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WO2004076600A1 - Procede de production de gaz de petrole liquefie contenant principalement du propane ou du butane - Google Patents

Procede de production de gaz de petrole liquefie contenant principalement du propane ou du butane Download PDF

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Publication number
WO2004076600A1
WO2004076600A1 PCT/JP2004/002168 JP2004002168W WO2004076600A1 WO 2004076600 A1 WO2004076600 A1 WO 2004076600A1 JP 2004002168 W JP2004002168 W JP 2004002168W WO 2004076600 A1 WO2004076600 A1 WO 2004076600A1
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Prior art keywords
gas
propane
low
catalyst
boiling
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English (en)
Japanese (ja)
Inventor
Kenji Asami
Kaoru Fujimoto
Sachio Asaoka
Xiaohong Li
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Japan Gas Synthesize Ltd
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Japan Gas Synthesize Ltd
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Priority claimed from JP2003049587A external-priority patent/JP2006182646A/ja
Priority claimed from JP2003356490A external-priority patent/JP2006143752A/ja
Application filed by Japan Gas Synthesize Ltd filed Critical Japan Gas Synthesize Ltd
Publication of WO2004076600A1 publication Critical patent/WO2004076600A1/fr
Anticipated expiration legal-status Critical
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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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/12—Liquefied petroleum 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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process

Definitions

  • the present invention relates to a method for producing liquefied petroleum gas whose main component is propane or butane from synthesis gas.
  • the present invention also relates to a method for producing a liquefied petroleum gas whose main component is propane or butane from a carbon-containing raw material such as natural gas.
  • Liquefied petroleum gas is obtained by compressing petroleum or natural gas hydrocarbons that exhibit a gaseous state at normal temperature and pressure, or cooling them at the same time to make them liquid, the main component of which is propane or propane. It is. LPG, which can be stored and transported in liquid form, is highly portable and, unlike natural gas, which requires a pipeline for supply, can be supplied to any location in a packed state There is a feature. Therefore, LPG containing propane as a main component, that is, propane gas, is widely used as fuel for home and business use. At present, even in Japan, provangas is supplied to approximately 25 million households (over 50% of all households). In addition to LPG, LPG is used not only for household and commercial fuels, but also as mobile fuels (mainly butane gas) such as casset stoves, disposable lit-airs, industrial fuels, and automotive fuels.
  • mobile fuels mainly butane gas
  • LPG has been separated from 1) a method of recovering from wet natural gas, 2) a method of recovering crude oil from a sulfurizing (vapor pressure adjustment) process, and 3) a product generated in a petroleum refining process. It is produced by such methods.
  • LPG especially propane gas
  • propane gas which is used as a fuel for home and business use, is expected to be demanded in the future and is very useful if a new production method that can be implemented industrially can be established.
  • the main component of the product obtained is butane.
  • LPG used as fuel for domestic and commercial use is propane gas as mentioned above.
  • Propane gas has the advantage that it can continue burning at a stable and high output even at low temperatures, compared to butane gas.
  • An object of the present invention is to produce propane and / or pulp from synthesis gas with high selectivity, to produce LPG having a low concentration of components having 2 or less carbon atoms and a high concentration of propane and / or butane. To provide a way to do it. Furthermore, An object of the present invention is to provide a method for producing LPG having a low concentration of components having 2 or less carbon atoms and a high concentration of propane and / or butane from a synthesis gas more economically.
  • Another object of the present invention is to provide a method capable of producing LPG having a low concentration of components having 2 or less carbon atoms and a high concentration of propane and / or butane from a carbon-containing raw material such as natural gas. is there. Furthermore, by providing a more economical method for producing LPG with low concentrations of components with 2 or less carbon atoms and high concentrations of propane and Z or butane from carbon-containing raw materials such as natural gas. is there.
  • a low-boiling component which is a substance having a boiling point or a sublimation point lower than that of propane from a synthesis gas in the presence of a catalyst, and the main component of the contained hydrocarbon is propane or butane
  • a method for producing a liquefied petroleum gas containing propane or butane as a main component (the method for producing the 1-1_1 LPG).
  • synthesis gas production process for producing synthesis gas from low-boiling components recycled as a raw material of the synthesis gas production process in the recycling process;
  • a method for producing a liquefied petroleum gas containing propane or pulp as a main component (a method for producing LPG of 1-2) is provided.
  • a lower-paraffin-producing process for producing a lower-paraffin-containing gas containing a low-boiling component that is a substance having a boiling point or a sublimation point lower than the boiling point of, and the main component of the contained hydrocarbon is propane or butane.
  • a method for producing a liquefied petroleum gas containing propane or butane as a main component (a method for producing the 2_1st LPG).
  • a carbon-containing raw material and a low-boiling component separated from a lower paraffin-containing gas in a separation step and recycled as a raw material in a synthesis gas production step in a recycling step
  • a synthesis gas production process for producing a synthesis gas containing carbon oxide and hydrogen in a ratio of CO: H 2 1: 0.5 to 1: 1.4 (molar ratio);
  • the synthesis gas obtained in the synthesis gas production process in the presence of a catalyst contains low-boiling components that are substances having a boiling point or sublimation point lower than the boiling point of propane, and the main component of the contained hydrocarbon is propane. Or a lower paraffin production process for producing a lower noraffin-containing gas that is butane;
  • the present invention provides a method for producing a liquefied petroleum gas containing propane or butane as a main component (the second method for producing LPG).
  • the above-described method for producing a liquefied petroleum gas wherein the content of the recycled low-boiling component in the raw material is 40 to 75 mol% in the synthesis gas production process. .
  • the liquefied petroleum according to the above wherein the content of low-boiling components (excluding hydrogen) in the lower-paraffin-containing gas produced in the lower-paraffin production step is 60% or less on a carbon basis.
  • a method for producing a gas is provided.
  • the above-described method for producing a liquefied petroleum gas wherein the low-boiling component is at least one selected from the group consisting of ethane, ethylene and methane.
  • the synthesis gas refers to a mixed gas containing hydrogen and carbon monoxide, and is not limited to a mixed gas composed of hydrogen and carbon monoxide.
  • the synthesis gas may be, for example, a mixed gas containing carbon dioxide, water, methane, ethane, ethylene and the like.
  • the synthesis gas obtained by reforming natural gas usually contains carbon dioxide and water vapor in addition to hydrogen and carbon monoxide.
  • the synthesis gas may be a coal gas obtained by coal gasification or a water gas produced from coal coke.
  • propane and / or butane can be produced from carbon-containing raw materials such as natural gas or synthesis gas with high selectivity.
  • liquefied petroleum gas having a low concentration of components having 2 or less carbon atoms and a high concentration of propane and / or butane can be produced from a carbon-containing raw material such as natural gas or a synthesis gas.
  • an LPG having a total content of propane and butane of 90 mol% or more, and more preferably 95 mol% or more (including 100 mol%) can be produced.
  • LPG having a propane content of 50 mol% or more, and more preferably 60 mol% or more (including 100 mol%). can be.
  • the concentration of the component having 2 or less carbon atoms from the carbon-containing raw material such as natural gas or the synthesis gas is reduced.
  • LPG which has a lower concentration of propane and / or butane, can be produced more economically.
  • Such low-boiling components can be separated from the lower paraffin-containing gas and recycled as a raw material. However, if the amount of low-boiling components contained in the produced lower-paraffin-containing gas increases, the amount of recycle increases, which tends to lower the economic efficiency.
  • water is by-produced as shown in the following equations (3) and (4). This by-produced water is considered to react with carbon monoxide to generate hydrogen as shown in the following equation (5).
  • FIG. 1 is a process flow diagram showing a main configuration of an example of an LPG manufacturing apparatus suitable for carrying out the present invention.
  • Low boiling components are substances that have a boiling point or sublimation point lower than that of propane.
  • the carbon-containing material a substance containing carbon
  • H 2 0, 0 can generate 2 and reacted with at least one selected from the group consisting of C0 2 H 2 and CO .
  • the carbon-containing raw material those known as raw materials for synthesis gas can be used.
  • lower hydrocarbons such as methyl ethane and the like, natural gas, naphtha, coal and the like can be used.
  • the content of catalyst poisoning substances such as sulfur and sulfur compounds as carbon-containing raw materials is reduced. Less is preferred. If the carbon-containing raw material contains a catalyst poisoning substance, if necessary, Prior to this, a step of removing catalyst poisoning substances such as desulfurization can be performed.
  • the synthesis gas can be produced by a known method.
  • natural gas methane
  • synthesis gas can be produced by a steam reforming method, an autothermal reforming method, or the like.
  • steam necessary for steam reforming, oxygen necessary for autothermal reforming, and the like can be supplied as needed.
  • synthesis gas can be produced using an air-blown gasifier.
  • H 2 1: 0.5 to 1: 1.4 (molar ratio)
  • natural gas (methane) and carbon dioxide are produced.
  • C_ ⁇ 2 reforming a method of reacting with (molar ratio) degree
  • Low boiling components include hydrogen, carbon monoxide, carbon dioxide, ethane, ethylene, methane, and the like. Of these, methane, ethylene and ethylene are carbon-containing raw materials. Also, carbon dioxide, for example, can be returned to by connexion syngas C 0 2 Rifo gang ing reaction represented by the following formula (6). By recycling low-boiling components as raw materials in the synthesis gas production process, it is possible to reduce the raw material unit consumption.
  • the content of low-boiling components in the raw material is determined as appropriate For example, it can be 40 to 75 mol%. From the viewpoint of economy and the like, the content of the low boiling component in the raw material is more preferably 55 mol% or less.
  • the shift reactor provided downstream of the reformer which is a reactor for producing synthesis gas from a raw material as described above, the shift reaction (CO + H 2 0 C0 2 + H 2) Niyotsu Te Synthesis
  • the composition of the gas can also be adjusted.
  • the content ratio (on a molar basis) of hydrogen to carbon monoxide in the synthesis gas is preferably 3 [ ⁇ , / CO] or less, more preferably 2.3 [H 2 / CO] or less.
  • the feed ratio of the carbon-containing raw material to steam (water), oxygen, and carbon dioxide, the content of low-boiling components in the raw material, and the synthesis gas production catalyst used And the operating conditions for the reaction may be appropriately selected.
  • reaction temperature (catalyst layer outlet temperature) 800 ⁇ 900 ° C, reaction pressure l ⁇ 4MPa, gas space velocity (GHSV) 200 in an externally heated multi-tube reaction tube type device filled with magnesia catalyst for reducing surface area Syngas can be produced under operating conditions such as Ohr- 1 You.
  • the ratio of steam to raw carbon is preferably 1.5 or less from the viewpoint of energy efficiency. .2 is more preferable.
  • S / C is set to such a low value, the possibility of carbon precipitation cannot be ignored.
  • the low-boiling components obtained in the separation process are recycled to the synthesis gas production process, not only methane contained in this component, but also ethylene and ethylene become carbon-containing raw materials.
  • the catalyst described in WO 98/46524 is a catalyst in which at least one catalyst metal selected from rhodium, ruthenium, iridium, palladium and platinum is supported on a support made of a metal oxide.
  • the specific surface area of the catalyst is 25 m 2 / g or less, the electronegativity of metal ions in the carrier metal oxide is 13.0 or less, and the amount of the catalyst metal carried is a carrier in terms of metal.
  • the catalyst is 0.0005 to 0.1 mol% based on the metal oxide. From the viewpoint of preventing carbon deposition, the degree of electric anisotropy is preferably from 4 to 12, and the specific surface area of the catalyst is preferably from 0.01 to 10 m 2 Zg.
  • the electronegativity of the metal ions in the metal oxide is defined by the following equation.
  • Xi (1 + 2 i) Xo
  • Xi is the electronegativity of the metal ion
  • Xo is the electronegativity of the metal
  • i is the number of valence electrons of the metal ion.
  • the metal oxide is a composite metal oxide
  • the average metal ion electronegativity is used, and the value is calculated based on the electronegativity of each metal ion contained in the composite metal oxide. The sum of the values multiplied by the mole fraction of the sword.
  • the electronegativity (Xo) of metals is based on Pauling's electronegativity. Pauling's electronegativity uses the values listed in Table 15.4 of "Ryo Fujishiro, Moore Physical Chemistry (2) (4th edition), Tokyo Kagaku Dojin, p. 707 (1974)".
  • the electronegativity (Xi) of metal ions in metal oxides is described in detail in, for example, “Catalysis Society of Japan, Catalyst Course, Vol. 2, p. 145 (1985)”.
  • examples of the metal oxide include metal oxides containing one or more metals such as Mg, Ca, Ba, Zn, AlZr, and La.
  • An example of such a metal oxide is magnesia (MO).
  • the reaction temperature is preferably 600 to 1200 ° C, more preferably 600 to 1000 ° C, and the reaction pressure is preferably 0.098 MPa aG. ⁇ 3.9MPaG, more preferably 0.49MPaG ⁇ 2.9MPaG (G indicates gauge pressure).
  • the gas space velocity is preferably 0.49MPaG ⁇ 2.9MPaG (G indicates gauge pressure).
  • the ratio of the use of steam to the carbon-containing raw material is as follows: 1 mol of carbon in the carbon-containing raw material (including the recycled raw material, excluding C ⁇ 2), preferably 0.5 to 2 mol of steam (H 20 ). The ratio is more preferably 0.5 to 1.5 mol, and even more preferably 0.8 to 1.2 mol.
  • the reaction temperature is preferably rather is 500 ⁇ 1200 ° C, more preferably from 600 to 1000 ° C
  • the reaction pressure is preferably 0 49 MPaG to 3.9MPaG ⁇ More preferably, it is 0.49MPaG to 2.9MPaG.
  • the gas space velocity (GHSV) preferably 000 ⁇ 1 0 3 000 hr ⁇ ⁇ more preferably 2, 000 ⁇ 8, 00 Oh r 1 It is.
  • C_ ⁇ except 2) carbon per mole in a proportion of preferably C_ ⁇ 2 from 20 to 0.5 mol, and more favorable Mashiku 10-1 mol.
  • the mixing of the steam and C0 2 is not particularly limited, in general, H 2 0 / C_ ⁇ 2 (molar ratio) is 0. 1 to a 10, the reaction temperature is preferably 5 50 ⁇ 1 200 ° C, more preferably Is from 600 to 1,000 ° C., and the reaction pressure is preferably from 0.29 MPa aG to 3.9 MPa, more preferably from 0.49 MPa aG to 2.9 MPa aG.
  • gas space velocity is preferably 1,000 to; L ⁇ , 00 Ohr, more preferably 2,000 to 8, OO Ohr 1 .
  • the ratio is more preferably 0.5 to: 0.5 mol, and further preferably 0.5 to 1.2 mol.
  • the catalyst described in JP-A-2000-288394 is composed of a composite oxide having a composition represented by the following formula (I), and M 1 and Co are highly dispersed in the composite oxide. It is a catalyst characterized by the above.
  • e 1 is the number necessary for the element to keep charge balance with oxygen.
  • M 1 is at least one of Group 6A elements, Group 7A elements, Group 8 transition elements except Co, Group IB elements, Group 2B elements, Group 4B elements, and Lanthanoid elements. Is also one type of element. )
  • the catalyst described in JP-A-2000-469 is composed of a composite oxide having a composition represented by the following formula (II), and M 2 and Ni are highly dispersed in the composite oxide.
  • e 2 is the number required for the element to be in charge balance with oxygen.
  • M 2 is a group 3B element, a group 4A element, a group 6B element, or a group 7B element of the periodic table. Element, at least one element of Group 1A element and lanthanide element.
  • H 2 1: 0.5 to 1: 1.4 (molar ratio).
  • Manufacturing is the ratio of hydrogen to carbon monoxide in the synthesis gas (molar basis), 0. 55 [H 2 / CO ] or preferably, 0. 6 [H 2 / CO ] above is more preferable.
  • a ratio (molar basis) of hydrogen to carbon monoxide in the synthesis gas produced is: 1. preferably 2 [H 2 / CO]
  • 1. favored more is 1 [H 2 / CO] or less correct .
  • the amount of low boiling components contained in the lower paraffin-containing gas obtained in the next lower paraffin production process is reduced, and as a result, the low boiling components are converted into raw materials. As a result, the amount to be recycled is reduced, and LPG can be produced more economically.
  • the shift reactor provided downstream of the reformer which is a reactor for producing synthesis gas from a raw material as described above, synthetic Te shift reaction (CO + H 2 0 ⁇ C0 2 + H) Niyotsu
  • the composition of the gas can be adjusted to the above range.
  • the supply ratio of the carbon-containing raw material to at least one selected from the group consisting of water, oxygen and carbon dioxide, the content of the low-boiling component in the raw material may be appropriately selected.
  • a reforming catalyst comprising a composite oxide having a composition represented by the following formula (III), a carbon-containing raw material (a carbon-containing raw material in a low-boiling component separated from a lower paraffin-containing gas) ), Oxygen, carbon dioxide, and steam (steam) in the raw material gas introduced into the reactor with a (carbon dioxide + steam) / carbon ratio of 0.5 to 3, and an oxygen / force-carbon ratio of 0.5.
  • M is a Group 6A element, a Group 7A element, a Group 8 transfer element other than Co and Ni, a Group 1B element, a Group 2B element, a Group 4B element and a
  • Represents at least one element selected from the group consisting of node elements, a, b, c, d and e represent the atomic ratio of each element, and when a + b + c + d + e l , 0 ⁇ a ⁇ 0.1, 0.01 ⁇ (b + c) ⁇ 0.3, 0 ⁇ b ⁇ 0.3, 0 ⁇ c ⁇ 0.3, 0.6 ⁇ (d + e) ⁇ 0.999, 0 ⁇ d ⁇ 0.999, 0 ⁇ e ⁇ 0.999, and f is the number required for each element to maintain charge balance with oxygen.)
  • the ratio of (carbon dioxide + steam) / carbon in the raw material gas introduced into the reactor is preferably about 0.5 to 2.
  • the temperature at the outlet of the reactor is preferably 950 to 1050 ° C.
  • the pressure at the outlet of the reactor is preferably 15 to 20 kg / cm 2 .
  • the space velocity of the raw material gas is usually 500 ⁇ 200000hr- 1, 1000 -100000 hr one 1 are preferred, 1000 to 70000 hr one 1 is more preferred.
  • MgO ⁇ CaO has a rock salt type crystal structure, and some of the Mg or Ca atoms located in the lattice are replaced with Co, Ni or M. It is a kind of solid solution that forms a single phase.
  • M may be at least one element selected from the group consisting of manganese, molybdenum, rhodium, ruthenium, platinum, palladium, copper, silver, zinc, tin, lead, lanthanum and cerium. preferable.
  • the content (a) of M is 0 ⁇ a 0.1, preferably 0 ⁇ .a ⁇ 0.05, and more preferably 0 ⁇ a ⁇ 0.03. If the M content (a) exceeds 0.1, the activity of the reforming reaction decreases.
  • the cobalt content (b) is 0 ⁇ b ⁇ 0.3, preferably O ⁇ b ⁇ O.25, and more preferably 0 ⁇ b ⁇ 0.2. If the content of the cobalt (b) exceeds 0.3, it is difficult to sufficiently obtain the effect of preventing carbonaceous deposition.
  • the nickel content (c) is 0 ⁇ c ⁇ 0.3, preferably 0 ⁇ c ⁇ 0.25, and more preferably 0 ⁇ c ⁇ 0.2. If the nickel content (c) exceeds 0.3, it is difficult to sufficiently obtain the effect of preventing carbonaceous deposition.
  • the total (b + c) of the cobalt content (b) and the nickel content (c) is 0.001 ⁇ (b + c) ⁇ 0.3, and 0.001 ⁇ (b + c) ⁇ 0.25, more preferably 0.001 ⁇ (b + c) ⁇ 0.2.
  • the total content (b + c) exceeds 0.3, it is difficult to sufficiently obtain the effect of preventing carbonaceous deposition.
  • the total content (b + c) is less than 0.001, the reaction activity decreases.
  • the sum of magnesium content (d) and calcium content (e) (d + e) is 0.6 ⁇ (d + e) ⁇ 0.9998, and 0.7 ⁇ (d + e) ⁇ 0 9998, and more preferably 0.9. (D + e) ⁇ 0.9998.
  • the magnesium content (d) is 0 ⁇ d ⁇ 0.999
  • the calcium content (e) is 0 ⁇ e ⁇ 0.999, preferably 0 ⁇ e ⁇ 0.5, and more preferably 0 ⁇ e ⁇ 0.3.
  • the catalyst may not contain calcium.
  • the total amount of magnesium content (d) and calcium content (e) (d + e) is determined by balancing M content (a), cobalt content (b) and nickel content (c).
  • Can be (D + e) exhibits an excellent effect on the reforming reaction at any ratio as long as it is within the above range.
  • the content of calcium (e) and M (a) is large, it is high in suppressing carbonaceous deposition. Although effective, the catalytic activity tends to be lower than when magnesium (d) is high.
  • calcium content (e) is preferably 0.5 or less
  • the M content (a) is preferably 0.1 or less.
  • the reforming catalyst used preferably has at least one of M, Co and Ni highly dispersed in the composite oxide.
  • the dispersion is defined as the ratio of the number of atoms exposed on the catalyst surface to the total number of atoms of the supported metal. That is, if the number of atoms of the Co, Ni or M metal element or its compound is A, and the number of these atoms exposed on the particle surface is B, BZA becomes the dispersion.
  • the reaction becomes more active and the reaction proceeds stoichiometrically. ) Is more effectively prevented.
  • Examples of a method for producing such a reforming catalyst include an impregnation-supporting method, a coprecipitation method, a sol-gel method (hydrolysis method), and a uniform precipitation method.
  • the above-mentioned reforming catalyst is usually subjected to an activation treatment before it is used for syngas production.
  • the activation treatment is performed in the presence of a reducing gas such as hydrogen gas at a temperature of 500 to 1000 ° C, preferably 600 to 1000 ° C, more preferably 650 to 0.5 to 30 ° C in a temperature range of L000 ° C. This is done by heating the catalyst for about an hour.
  • the reducing gas may be diluted with an inert gas such as nitrogen gas.
  • This activation treatment can also be performed in a reactor that performs a reforming reaction. By this activation treatment, catalytic activity is developed.
  • Another method of producing the synthesis gas used in the present invention is to partially oxidize a carbon-containing raw material (including a carbon-containing raw material in a low-boiling component separated from a lower paraffin-containing gas) to obtain unreacted carbon-containing material.
  • a mixed gas containing a raw material and having a temperature of at least 600 ° C. is generated.
  • At least one metal selected from the group consisting of rhodium, ruthenium, iridium, palladium and platinum on an oxide support, specific surface area of 25 m 2 / g or less, supporting catalyst metal
  • carbon dioxide gas and / or steam was added in the presence of a catalyst in an amount of 0.0005 to 0.1 mol% based on the carrier metal oxide in terms of metal.
  • a method of producing a synthesis gas by reacting is exemplified.
  • a mixed gas comprising a carbon-containing raw material (including a carbon-containing raw material in low-boiling components separated from a lower-paraffin-containing gas), an oxygen-containing gas (air, oxygen, etc.), and carbon dioxide gas and / or steam.
  • the mixing was carried out in the presence of a catalyst having a specific surface area of 25 m 2 / g or less and a supporting amount of catalyst metal of 0.0005 to 0.1 mol% in terms of metal relative to the supporting metal oxide.
  • the carbon-containing raw material in the gas is partially oxidized to generate a mixed gas containing unreacted carbon-containing raw material and having a temperature of at least 600 ° C. With carbon dioxide And / or reacting steam to produce synthesis gas.
  • the catalyst metal may be supported in a metal state, or may be supported in a state of a metal compound such as an oxide.
  • the metal oxide used as the carrier may be a single metal oxide or a composite metal oxide.
  • the electronegativity of the metal ions in the metal oxide for a carrier is 13 or less, preferably 12 or less, more preferably 10 or less. When the electronegativity of the metal ions in the metal oxide exceeds 13, carbon deposition becomes remarkable when the catalyst is used.
  • the lower limit of the electronegativity of metal ions in the metal oxide for a carrier is usually about 4.
  • the electronegativity of metal ions in the metal oxide is defined by the following equation.
  • the metal oxide is a composite metal oxide
  • the average metal ion electronegativity is used, and the value is calculated based on the electronegativity of each metal ion contained in the composite metal oxide.
  • the sum of the values obtained by multiplying the acid fraction by the mole fraction is used.
  • the electronegativity (Xo) of a metal uses the electronegativity of Pau1ing.
  • the electronegativity of Pauling is described in Table 15.4 of "Ryo Fujishiro, Moore Physical Chemistry (2) (4th edition), Tokyo Kagaku Dojin, p. 707 (1974)".
  • the electronegativity (Xi) of metal ions in metal oxides is described in detail in, for example, “Catalysis Society of Japan, Catalyst Course, Vol. 2, p. 145 (1985)”.
  • Examples of such a metal oxide include metal oxides containing one or more metals such as Mg, Ca, Ba, Zn, Al, Zr, and La.
  • a metal oxide specifically, magnesia (MgO), calcium oxide (CaO), barium oxide (B aO-), zinc oxide (ZnO), alumina (Al 2 ⁇ 3), Jirukonia (Z r 0 2), and single metal oxides such as lanthanum oxide (L a 2 0 3), MgO / CaO, Mg ⁇ / B aO, MgO / ZnO, MgO / a 1 2 0 3, MgO / Z r 0 2, C aO / BaO, C aO / Z nO, C a O / A 1 2 0 3 ⁇ C aO / Z r 0 2 , B a O / Z n ⁇ , BaO / Al 2 0 3N B aO / Z r0
  • Used specific surface area of the catalyst is at 25 m 2 Zg less, preferably 20 m 2 / g or less, more preferably 1 5 m 2 / g, particularly preferably 1 Om 2 / g or less.
  • the lower limit of the specific surface area of the catalyst used is usually about 0.0 lm 2 / g.
  • the specific surface area of the catalyst and the specific surface area of the metal oxide as a support are substantially the same. Therefore, the specific surface area of the metal oxide as a carrier is 25 m 2 / g or less, preferably 20 m 2 / g or less, more preferably 15 m 2 / g or less, and particularly preferably 10 m 2 / g or less.
  • the lower limit of the specific surface area of the metal oxide as a carrier is usually about 0.01 m 2 / g.
  • the specific surface area of the metal oxide as the catalyst or the carrier was measured at a temperature of 15 ° C. by the BET method.
  • 300 to 1300 metal oxides are used as carriers before the catalyst metal is supported.
  • it is obtained by calcining at 650 to 1200 ° C, and after carrying the catalyst metal, calcining the obtained catalyst metal support at 600 to 1300 ° C, preferably 650 to 1200 ° C.
  • the obtained catalyst metal support is fired at 600 to 1300 ° C, preferably 650 to 1200 ° C. Can be.
  • the specific surface area of the resulting metal oxide which is a catalyst or a support, can be controlled.
  • the supported amount of the catalyst metal with respect to the metal oxide serving as the support is 0.0005 to 0.1 mol% in terms of metal.
  • the amount of the catalytic metal supported on the metal oxide as a support is preferably 0.001 mol% or more, more preferably 0.002 mol% or more, in terms of metal.
  • the amount of the catalytic metal supported on the metal oxide as the carrier is preferably 0.09 mol% or less in terms of metal.
  • the above-mentioned catalyst has a small specific surface area of the catalyst and a very small amount of catalyst metal carried thereon, it has a sufficient syngasification activity for the carbon-containing raw material and significantly suppresses the carbon deposition activity.
  • Such a catalyst can be prepared according to a known method.
  • a method for producing a catalyst for example, a metal oxide serving as a carrier is dispersed in water, a catalyst metal salt or an aqueous solution thereof is added and mixed, and then the metal oxide supporting the catalyst metal is separated from the aqueous solution. Drying, baking (impregnating method) or exhausting the metal oxide as a carrier, adding a small amount of a metal salt solution for the pore volume little by little to make the carrier surface uniformly wet, and then drying and drying. Firing method (inc ipent—wet ne ss method).
  • reaction temperature 500 ⁇ 1200 ° C, 600 ⁇ 1000 ° C is preferred.
  • Reaction pressure is 5 ⁇ 40kg / cm 2 G, 5 ⁇ 30 kg / cm 2 G are preferred.
  • a gas hourly space velocity is 1, a 000 ⁇ 1 0, O OOhr- 1, 2 , 000 ⁇ 8, 000 hr * - 1 is preferred.
  • the reaction temperature is 600 to 1200 ° C, preferably 600 to 1000 ° C.
  • the reaction pressure is 1 to 40 kg / cm 2 G, preferably 5 to 30 kg / cm 2 G.
  • the gas space velocity (GHS V) is 1, a 000 ⁇ 1 0, O OOhr- 1, 2 , 000 ⁇ 8, 000 hr one 1 is preferred.
  • the content of steam in the feed gas to be introduced into the reactor, per one mole of carbon of the carbon-containing in the raw materials, steam (H 2 0) is 20 to 0.5 mol, 10-1 mol are preferred, 1.5 ⁇ 1 mole is more preferred.
  • the energy required for the reforming reaction is partially oxidized (partial combustion) of the carbon-containing raw material, which is a reaction raw material for the reforming, and is generated by combustion heat generated at that time. Replenished.
  • Partial oxidation reaction of the carbon-containing raw material 600 ⁇ 1500 ° C, preferably from 700 to 13 00 Temperature of ° C and 5 ⁇ 50 kg / cm 2 G, the pressure conditions of preferably 10 ⁇ 40 kg / cm 2 G Will be implemented.
  • Oxygen is used as an oxidizing agent for partially oxidizing the carbon-containing raw material.
  • an oxygen-containing gas such as air or oxygen-enriched air is used in addition to pure oxygen.
  • the oxygen content of the raw material gas introduced into the reactor is 0.1 to 4 as the atomic ratio of oxygen to carbon (0 / C) in the carbon-containing raw material. Yes, 0.5 to 2 is preferred.
  • a high-temperature mixed gas containing at least 600 ° C, preferably 700 to 1300 ° C, containing the unreacted carbon-containing raw material is obtained.
  • a synthesis gas By reacting carbon dioxide and / or steam with the unreacted carbon-containing raw material in this mixed gas under the above conditions, a synthesis gas can be produced.
  • Carbon dioxide and Z or steam may be added to and mixed with the mixed gas obtained by partial oxidation of the carbon-containing raw material, or may be added and mixed in advance to the carbon-containing raw material to be subjected to the partial oxidation reaction. You may leave. In the latter case, it becomes possible to simultaneously perform the partial oxidation of the carbon-containing raw material and the reforming reaction.
  • the reforming reaction of the carbon-containing raw material can be carried out in various types of reactors, but is usually preferably carried out in a fixed bed system or a fluidized bed system.
  • a low-boiling component which is a substance having a boiling point or sublimation point lower than the boiling point of propane, from the synthesis gas obtained in the above synthesis gas production process.
  • a low-boiling component which is a substance having a boiling point or sublimation point lower than the boiling point of propane
  • mixed catalyst obtained by mixing the Y-type Zeorai bets 6 Can be used.
  • the mixing ratio of the former and the latter can be, for example, about 1: 1 by mass.
  • Examples of the lower paraffin-producing catalyst including the above-mentioned catalyst include, for example, a catalyst containing one or more methanol synthesis catalyst components and one or more zeolite catalyst components.
  • the methanol synthesis catalyst component refers to a component that exhibits a catalytic action in the reaction of C ⁇ + 2H 2 CH 3 OH.
  • the zeolite catalyst component refers to methanol Refers to zeolite that exhibits a catalytic action in the condensation reaction to hydrogen chloride and / or the condensation reaction of dimethyl ether to hydrocarbon.
  • methanol is synthesized from carbon monoxide and hydrogen on the methanol synthesis catalyst component.
  • the synthesized methanol is converted into a lower olefin hydrocarbon whose main component is propylene or putene at an active site in the pores of the zeolite catalyst component.
  • carbene H 2 C :
  • carbene H 2 C :
  • lower olefins are formed by polymerization of the carbene.
  • the generated lower olefins escape from the pores of the zeolite catalyst component and are rapidly hydrogenated on the methanol synthesis catalyst component to become paraffins whose main component is propane or butane.
  • the content ratio (by mass) of the methanol synthesis catalyst component to the zeolite catalyst component is preferably 0.5 or more [methanol synthesis catalyst component / zeolite catalyst component], and 0.8 or more [methanol synthesis catalyst].
  • the content ratio (by mass) of the methanol synthesis catalyst component to the zeolite catalyst component is preferably 3 or less [methanol synthesis catalyst component / zeolite catalyst component], and 2 or less [methanol synthesis catalyst component].
  • / Zeolite catalyst component By setting the content ratio of the methanol synthesis catalyst component to the zeolite catalyst component within the above range, propane and / or pentane can be produced with higher selectivity and higher yield.
  • the methanol synthesis catalyst component has a function as a methanol synthesis catalyst
  • the zeolite catalyst component is a solid acid zeolite catalyst whose acidity is adjusted to the condensation reaction of methanol and / or dimethyl ether to hydrocarbons. It has the function of Therefore, the content ratio of the methanol synthesis catalyst component to the zeolite catalyst component is determined by the function of the catalyst to synthesize methanol and the function of generating hydrocarbons from methanol. It is reflected in the relative ratio.
  • paraffins whose main components are propane or butane by reacting carbon monoxide and hydrogen in the present invention, carbon monoxide and hydrogen must be sufficiently converted to methanol by a methanol synthesis catalyst component.
  • the produced methanol is sufficiently converted to olefins whose main component is propylene or butene by the zeolite catalyst component, and the main component is converted to propane or butane by the methanol synthesis catalyst component. It must be converted to certain paraffins.
  • the content ratio (by mass) of the methanol synthesis catalyst component to the zeolite catalyst component By setting the content ratio (by mass) of the methanol synthesis catalyst component to the zeolite catalyst component to 0.5 or more [methanol synthesis catalyst component / zeolite catalyst component], higher conversion of carbon monoxide and hydrogen can be achieved. Can be converted to methanol.
  • the content ratio (mass basis) of the methanol synthesis catalyst component to the zeolite catalyst component to 0.8 or more [methanol synthesis catalyst component / zeolite catalyst component]
  • the produced methanol can be more selectively treated with propane or methanol. It can be converted to paraffins whose main component is butane.
  • the content ratio (by mass) of the methanol synthesis catalyst component to the zeolite catalyst component is 3 or less [methanol synthesis catalyst component / zeolite catalyst component], more preferably 2 or less [methanol synthesis catalyst component / zeolite catalyst component]. ]
  • the produced methanol can be converted into paraffins whose main component is propane or butane at a higher conversion rate.
  • Examples of the methanol synthesis catalyst component include known methanol synthesis catalysts, specifically, Cu—Zn system, Cu—Zn—Cr system, Cu—Zn—A1 system, Cu—Zn—Ag system, Cu — Zn— Mn— V system, Cu—Zn— Mn— Cr system, Cu-Zn-Mn-Al—Cr—Zn system and others with a third component added, or Ni— Examples include those based on Zn, those based on Mo, those based on Ni-carbon, and those based on noble metals such as Pd. Also, a commercially available methanol synthesis catalyst can be used.
  • the zeolite catalyst component has a three-dimensional expansion of pores through which reactive molecules can diffuse.
  • a medium pore zeolite or a large pore zeolite is preferred. These include, for example, ZSM_5, MCM-22, Peter, Y-type, and the like.
  • small pore zeolites such as SAPO-34 or porphyrins such as mordenite generally exhibit high selectivity for the condensation reaction of methyl and / or dimethyl ether to lower olefin hydrocarbons.
  • ZSM-5, MCM-22, etc. which generally show higher selectivity for the condensation reaction of methanol and / or dimethyl ether to alkyl-substituted aromatic hydrocarbons than zeolite, in which the diffusion of reactive molecules in the pores is not three-dimensional.
  • Zeolite in which the diffusion of reactive molecules in pores such as medium-pore zeolite or large-pore zeolite such as Y-type is preferred.
  • the use of zeolite 1, which has three-dimensional diffusion of reactive molecules in pores such as medium pore zeolite and large pore zeolite, allows methane or butene to be used as a main component in order to more selectively produce the generated methanol.
  • Olefins, or paraffins containing propane or pentane as a main component.
  • the medium pore zeolite refers to a zeolite having a pore diameter of 0.44 to 0.65 nm formed mainly by a 10-membered ring
  • the large pore zeolite has a pore diameter of Is a zeolite of 0.66-0.76 nm formed mainly by a 12-membered ring.
  • the pore size of the zeolite catalyst component is more preferably 0.5 nm or more from the viewpoint of the selectivity of the C3 component and the C4 component in the gaseous product.
  • the skeleton pore diameter of the zeolite catalyst component is more preferably 0.77 nm or less from the viewpoint of suppressing the production of liquid products such as aromatic compounds such as benzene and gasoline components such as C5 component.
  • the so-called ⁇ Shirikazeorai DOO specifically S i 0 2 / A 1 2 0 3 molar ratio Zeorai bets 1 0-5 0 preferred.
  • S I_ ⁇ 2 / A 1 2 0 3 molar ratio is used high Shirikazeorai bets 1 0-5 0, Orefin such that the generated main component more selectively propylene or butene with methanol, more propane or It can be converted to paraffins containing butane as the main component.
  • a medium pore zeolite or a large pore zeolite having three-dimensional expansion of pores through which a reactive molecule can diffuse is particularly preferable.
  • a solid acid zeolite such as USY ⁇ high silica type Beiyu can be mentioned.
  • zeolite catalyst component a solid acid zeolite as described above whose acidity is adjusted by ion exchange or the like is used.
  • a mixture prepared by separately preparing a methanol synthesis catalyst component and a zeolite catalyst component and mixing them is preferable.
  • a methanol synthesis catalyst component and a zeolite catalyst component By separately preparing the methanol synthesis catalyst component and the zeolite catalyst component, it is easy to optimally design the composition, structure, and physical properties of each function for each function.
  • Some methanol synthesis catalysts need to be activated by reduction before use. In the present invention, it is not always necessary to preliminarily reduce and activate the methanol synthesis catalyst component, and the methanol synthesis catalyst component and the zeolite catalyst component are mixed and molded to form a lower paraffin production catalyst. After the production, a reduction treatment can be performed before starting the reaction to activate the methanol synthesis catalyst component.
  • the lower paraffin-producing catalyst may contain other additional components as needed, as long as the desired effect is not impaired.
  • paraffins whose main component is propane or butane, preferably paraffins whose main component is propane.
  • the gas fed into the reactor is the synthesis gas obtained in the above synthesis gas production process.
  • the gas fed into the reactor contains carbon monoxide and hydrogen.
  • CO: H 2 1: 0.5 to 1: 1.4 (molar ratio). Ratio of hydrogen to carbon monoxide in the gas fed to the reactor (mol basis), 0. 55 [H 2 / CO ] or preferably, 0. 6 [H 2 / CO ] on more than more preferable.
  • 1. 1 [H 2 / CO] is more preferable.
  • the concentration of carbon monoxide in the gas fed into the reactor is preferably at least 20 mol% from the viewpoints of securing a pressure (partial pressure) of carbon monoxide suitable for the reaction and improving the unit consumption of raw materials. , 25 mol% or more is more preferable. Further, the concentration of carbon monoxide in the gas fed into the reactor is preferably 67 mol% or less, more preferably 60 mol% or less, from the viewpoint that the conversion of carbon monoxide becomes sufficiently high. .
  • the concentration of carbon monoxide in the synthesis gas produced in the synthesis gas production process is preferably 20 mol% or more, more preferably 25 mol% or more, and preferably 67 mol% or less. 0 mol% or less is more preferable.
  • the concentration of carbon monoxide in the gas fed into the reactor is preferably 40 mol% or less, more preferably 35 mol% or less.
  • the gas fed into the reactor may contain, for example, carbon dioxide, water, methane, ethane, ethylene, an inert gas, and the like, in addition to carbon monoxide and hydrogen.
  • the gas fed into the reactor may be a mixture of carbon monoxide and hydrogen, which are raw materials for producing lower paraffin, and carbon dioxide.
  • the gas fed into the reactor may be a mixture of carbon monoxide and hydrogen, which are raw materials for producing lower paraffin, and carbon dioxide.
  • the gas fed into the reactor may contain steam.
  • the reaction temperature is preferably at least 270 ° C, more preferably at least 300 ° C, from the viewpoint that the methanol synthesis catalyst component and the zeolite catalyst component exhibit sufficiently higher activities, respectively.
  • the reaction temperature is preferably 400 ° C or lower, more preferably 380 ° C or lower, in view of the limit temperature for use of the catalyst, the regulation of equilibrium, and the ease of removing and recovering the reaction heat. .
  • the reaction pressure is set to 1 because the methanol synthesis catalyst component shows a sufficiently high activity. It is preferably at least MPa, more preferably at least 2 MPa. The reaction pressure is preferably 1 OMPa or less, more preferably 5 MPa or less, from the viewpoint of economy.
  • Gas space velocity in terms of economic efficiency, 5 0 O hr-1 or more preferably, 2 0 0 0 hr one 1 or more is more preferable. Further, the gas hourly space velocity is preferably 100 Ohr-11 or less from the viewpoint that the methanol synthesis catalyst component and the zeolite catalyst component each provide a contact time showing a sufficiently high conversion. , 5 0 0 O hr one 1 or less is not more preferable.
  • the gas sent to the reactor can be split and sent to the reactor, thereby controlling the reaction temperature.
  • the reaction can be carried out in a fixed bed, a fluidized bed, a moving bed or the like, but it is preferable to select from both the control of the reaction temperature and the method for regenerating the catalyst.
  • fixed beds include quench-type reactors such as internal multi-stage quench type, multi-tube type reactors, multi-stage type reactors including multiple heat exchangers, multi-stage cooling radial type single-hole type, and double-tube heat type.
  • Other reactors such as an exchange type, a cooling coil built-in type, and a mixed flow type can be used.
  • the catalyst for producing lower paraffins can be diluted with silica, alumina or the like or an inert and stable heat conductor for the purpose of controlling the temperature.
  • the catalyst for producing lower paraffin can be used by coating it on the surface of a heat exchanger for the purpose of controlling temperature.
  • the main component of the contained hydrocarbon is propane or butane.
  • propane and butane the main component of the contained hydrocarbon.
  • the total content of propane and pentane in the lower paraffin-containing gas is as high as possible.
  • the total content of propane and butane is 50 mol% or more, more preferably 60 mol% or more, and even 70 mol% or more (including 100 mol%) of the contained hydrocarbon.
  • a lower paraffin-containing gas can be obtained.
  • the lower paraffin-containing gas obtained in the lower paraffin production step preferably contains more propane than butane from the viewpoint of flammability and vapor pressure characteristics.
  • the content of propane is 50 mol% or more, more preferably 55 mol% or more, and even 60 mol% or more (including 100 mol%) of lower hydrocarbons contained. Gas can be obtained.
  • the lower paraffin-containing gas obtained in the lower paraffin production step contains a low-boiling component having a boiling point or a sublimation point lower than that of propane.
  • low boiling components include by-products ethane, methane, and ethylene.
  • the low-boiling components include carbon dioxide generated by the shift reaction, and unreacted raw materials such as hydrogen and carbon monoxide.
  • the low boiling point component contained may be one kind or two or more kinds.
  • a low-paraffin-containing gas having a low content of low-boiling components can be obtained.
  • low-paraffin-containing gas containing 75% or less, more preferably 70% or less, and even 60% or less (excluding ⁇ %) of low-boiling components excluding hydrogen is based on carbon.
  • a lower paraffin-containing gas having a hydrogen content of 40 mol% or less, or even 38 mol% or less (excluding 0 mol%) can be obtained.
  • high-boiling components that are substances with a boiling point higher than that of butane, such as high-boiling paraffin gas, are separated from lower-paraffin-containing gas. May be. Separation of the high boiling component can be carried out by a known method.
  • Separation of low-boiling components can be performed by a known method such as gas-liquid separation, absorption separation, or distillation. More specifically, gas-liquid separation or absorption separation at pressurized room temperature, cooling Alternatively, it can be performed by gas-liquid separation, absorption separation, or a combination thereof. Further, it can be carried out by membrane separation or adsorption separation, and can also be carried out by combining these with gas-liquid separation, absorption separation, and distillation.
  • gas recovery processes commonly used in refineries (“Petroleum Refining Process"
  • an absorption process in which a liquefied fossil oil gas containing propane or butane as a main component is absorbed by a high-boiling paraffin gas having a boiling point higher than that of butane or an absorbent such as gasoline is preferable.
  • the total content of propane and butane in the LPG thus produced can be at least 90 mol%, and more preferably at least 95 mol% (including 100 mol%). Further, the content of propane in the LPG to be produced can be 50 mol% or more, and further, 60 mol% or more (including 100 mol%). According to the present invention, it is possible to produce LPG having a composition suitable for propane gas widely used as a fuel for home and business use.
  • the low-boiling components separated from the lower paraffin-containing gas in the above separation process are recycled as raw materials for the synthesis gas production process (reforming process).
  • the low-boiling components separated from the lower paraffin-containing gas include substances that can be reused as raw materials in the synthesis gas production process, such as methane, ethane, and ethylene. Furthermore, carbon dioxide contained in the low-boiling components can be returned to the synthesis gas by Rei_0 2 Li follower one timing reaction. Further, the low-boiling components include unreacted raw materials such as hydrogen and carbon monoxide. Therefore, the low-boiling components separated from the lower paraffin-containing gas are recycled to the synthesis gas production process.
  • All the low-boiling components separated from the lower paraffin-containing gas may be recycled to the synthesis gas production process, or a part may be extracted out of the system and the rest may be recycled to the synthesis gas production process .
  • Low boiling components can be recycled to the synthesis gas production process by separating only the desired components.
  • FIG. 1 shows an example of an LPG manufacturing apparatus suitable for carrying out the LPG manufacturing method of the present invention.
  • methane is supplied to the reformer 1 via the lines 11 and 12 as a carbon-containing raw material.
  • steam is supplied to the line 12 to perform steam reforming.
  • a low-boiling component having a boiling point or a sublimation point lower than that of propane is supplied from the separator 3 to the line 12 via the recycle line 16.
  • a reforming catalyst 1a is provided in the reformer 1.
  • the reformer 1 includes a heating means (not shown) for supplying heat required for reforming.
  • methane is reformed in the presence of the reforming catalyst 1a to obtain a synthesis gas containing hydrogen, carbon monoxide, carbon dioxide, and steam.
  • the synthesis gas thus obtained is supplied to the reactor 2 via the line 13.
  • the reactor 2 is provided with a lower paraffin production catalyst 2a.
  • a lower paraffin-containing gas containing ethane, propane and butane is synthesized from the synthesis gas in the presence of the lower paraffin production catalyst 2a.
  • the synthesized lower paraffin-containing gas is supplied to a separator 3 as a distillation column via a line 14. Then, a substance having a boiling point higher than the boiling point of propane, that is, LPG as a product, is obtained from the bottom of the column by pressure distillation at room temperature, and a substance having a boiling point or sublimation point lower than the boiling point of propane from the top of the column, that is, a low boiling point Components are obtained as residual gas Can be In this way, a product LPG is obtained from the line 15. On the other hand, the residual gas (low-boiling components) obtained from the top of the tower is recycled to the reformer 1 by the recycling line 16.
  • the LPG manufacturing apparatus is provided with a booster, a heat exchanger, a valve, an instrumentation control device, and the like as necessary.
  • a commercially available Cu—Zn based methanol synthesis catalyst (manufactured by Nippon Suede Hemi Co., Ltd.), which was mechanically powdered, was used as the methanol synthesis catalyst component.
  • Zeorai preparative catalysts component S i 0 2 / A 1 2 0 3 molar ratio was prepared pro ton Z SM- 5 peptidase Orai preparative powder 14.5. Then, the methanol synthesis catalyst component and the zeolite catalyst component are uniformly mixed in the same amount on a mass basis, press-molded and sized, and then reduced in a hydrogen stream at 300 ° C for 3 hours to obtain a lower grade. A catalyst for paraffin production was obtained.
  • the prepared catalyst was charged into a reaction tube, and a raw material gas having a composition of 62.0 mol% of hydrogen, 31.0 mol% of carbon monoxide, 5.0 mol% of carbon dioxide, and 2.0 mol% of methane was supplied. It was distributed.
  • the reaction conditions were as follows: reaction temperature 325 ° C, reaction pressure 2. OMP a ⁇ gas space velocity 3000 hr- 1 .
  • reaction gas After gas-liquid separation of the reaction gas from the production of LPG (production of lower paraffin), the reaction gas is dried with a molecular sieve, and then methane is added to an octane solution maintained at around 0 ° C.
  • a low-boiling gas having a composition of 7 mol%, ethylene and ethylene 1.2 mol%, carbon dioxide 21.1 mol%, unreacted carbon monoxide 12.0 mol% and hydrogen 62.0 mol%. Minutes.
  • the separated low boiling point component was pressurized to 2.5 MPa by a compressor and fed into the synthesis gas production process as 67 mol% of the raw material gas.
  • the raw material gas having the composition of low boiling point recycled gas from the LPG production process of 67.0 mol%, natural gas of 14.7 mol%, steam of 14.8 mol%, and carbon dioxide of 3.5 mol% was obtained from WO 98 /
  • the catalyst was prepared in advance in a stream of hydrogen in an externally heated reaction tube type apparatus filled with a Ru / sintered low surface area magnesia catalyst prepared according to Catalyst Preparation Example 9 of 46524, 900. After performing a reduction treatment with C for 1 hr, the reaction temperature is 870 ° C, the reaction pressure is 2.
  • the obtained synthesis gas can be used as a raw material in the production of lower paraffin.
  • the reforming catalyst (synthesis gas production catalyst) and the lower paraffin production catalyst used were prepared as follows.
  • Magnesium oxide calcined at 920 ° C for 2 hours in air was sized to 0.27 to 0.75 mm, and Ru was supported by impregnation.
  • the Ru-impregnated body was obtained by repeatedly dropping an aqueous solution of ruthenium (III) chloride hydrate (Ru content: 1.0% by weight) into calcined MgO little by little and shaking. And this Ru impregnated body After drying in air at 120 ° C for 2.5 hours, it was calcined in air at 920 ° C for 2 hours to obtain a reforming catalyst (1 ⁇ 11 supported ⁇ [0 catalyst).
  • Ru-supporting MgO catalyst 1. 5x 10- 3 g supported amount of Ru is relative to MgO 1 g, is 0. 06mo 1% by mo 1 terms, a surface area of 9. 6 m 2 / g Atsushi.
  • a methanol synthesis catalyst component As a methanol synthesis catalyst component, a commercially available Cu—Zn-based methanol synthesis catalyst (manufactured by Nippon Sudohemi Co., Ltd.) that was mechanically powdered was used.
  • the Zeorai preparative catalyst Ingredients S i0 2 / Al 2 0 3 molar ratio which is separately prepared proton type Z SM- 5 Zeorai bets 14. 5 (pore diameter: minor 0. 53 nm, major axis 56 nm) powder Using.
  • This methanol synthesis catalyst component and the same weight of zeolite catalyst component are uniformly mixed, press-molded and sized, and then reduced at 300 ° C for 3 hours in a hydrogen stream to obtain a lower paraffin production catalyst. Obtained.
  • reaction temperature 870 ° C 7.8 mol% of natural gas, 14.3 mol% of steam, 3.9 mol% of carbon dioxide, and 74 mol% of low-boiling components separated from the lower paraffin-containing gas described below and recycled as a raw material for syngas production was passed through the reforming catalyst layer.
  • LMPA was GHS V (gas space velocity) 2000 hr 1.
  • the synthesis gas obtained in the synthesis gas production process was passed through the lower paraffin production catalyst layer.
  • the reaction conditions were a reaction temperature of 325 ° C, a reaction pressure of 2.0 MPa, and GHS V3000 hr- 1 .
  • the lower paraffin-containing gas After gas-liquid separation of the lower paraffin-containing gas obtained in the lower paraffin production process, the lower paraffin-containing gas is dried by a molecular sieve and bubbled into an octane solution maintained at about 0 ° C.
  • a gas consisting of 0.6 mol% of methane, 0.8 mol% of ethane and ethylene, 39 mol% of carbon dioxide, 22 mol% of unreacted carbon monoxide and 38 mol% of hydrogen was separated as a low-boiling component, and LPG was separated.
  • LPG Low-boiling component
  • the separated low-boiling components were pressurized to 2.5 MPa by a compressor and then recycled as raw materials for the synthesis gas production process.
  • the raw material gas composition is separated from natural gas 14.7 mol%, steam 14.8 mol%, carbon dioxide 3.5 mol%, and gas containing lower paraffin, and recycled as a raw material for syngas production.
  • IMP a, GHSV of 2000 hr " 1 , 58 mol% of hydrogen, 29 mol% of carbon monoxide, 6 mol of carbon dioxide % Of methane and 7 mol% of methane, and LPG was produced in the same manner as in Example 1 except that a lower paraffin-containing gas was produced from this synthesis gas.
  • the product in the lower paraffin production process (lower paraffin-containing gas before the separation of low-boiling components) was analyzed by gas chromatography.
  • the conversion of carbon monoxide was 73%.
  • the conversion to shift reaction to methane was 34%, and the conversion to hydrocarbons was 37%.
  • Propane and butane accounted for 78% of the generated hydrocarbons on a carbon basis, and the proportion of propane and butane was 40% for propane and 60% for butane on a carbon basis.
  • the content of low-boiling components (excluding hydrogen) in the gas containing lower paraffins was 69% on a carbon basis.
  • the composition of low-boiling components separated from the lower paraffin-containing gas was 0.7 mol% of methane, 1.2 mol% of ethylene and ethylene, 15 mol% of carbon dioxide, The content was 10 mol% of carbon monoxide and 73 mol% of hydrogen.
  • Comparative Example 1 the amount of low boiling components contained in the lower paraffin-containing gas produced from the synthesis gas was larger than that in Example 1. Specifically, in Comparative Example 1, the content of low-boiling components (carbon-containing low-boiling components) other than hydrogen in the lower paraffin-containing gas was the same as in Example 1, but the content of lower paraffin-containing gas was lower. Has a large hydrogen content. In Comparative Example 1, the entire low-boiling component separated from the lower paraffin-containing gas could not be recycled as a raw material in the synthesis gas production process. Available items
  • propane and / or butane can be produced from carbon-containing raw materials such as natural gas or synthesis gas with high selectivity.
  • LPG having a low concentration of components having 2 or less carbon atoms and a high concentration of propane and / or butane from a carbon-containing raw material such as natural gas or a synthesis gas.
  • a carbon-containing raw material such as natural gas or a synthesis gas.

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Abstract

Un gaz de synthèse contenant du monoxyde de carbone et de l'hydrogène est produit à partir d'une matière contenant du carbone, tel que du gaz naturel, au moins un type sélectionné dans le groupe comprenant du H2O, du O2 et du CO2, et un composant recyclé à point d'ébullition bas séparé d'un gaz contenant de la paraffine inférieure. Un gaz contenant de la paraffine inférieure contenant le composant à point d'ébullition bas ayant un point d'ébullition ou un point de sublimation plus bas que le point d'ébullition du propane est produit à partir du gaz de synthèse en présence d'un catalyseur. Les hydrocarbures contenus dans le gaz contenant de la paraffine inférieure sont principalement composés de propane ou de butane. Un GPL contenant principalement du propane ou du butane est obtenu par séparation du composant à point d'ébullition bas du gaz contenant de la paraffine inférieure, et le composant à point d'ébullition bas séparé est recyclé pour la production de gaz de synthèse.
PCT/JP2004/002168 2003-02-26 2004-02-25 Procede de production de gaz de petrole liquefie contenant principalement du propane ou du butane Ceased WO2004076600A1 (fr)

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JP2003049587A JP2006182646A (ja) 2003-02-26 2003-02-26 プロパンまたはブタンを主成分とする液化石油ガスの製造方法
JP2003-049587 2003-02-26
JP2003356490A JP2006143752A (ja) 2003-10-16 2003-10-16 プロパンまたはブタンを主成分とする液化石油ガスの製造方法
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006016583A1 (fr) * 2004-08-11 2006-02-16 Japan Gas Synthesize, Ltd. Méthode de production de gaz de pétrole liquefié
WO2006030828A1 (fr) * 2004-09-15 2006-03-23 Japan Gas Synthesize, Ltd. Procede de production de gaz de petrole liquefie
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WO2023039426A1 (fr) * 2021-09-09 2023-03-16 Gas Technology Institute Production d'hydrocarbures de type gaz de pétrole liquéfié (gpl) à partir de charges contenant du dioxyde de carbone

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006016583A1 (fr) * 2004-08-11 2006-02-16 Japan Gas Synthesize, Ltd. Méthode de production de gaz de pétrole liquefié
WO2006030828A1 (fr) * 2004-09-15 2006-03-23 Japan Gas Synthesize, Ltd. Procede de production de gaz de petrole liquefie
WO2006070516A1 (fr) * 2004-12-28 2006-07-06 Japan Gas Synthesize, Ltd. Procede de production de gaz de petrole liquefie
WO2023039426A1 (fr) * 2021-09-09 2023-03-16 Gas Technology Institute Production d'hydrocarbures de type gaz de pétrole liquéfié (gpl) à partir de charges contenant du dioxyde de carbone

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