, and the off-gas from the hydrogen separation process that has been used as a fuel in the past is taken back into the process and reused as a raw material. As a result, the raw material intensity can be greatly improved.
- the hydrogen purity of the gas introduced into the hydrogen separation process is improved by about 10% compared to the conventional example.
- the increased carbon dioxide can be reused as a carbon dioxide reforming feedstock, and the yield of liquid hydrocarbon products can be increased.
- Industrial applicability It can be used for GTL (Gas To Liquids) process, etc. to produce natural hydrocarbons by chemically converting natural gas.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2718506A CA2718506C (en) | 2008-03-14 | 2009-03-11 | Production method of liquid hydrocarbons from natural gas |
EP09719518.4A EP2253585B8 (en) | 2008-03-14 | 2009-03-11 | Process for producing liquid hydrocarbons from natural gas |
BRPI0910334A BRPI0910334B1 (pt) | 2008-03-14 | 2009-03-11 | método de produção de hidrocarbonetos líquidos a partir de gás natural |
CN2009801089518A CN101970344B (zh) | 2008-03-14 | 2009-03-11 | 由天然气制造液态烃的方法 |
EA201071079A EA017725B1 (ru) | 2008-03-14 | 2009-03-11 | Способ получения жидких углеводородов из природного газа |
AU2009224187A AU2009224187B8 (en) | 2008-03-14 | 2009-03-11 | Production Method of Liquid Hydrocarbons from Natural Gas |
US12/920,751 US8268898B2 (en) | 2008-03-14 | 2009-03-11 | Production method of liquid hydrocarbons from natural gas |
ZA2010/06261A ZA201006261B (en) | 2008-03-14 | 2010-09-01 | Process for producing liquid hydrocarbons from nayural gas |
EG2010091506A EG26230A (en) | 2008-03-14 | 2010-09-07 | Method of production of liquid hydrocarbons from natural gas |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008-065465 | 2008-03-14 | ||
JP2008065465A JP5424566B2 (ja) | 2008-03-14 | 2008-03-14 | 天然ガスからの液状炭化水素製造プロセスにおける合成ガスの製造方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009113714A1 true WO2009113714A1 (ja) | 2009-09-17 |
Family
ID=41065365
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2009/055217 WO2009113714A1 (ja) | 2008-03-14 | 2009-03-11 | 天然ガスから液状炭化水素を製造する方法 |
Country Status (12)
Country | Link |
---|---|
US (1) | US8268898B2 (ja) |
EP (1) | EP2253585B8 (ja) |
JP (1) | JP5424566B2 (ja) |
CN (1) | CN101970344B (ja) |
AU (1) | AU2009224187B8 (ja) |
BR (1) | BRPI0910334B1 (ja) |
CA (1) | CA2718506C (ja) |
EA (1) | EA017725B1 (ja) |
EG (1) | EG26230A (ja) |
MY (1) | MY150064A (ja) |
WO (1) | WO2009113714A1 (ja) |
ZA (1) | ZA201006261B (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103582610A (zh) * | 2011-03-31 | 2014-02-12 | 独立行政法人石油天然气·金属矿物资源机构 | 向合成气制造装置中的金属混入抑制方法 |
JP2015529618A (ja) * | 2012-07-17 | 2015-10-08 | 武▲漢凱▼迪工程技▲術▼研究▲総▼院有限公司 | 炭素低排出のフィッシャートロプシュ合成排ガス総合利用方法 |
JP2016534180A (ja) * | 2013-07-25 | 2016-11-04 | デウ シップビルディング アンド マリン エンジニアリング カンパニー リミテッド | Fpsoのgtl生産方法およびgtl生産システム |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2543626B1 (en) * | 2010-03-02 | 2018-05-30 | Japan Oil, Gas and Metals National Corporation | Synthesis gas production method |
JP5887063B2 (ja) * | 2011-03-30 | 2016-03-16 | 独立行政法人石油天然ガス・金属鉱物資源機構 | 炭化水素合成反応装置及びそのスタートアップ方法、並びに炭化水素合成反応システム |
GB201118465D0 (en) * | 2011-10-26 | 2011-12-07 | Compactgtl Plc | Gas-to-liquid technology |
CN104232193A (zh) * | 2013-06-07 | 2014-12-24 | 中国海洋石油总公司 | 一种由炭质材料生产甲烷联产液体燃料的方法 |
US9695365B2 (en) | 2013-07-31 | 2017-07-04 | Saudi Basic Industries Corporation | Process for the production of olefins through FT based synthesis |
WO2015015312A2 (en) | 2013-07-31 | 2015-02-05 | Saudi Basic Industries Corporation | A process for the production of olefins through ft based synthesis |
WO2015082216A1 (en) | 2013-12-02 | 2015-06-11 | Haldor Topsøe A/S | A process for conversion of natural gas to hydrocarbon products and a plant for carrying out the process |
AU2015336109B2 (en) * | 2014-10-24 | 2020-11-19 | Research Triangle Institute | Integrated system and method for removing acid gas from a gas stream |
KR101694221B1 (ko) | 2014-12-24 | 2017-01-09 | 한국과학기술연구원 | 한계 가스전의 천연가스를 이용한 gtl-fpso 공정에 의한 합성연료의 제조방법과 그 제조장치 |
US20200180955A1 (en) * | 2017-06-27 | 2020-06-11 | L'Air Liquide, Société Anonyme pour I'Etude et I'Exploitation des Procédés Georges Claude | Process for high-yield production of hydrogen from a synthesis gas, and debottlenecking of an existing unit |
CN107721071A (zh) * | 2017-10-25 | 2018-02-23 | 山西潞安煤基精细化学品有限公司 | F‑t合成水相处理装置 |
US10738247B2 (en) * | 2017-11-15 | 2020-08-11 | Gas Technology Institute | Processes and systems for reforming of methane and light hydrocarbons to liquid hydrocarbon fuels |
BR102018068334B1 (pt) * | 2018-09-11 | 2021-12-07 | Petróleo Brasileiro S.A. - Petrobras | Processo para a preparação de hidrocarbonetos líquidos por processo de fischer- tropsch integrado a unidades de refino |
EP3878807A1 (en) * | 2020-03-13 | 2021-09-15 | Clariant International Ltd | Process for the production of synthesis gas via allothermic gasification with controlled carbon dioxide reduction |
JP7122042B1 (ja) | 2021-12-22 | 2022-08-19 | 独立行政法人石油天然ガス・金属鉱物資源機構 | パージ方法およびシステム |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03242302A (ja) * | 1990-02-20 | 1991-10-29 | Mitsubishi Kakoki Kaisha Ltd | 水素及び一酸化炭素の製造方法 |
JP2001342003A (ja) * | 2000-05-30 | 2001-12-11 | Mitsubishi Heavy Ind Ltd | ガソリン、軽油および灯油用合成ガスの製造方法 |
JP2002502833A (ja) * | 1998-02-10 | 2002-01-29 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | 合成ガスおよび水素転化テールガスから得られる水素を用いるガス転化 |
WO2007114274A1 (ja) * | 2006-03-30 | 2007-10-11 | Nippon Steel Engineering Co., Ltd. | 液体燃料合成システム |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2473032A1 (fr) | 1980-01-07 | 1981-07-10 | Banquy David | Procede de production d'ammoniac et du gaz de synthese correspondant |
WO1987002347A1 (en) | 1985-10-21 | 1987-04-23 | Union Carbide Corporation | Enhanced hydrogen recovery from effluent gas streams |
NZ242569A (en) * | 1991-05-30 | 1994-07-26 | British Petroleum Co Plc | Process for the conversion of natural gas into higher hydrocarbons by reforming combined with a fischer-tropsch process |
US6489370B2 (en) | 2000-05-30 | 2002-12-03 | Mitsubishi Heavy Industries, Ltd. | Method of manufacturing a synthesis gas to be employed for the synthesis of gasoline, kerosene and gas oil |
US6495610B1 (en) * | 2000-06-19 | 2002-12-17 | Imperial Chemical Industries Plc | Methanol and hydrocarbons |
CN1167650C (zh) * | 2000-07-17 | 2004-09-22 | 中国科学院山西煤炭化学研究所 | 一种由合成气合成烃的生产方法 |
MY139324A (en) | 2001-06-25 | 2009-09-30 | Shell Int Research | Integrated process for hydrocarbon synthesis |
CN1417291A (zh) * | 2001-11-05 | 2003-05-14 | 中国科学院大连化学物理研究所 | 一种通过费托合成由合成气选择性地制备柴油馏分的工艺过程 |
US7168265B2 (en) * | 2003-03-27 | 2007-01-30 | Bp Corporation North America Inc. | Integrated processing of natural gas into liquid products |
US20060106119A1 (en) | 2004-01-12 | 2006-05-18 | Chang-Jie Guo | Novel integration for CO and H2 recovery in gas to liquid processes |
US7037485B1 (en) * | 2004-11-18 | 2006-05-02 | Praxair Technology, Inc. | Steam methane reforming method |
JP4866139B2 (ja) * | 2006-04-28 | 2012-02-01 | 千代田化工建設株式会社 | 天然ガスからの灯軽油製造プロセスにおける合成ガスの製造方法 |
CN100575457C (zh) * | 2006-10-08 | 2009-12-30 | 神华集团有限责任公司 | 一种费托合成方法 |
CN101215213B (zh) * | 2007-12-29 | 2011-05-25 | 浙江工业大学 | 一种超临界费托合成的方法 |
-
2008
- 2008-03-14 JP JP2008065465A patent/JP5424566B2/ja not_active Expired - Fee Related
-
2009
- 2009-03-11 CA CA2718506A patent/CA2718506C/en not_active Expired - Fee Related
- 2009-03-11 AU AU2009224187A patent/AU2009224187B8/en not_active Ceased
- 2009-03-11 EP EP09719518.4A patent/EP2253585B8/en not_active Not-in-force
- 2009-03-11 EA EA201071079A patent/EA017725B1/ru not_active IP Right Cessation
- 2009-03-11 US US12/920,751 patent/US8268898B2/en active Active
- 2009-03-11 BR BRPI0910334A patent/BRPI0910334B1/pt not_active IP Right Cessation
- 2009-03-11 MY MYPI2010004273A patent/MY150064A/en unknown
- 2009-03-11 WO PCT/JP2009/055217 patent/WO2009113714A1/ja active Application Filing
- 2009-03-11 CN CN2009801089518A patent/CN101970344B/zh not_active Expired - Fee Related
-
2010
- 2010-09-01 ZA ZA2010/06261A patent/ZA201006261B/en unknown
- 2010-09-07 EG EG2010091506A patent/EG26230A/en active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03242302A (ja) * | 1990-02-20 | 1991-10-29 | Mitsubishi Kakoki Kaisha Ltd | 水素及び一酸化炭素の製造方法 |
JP2002502833A (ja) * | 1998-02-10 | 2002-01-29 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | 合成ガスおよび水素転化テールガスから得られる水素を用いるガス転化 |
JP2001342003A (ja) * | 2000-05-30 | 2001-12-11 | Mitsubishi Heavy Ind Ltd | ガソリン、軽油および灯油用合成ガスの製造方法 |
WO2007114274A1 (ja) * | 2006-03-30 | 2007-10-11 | Nippon Steel Engineering Co., Ltd. | 液体燃料合成システム |
Non-Patent Citations (1)
Title |
---|
See also references of EP2253585A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103582610A (zh) * | 2011-03-31 | 2014-02-12 | 独立行政法人石油天然气·金属矿物资源机构 | 向合成气制造装置中的金属混入抑制方法 |
JP2015529618A (ja) * | 2012-07-17 | 2015-10-08 | 武▲漢凱▼迪工程技▲術▼研究▲総▼院有限公司 | 炭素低排出のフィッシャートロプシュ合成排ガス総合利用方法 |
JP2016534180A (ja) * | 2013-07-25 | 2016-11-04 | デウ シップビルディング アンド マリン エンジニアリング カンパニー リミテッド | Fpsoのgtl生産方法およびgtl生産システム |
Also Published As
Publication number | Publication date |
---|---|
AU2009224187B8 (en) | 2012-01-12 |
EP2253585A4 (en) | 2012-07-11 |
MY150064A (en) | 2013-11-29 |
JP2009221036A (ja) | 2009-10-01 |
ZA201006261B (en) | 2011-05-25 |
CN101970344A (zh) | 2011-02-09 |
EA017725B1 (ru) | 2013-02-28 |
CA2718506C (en) | 2013-05-28 |
EG26230A (en) | 2013-05-02 |
EP2253585A1 (en) | 2010-11-24 |
US20110003900A1 (en) | 2011-01-06 |
AU2009224187A1 (en) | 2009-09-17 |
EP2253585B8 (en) | 2016-08-31 |
BRPI0910334B1 (pt) | 2019-02-05 |
EA201071079A1 (ru) | 2011-04-29 |
US8268898B2 (en) | 2012-09-18 |
CA2718506A1 (en) | 2009-09-17 |
JP5424566B2 (ja) | 2014-02-26 |
AU2009224187B2 (en) | 2011-07-21 |
CN101970344B (zh) | 2013-01-23 |
EP2253585B1 (en) | 2016-06-08 |
BRPI0910334A2 (pt) | 2015-10-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5424566B2 (ja) | 天然ガスからの液状炭化水素製造プロセスにおける合成ガスの製造方法 | |
JP5424569B2 (ja) | 天然ガスからの液状炭化水素製造プロセスにおける合成ガスの製造方法 | |
JP5411133B2 (ja) | 二酸化炭素の合成ガスへの接触水素化 | |
EP2569266B1 (en) | Process for the production of light olefins from synthesis gas | |
EA010025B1 (ru) | Способ удаления cos из потока синтез-газа, включающего hs и cos | |
CA2843845C (en) | Fischer-tropsch catalyst activation procedure | |
JP4866139B2 (ja) | 天然ガスからの灯軽油製造プロセスにおける合成ガスの製造方法 | |
CN102917792A (zh) | 费托合成反应用活化催化剂的制造方法、催化剂浆料的制造方法及向费托合成反应器供给催化剂浆料的方法 | |
WO2009008092A1 (ja) | 天然ガスからの灯軽油製造プロセスにおける合成ガスの製造方法 | |
EA016875B1 (ru) | Способ стабилизации эксплуатационных характеристик катализатора реакции фишера-тропша | |
JP2002316043A (ja) | 有機硫黄化合物含有燃料油用脱硫剤及び燃料電池用水素の製造方法 | |
CN105312092B (zh) | 一种催化剂及其制备方法和费托合成方法 | |
CN106391019B (zh) | 用于制备意图在费托反应中使用的催化剂的方法 | |
AU2007274285A1 (en) | Fischer-Tropsch catalyst | |
RU2440401C2 (ru) | Способ получения синтез-газа в способе получения керосина и газойля из природного газа | |
RU2533731C2 (ru) | Способ получения синтез-газа |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200980108951.8 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09719518 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 12920751 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009719518 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: PI 2010004273 Country of ref document: MY |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2718506 Country of ref document: CA |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009224187 Country of ref document: AU |
|
ENP | Entry into the national phase |
Ref document number: 2009224187 Country of ref document: AU Date of ref document: 20090311 Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: DZP2010000620 Country of ref document: DZ |
|
WWE | Wipo information: entry into national phase |
Ref document number: 201071079 Country of ref document: EA |
|
ENP | Entry into the national phase |
Ref document number: PI0910334 Country of ref document: BR Kind code of ref document: A2 Effective date: 20100910 |