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
  • C01B3/384—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 the catalyst being continuously externally heated
• • 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
  • C01B3/382—Multi-step processes
• • 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
  • C01B3/386—Catalytic partial combustion
• • 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
  • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
  • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
• • 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
  • C01B2203/1205—Composition of the feed
  • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
  • C01B2203/1235—Hydrocarbons
  • C01B2203/1247—Higher hydrocarbons
• • 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
  • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series

Definitions

• the present invention relates to a method and an apparatus for producing a synthesis gas containing carbon monoxide and hydrogen by catalytic partial oxidation of a raw gas containing light hydrocarbons such as natural gas, and carbon in the catalytic partial oxidation step. This is designed to suppress self-combustion of hydrocarbons of number 2 or more.
• CPO catalytic partial oxidation method
• oxygen is added to a raw material gas such as natural gas containing light hydrocarbons such as methane, and then fed into the reactor, and nickel, ruthenium, rhodium, platinum, etc. in the reactor are added.
• a raw material gas such as natural gas containing light hydrocarbons such as methane
• nickel, ruthenium, rhodium, platinum, etc. in the reactor are added.
• This is a method for producing synthesis gas by converting light hydrocarbons such as methane and ethane into carbon monoxide and hydrogen by the action of this catalyst (see the following chemical formula).
• the source gas such as natural gas usually contains hydrocarbons having 2 or more carbon atoms such as ethane, propane, and butane. Many. Since these hydrocarbons having 2 or more carbon atoms have a lower ignition temperature than methane, they tend to burn when they are mixed with oxygen and subjected to catalytic oxidation. For this reason, the oxygen mixer located upstream from the catalytic layer of the catalytic partial oxidation reactor is a significant obstacle to safety in the design of a device that is likely to self-combust in the preheating section.
• WO98Z49095 has a high line that does not self-combust hydrocarbon gas and oxygen gas by attaching an injector equipped with a plurality of mixing nozzles to the inlet of the catalytic partial acid-sodium reactor.
• An invention is disclosed that mixes under fast conditions and feeds to the catalyst layer of the partial oxidation reactor.
• Patent Document 1 Pamphlet of International Publication No. WO98Z49095
• the problem in the present invention is to convert hydrocarbons having 2 or more carbon atoms in the raw material gas when producing synthesis gas from the raw material gas containing light hydrocarbons such as natural gas by the catalytic partial oxidation method.
• the purpose is to prevent the self-combustion caused.
• a first aspect of the present invention is a process for producing a synthesis gas containing a raw material gas power containing light hydrocarbons, carbonic acid and carbon, and adding low temperature steam reforming to the source gas by adding steam. And a process for converting a hydrocarbon having 2 or more carbon atoms in the raw material gas into methane, and a process for synthesizing partial synthesis by adding oxygen after the low temperature steam reforming.
• the pressure in the first reactor for low-temperature steam reforming is normal pressure to 8 MPa
• the inlet temperature is 200 to 500 ° C
• the outlet temperature is 300 to 600 ° C
• the amount of added calories may be 0.1 to 3.0 moles per mole of carbon in the source gas.
• the inlet temperature in the second reactor for catalytic partial oxidation is 300 ° C or higher, and the oxygen loading is 1 mol of carbon in the gas. As opposed to 0.2 mol or more.
• the raw material gas may be natural gas, naphtha or liquid petroleum gas.
• a second aspect of the present invention is a carbonization having 2 or more carbon atoms in a raw material gas containing light hydrocarbons.
• a synthesis gas comprising a low-temperature steam reforming reactor that converts hydrogen to methane, and a catalytic partial oxidation reactor that uses the product gas from the low-temperature steam reforming reactor as a synthesis gas containing carbon monoxide and hydrogen. It is a manufacturing apparatus.
• the synthesis gas production apparatus may include a heat exchanger that is provided between the low-temperature steam reforming reactor and the catalytic partial oxidation reactor and that heats the gas from the low-temperature steam reforming reactor. Yes.
• the syngas production apparatus is provided between the desulfurization reactor provided in the front stage of the low-temperature steam reforming reactor and the desulfurization reactor and the low-temperature steam reforming reactor. With heat exchange that heats the gas.
• hydrocarbons having 2 or more carbon atoms contained in light hydrocarbons such as natural gas and naphtha are converted to methane by low-temperature steam reforming. For this reason, the self-combustion of the raw material gas does not occur in the subsequent contact partial oxidation process.
• the temperature of the gas sent to the catalytic partial oxidation reactor can be increased by about 200 ° C compared to the conventional method, so the amount of oxygen required for the catalytic partial oxidation reaction can be reduced. .
• FIG. 1 is a schematic configuration diagram showing an example of a synthesis gas production apparatus according to the present invention.
• FIG. 1 is a schematic configuration diagram showing an example of the synthesis gas production apparatus of the present invention.
• Source gas containing light hydrocarbons such as natural gas is sent from pipe 1 to desulfurization reactor 2 Be turned. At this time, hydrogen for hydrogenation is simultaneously supplied from the pipe 3 to the desulfurization reactor 2.
• an adsorber or the like that reduces sulfur compound in the raw material gas with hydrogen to form hydrogen sulfide, and adsorbs and removes this sulfur hydrogen is used.
• the desulfurized raw material gas is led out from the pipe 4 and the water vapor from the pipe 5 is mixed therewith and sent to the first heat exchanger 6 where it is heated to 200 to 500 ° C. Then, it is sent to the low-temperature steam reforming reactor 8 through the pipe 7.
• the low-temperature steam reforming reactor 8 includes a catalyst bed filled with a catalyst formed by supporting a metal such as nickel and Z or ruthenium on a carrier such as aluminum oxide.
• a catalyst formed by supporting a metal such as nickel and Z or ruthenium on a carrier such as aluminum oxide.
• hydrocarbons having 2 or more carbon atoms in the raw material gas are converted into methane by reacting with water vapor by the action of the catalyst, and oxygen is by-produced as a by-product.
• the operating conditions in the low-temperature steam reforming reactor 8 are that the pressure is normal pressure to 8 MPa, preferably 1 to 4 MPa, and the artificial temperature force is 200 to 500 ° C, preferably 300 to 400 ° C.
• the outlet temperature is 300 to 600 ° C, preferably 400 to 550 ° C, and the amount of water vapor added is 0.1 to 3.0 monolayers, preferably 0 to one carbon monolayer in the raw material gas. 3 to 1.0 Mono is set.
• the product gas containing methane and oxygen from the low-temperature steam reforming reactor 8 is sent to the second heat exchanger ⁇ 11 together with the steam from the tube 9 to the tube 10, where it is heated to 300 to 550 ° C. Is sent to the mixer 12.
• the mixer 12 is separately supplied with oxygen from a pipe 13 where oxygen is mixed with the mixed gas of the product gas and water vapor.
• the steam added here prevents coking of the catalyst in the catalytic partial oxidation reactor 15.
• the amount of oxygen added in the mixer 12 is 0.2 to 1.0 mol, preferably as oxygen content at the outlet of the mixer 12 with respect to 1 mol of carbon in the gas. Is adjusted to be in the range of 0.3 to 0.8 mol, and can be higher than the oxygen content in the conventional method. This is because self-combustion hardly occurs in the catalytic partial oxidation reaction step in the next stage.
• the gas from the mixer 12 is fed into the catalytic partial oxidation reactor 15 via the tube 14.
• the catalytic partial oxidation reactor 15 is filled with a catalyst in which one or more metals selected from the group force consisting of nickel, ruthenium, rhodium and platinum are supported on a carrier such as alumina or silica. Provide a catalyst bed.
• a catalyst in which one or more metals selected from the group force consisting of nickel, ruthenium, rhodium and platinum are supported on a carrier such as alumina or silica.
• a carrier such as alumina or silica.
• Methane and oxygen react with each other to obtain a synthesis gas containing carbon monoxide and hydrogen.
• the operating conditions in the catalytic partial oxidation reactor 15 are that the pressure is normal pressure to 8 MPa, the inlet temperature force S300 to 550 ° C, and the outlet temperature 700 to 1200 ° C.
• the synthesis gas produced in the catalytic partial oxidation reactor 15 is led out from the pipe 16 and sent to the next process.
• a low-temperature water steam reforming reactor 8 is provided upstream of the catalytic partial oxidation reactor 15, and in the low-temperature steam reforming reactor 8,
• the hydrocarbons having 2 or more carbon atoms are converted into methane in advance, and this is led to the catalytic partial oxidation reactor 15.
• hydrocarbons having 2 or more carbon atoms do not flow into the catalytic partial oxidation reactor 15, so there are 2 carbon atoms between the mixer 12 and the upstream of the catalyst layer of the catalytic partial acid reactor 15. Self-combustion of the above hydrocarbons can be suppressed.
• Table 1 shows an example of gas composition change at the inlet and outlet of the low-temperature steam reforming reactor 8 using natural gas as a raw material as an example. It can be seen that the above ethane, propane and the like are hardly contained and converted into a composition.
• the ignition temperature of the product gas from the low-temperature steam reforming reactor 8 is increased, the temperature of the gas fed into the catalytic partial oxidation reactor 15 can be increased. For this reason, the amount of oxygen required for the contact partial oxidation reaction can be reduced.
• the ignition temperature of the raw material gas at the inlet of the low temperature steam reforming reactor 8 is about 250 to 350 ° C. depending on its composition, but the ignition temperature of the product gas at the outlet is about 450 to 350 ° C. 530 ° C.
• the catalyst used in the low temperature steam reforming reaction may be a relatively inexpensive one such as nickel. By using a large amount of this inexpensive catalyst to collect residual sulfur in the raw material gas, it is possible to reduce deterioration of the catalyst in the catalytic partial oxidation reactor 15 due to sulfur.
• methane: ethane: propane: normal butane: isobutane: hydrogen 87: 7: 2. 8: 0. 6: 0. 6: 2 (mol 0 / 0 )) 1.
• steam was mixed at 0.95 kgZ, heated to 300 ° C with a heater, mixed with heated oxygen, and fed to the catalytic partial oxidation reactor .
• the temperature of the mixed gas in the oxygen mixer was about 290 ° C.
• This catalytic partial oxidation reactor is a tubular reactor having a length of lm and an inner diameter of 22 mm, and inside thereof, a catalyst bed having a catalytic force in which rhodium and nickel are supported on alumina is formed. A space with a length of 10 cm is formed in the upper part, and this space is filled with ceramic balls with a diameter of 3 mm.
• the temperature of the steam mixed natural gas and the temperature of the added oxygen are lowered so that the temperature of the mixed gas in the oxygen mixer becomes 250 ° C, and oxygen is gradually supplied. It was introduced into a catalytic partial oxidation reactor. Even with 0.6 mol of oxygen per 1 mol of carbon in natural gas, self-combustion did not occur in the ceramic ball packed part on the catalyst bed, and the original catalytic partial oxidation reaction could be maintained.
• the ratio of hydrogen to carbon monoxide is about 2.1, which is suitable as a synthesis gas feedstock.
• the low-temperature steam reforming reactor is a tubular reactor with a length of 2 m and an inner diameter of 50 mm, and inside it is formed a catalyst bed consisting of a catalyst with nickel supported on alumina! Speak.
• the reformed gas was heated with a second heater, and heated oxygen was added to the contact partial oxidation reactor in an amount of 0.53 mol per mol of carbon in the gas.
• the temperature of the gas in the oxygen mixer was 500 ° C, but no self-combustion occurred between the oxygen mixer and the upstream side of the catalytic partial oxidation reactor, and the predetermined catalytic partial oxidation reaction was maintained. It was done.
• the catalyst of the low-temperature steam reforming reactor was replaced with a catalyst for catalytic partial oxidation, changed to a low-temperature partial oxidation reactor, and oxygen could be supplied immediately before the steam mixed natural gas heater.
• the device configuration was such that the catalytic partial oxidation reaction was performed in two stages, low and high.
• the total amount of synthesis gas hydrogen and carbon monoxide was 5. INm 3 Z.
• the ratio of hydrogen to carbon monoxide is about 2.1, which is suitable for synthesis gas feedstock. there were.
• the present invention can also be applied to the production of synthesis gas such as naphtha and LPG (liquid petroleum gas).
• synthesis gas such as naphtha and LPG (liquid petroleum gas).
• the desulfurization reactor 2, the first heat exchanger 6, the second heat exchanger 11, and the mixer 12 in the apparatus shown in FIG. 1 are not essential and can be omitted.
• the catalytic partial oxidation reactor may be a multistage with two or more stages instead of a single stage, or it may be a reactor that combines catalytic partial oxidation reaction and autothermal reforming reaction (ATR)! / ,.

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• 2004
  • 2004-10-13 JP JP2004298971A patent/JP4781652B2/ja not_active Expired - Fee Related
• 2005
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• 2007
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