US3882636A - Two-stage steam reforming process of hydrocarbons - Google Patents

Two-stage steam reforming process of hydrocarbons Download PDF

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US3882636A
US3882636A US295120A US29512072A US3882636A US 3882636 A US3882636 A US 3882636A US 295120 A US295120 A US 295120A US 29512072 A US29512072 A US 29512072A US 3882636 A US3882636 A US 3882636A
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reaction
reaction zone
catalyst
reforming
steam
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US295120A
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English (en)
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Akira Horie
Seiichi Matsuoka
Kenzo Yamamoto
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JGC Corp
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Japan Gasoline Co Ltd
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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
    • 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
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/26—Fuel gas

Definitions

  • ABSTRACT A process of producing a gas rich in methane by subjecting hydrocarbons having at least two carbon atoms per molecule to steam reforming in two stages.
  • a two-stage steam reforming process of said hydrocarbons which is characterized by the steps: supplying a mixture consisting of said feed hydrocarbon and steam as pre-heated at a temperature in the range of from 350 to 550C to the first reaction zone charged with nickel catalyst to thereby effect a reforming reaction adiabatically to the extent of leaving some hydrocarbon substantially unreacted; introducing the mixture gas flowing out of the first reaction zone, that is, the mixture gas substantially comprising the reaction product gas arising from the first-stage reforming reaction, the unreacted hydrocarbon and the unreacted steam, and falling short of the state of so-called equilibrium, into a heater to thereby heat said mixture gas; and supplying the thus heated mixture gas to the second reaction zone charged with nickel catalyst to thereby effect a reforming reaction adiabatically again; through which said feed hydrocarbon is completely converted into a methane-rich gas in the state of so-called equilibrium.
  • the present invention relates to a process of producing a gas rich in methane by effecting the steam reforming reaction of hydrocarbons in two stages.
  • Japanese Patent Publication No. 817/1971 As to the cause of said deterioration of the activity of the catalyst, a view attributing it to a very thin coating layer of polymer which might be formed on the surface of the catalyst by the product arising from decomposition of the feed hydrocarbon has been expressed in Japanese Patent Publication No. 817/1971, (U.S. Pat. No. 3,459,520) etc. Based on this view, said Japanese Patent Publication No. 817/1971 has proposed a process for preventing the above mentioned deterioration of the catalyst by circulating a part of the hot reacted gas flowing out of the catalyst bed, as it is, so as to mix with the mixture of the vapor of feed hydrocarbon and steam before it passes through the nickel catalyst bed.
  • U.S. Pat. No. 3,441,395 has proposed a process of producing combustible gases having a relatively low calorific value, which comprises the steps: supplying a mixture of the feed hydrocarbon and steam to the first gasification stage charged with nickel catalyst; adiabatically effecting the reforming reaction at a temperature below 600C so as to convert said feed hydrocarbon completely; introducing the product gas arising from the foregoing reforming reaction into a fired preheater to subject it to heating therein; and supplying the thus preheated gas to the second reforming stage charged with the reforming catalyst to thereby effect the reforming reaction for decomposing methane produced in the first gasification stage by applying a temperature in the range of from 620 to 800C.
  • the present invention has been achieved as a result of investigation of the steam reforming reaction of hydrocarbons from the viewpoint of chemical equilibrium and is intended to provide a two-stage steam reforming process which renders it possible to continue a smooth operation of the apparatus extending over a long period of time.
  • FIG. 1 is a graph illustrative of relation between the length of the catalyst bed (layer) employed for the conventional single-stage steam reforming process and the distribution of temperature as observed with the passage of time.
  • FIG. 2 shows graphs illustrative of the relation between the length of the catalyst bed employed for the two-stage steam reforming process in Example 1 embodying the present invention and the distribution of temperature as observed with the passage of time, wherein (a) shows one mode of said distribution in the first reaction zone and (b) shows one mode of said distribution in the second reaction zone.
  • FIG. 3 is a flow scheme diagrammatically representing one embodiment of the process according to the present invention, wherein the numeral reference 1 denotes a feed inlet, 2 denotes the first reaction zone, 2 denotes the first reaction zone for switchover, 3 denotes a heater, 4 denotes the second reaction zone, 5 denotes an outlet for the product gas, and V,, V V and V respectively denote valves.
  • the numeral reference 1 denotes a feed inlet
  • 2 denotes the first reaction zone
  • 2 denotes the first reaction zone for switchover
  • 3 denotes a heater
  • 4 denotes the second reaction zone
  • 5 denotes an outlet for the product gas
  • V, V V and V respectively denote valves.
  • the condition in which the steam reforming reaction of feed hydrocarbons has been completed is meant by the so-called equilibrium state, namely, said reaction resulting in the production of a gaseous mixture consisting of methane, hydrogen and oxides of carbon due to the complete conversion of feed hydrocarbons with steam.
  • the relation between the length of catalyst bed indicated by the abscissa and the temperature indicated by the axis of ordinate can be expressed by the curve 1 in FIG. 1.
  • This curve gradually changes to a curve having a widely depressed portion such as the curve 2 in FIG. 1 with the passage of time of the steam reforming reaction of hydrocarbon, and it becomes a curve having a flatly depressedportion such as the curve 3 in FIG. 1 with the passage.
  • a process wherein hydrogen is introduced into the steam reforming reaction system with the hydrocarbon and the exothermic reaction between the hydrocarbon and the supplied hydrogen to generate methane is effected simulutaneously with the aforementioned endothermic reaction to generate carbon monoxide, hydrogen, etc., to thereby minimize the lowering of the temperature in the reforming reaction zone.
  • a process comprising the steps that a fluid whose temperature has been lowered as a result of the endothermic reaction effected in the steam reforming reaction zone is temporarily taken out of the reaction system to elevate its temperature by means of a heater, and subsequently the thus treated fluid is again subjected to reforming reaction in the second reforming reaction zone, whereby the feed hydrocarbon is completely converted.
  • the present invention relates to the process (iii) in the foregoing.
  • Typical hydrocarbons having two or more carbon atoms per molecule to be subjected to the process according to the present invention include the exhaust gas arising from petroleum oil refining, LPG, light naphtha, heavy naphtha, kerosene, and the like.
  • the steam reforming reaction in the first reaction zone is adiabatically effected in the presence of a nickel catalyst under the reaction conditions of the molar ratio of steam per carbon atom of the feed hydrocarbon being 1.0 to 5.0, the inlet temperature being 350 to 550C and the pressure being to 100 Kglcm
  • This nickel catalyst is selected from among the conventional catalysts used in low-temperature steam reforming reaction. Suitable catalysts include those comprising the metals belonging to Group. VIII, the I I metals belonging to the left column in Group VII, the
  • This nickel catalyst is also applicable to the reforming reactioncarried out in the second reaction zone.
  • the catalyst charged in' the first reaction zone and thatin the second reaction zone are identical, but they maybe different from each other.
  • reaction in the firstreaction zone according to the process of the present invention is effected on the premise that it should be stopped while.
  • the steam reforming reaction of the feed hydrocarbon is short of attaining the state of so-called equilibrium
  • the quantity of i catalyst to be charged in thefirst reaction zone should be sufficient for attaining the conversion rate of the feed hydrocarbon to the extent of about 20. to 80% preferably 20 to 35%.
  • first reaction zone that is, the quantityof catalyst necessary for converting 20 to 80% of thefeed hydrocar-
  • the present invention proposes the provision of a reaction zone for switchover denoted by 2 in FIG. 3 disposed parallel with the first reaction zone denoted by 2 in FIG. 3.
  • a pair of the first reaction zones disposed parallel to each i other as above are alternately employed through operation of the relevant valve.
  • the feed hydrocarbon and steam supplied through the line 1 is introduced into the first reaction zone 2 through the opened valve V and is subjected to adiabatic 'steam reforming to the extent of conversion rate in the jected to steam reforming adiabatically.
  • saidfeed hydrocarbon is completely converted and is taken out through the line 5.
  • the first reaction zone 2 is charged with active catalyst and is employed alternately until the activity of the catalyst charged in the second reaction zone 4 deteriorates.
  • the feed hydrocarbon supplied through the line 1 is introduced into the first reaction zone 2' and subjected to adiabatic steam reforming at the aforementioned conversion rate again, so that a continuous operation extending over a long in the second reaction zone, it is required to be sufficient for effecting complete conversion of undecomposed feed hydrocarbon extending over a long period of time.
  • the second reaction zone with said catalyst it is desirable to charge the second reaction zone with said catalyst to the extent of 1 to 20 parts by weight per part by weight of the catalyst charged in the first reaction zone, namely, the weight ratio (W jF) of the charged catalyst in the second reaction zone to the feed hydrocarbon per hour being 1 to 20 times as much as that (W /F) of the charged catalyst in the first reaction zone to the feed hydrocarbon per hour.
  • the process of the present invention is intended to produce the methane-rich gas at the desired conversion rate byeffecting a steam reforming reaction of hydrocarbons in two stages, not in a single stage as in'the conventional process, and further minimizing the effect of the lowering of temperature of the catalyst bed within the steam reforming reaction zones for hydrocarbons by virtue of the provision of a heater to heat the reacted gas between the first reaction zone and second reaction zone.
  • the life span of the catalyst applied is about twice as long as that of the catalyst applied to the conventional process employing a single-stage reaction zone when the steam reforming reaction is effected under the same reaction conditions by employing the same catalyst in the same quantity. This is considered attributable to the avoidance of the lowering of temperature of the catalyst bed as shown by the curve 2 and curve 3 in FIG. 1 which is rendered possible by the present process.
  • the outlet temperature became 535C as shown in FIG. 1l.
  • the distribution of temperature in the nickel catalyst bed in the adiabatic reaction zone on this occasion was as shown in FIG. l, and, with the lapse of reaction time, the curve i changed to the curve 3 through the curve 2.
  • the content of the undecomposed hydrocarbon in the mixture gas flowing out of the first reaction zone showed a tendency toward gradual increase, though in small increments.
  • the mixture gas thus flowing out of the first reaction zone was introduced into a fired heater, whereby heat was supplied to the mixture gas at the rate of 14 Kcal per Kg of said gas.
  • the thus heated mixture gas was then introduced into the second reaction zone charged with 0.60 Kg of the same nickel catalyst as that charged in the first reaction zone and was again subjected to a steam reforming reaction adiabatically under the absolute pressure of 21 atm.
  • the outlet temperature ofthe second reaction zone on this occasion was 535C.
  • Table 2 the outlet temperature of duration of effective operation of steam reforming reaction 753 hrs. 1533 hrs.
  • the feed hydrocarbon was first mixed with steam at the rate of 4.0 mols of steam per carbon atom of hydrocarbon. Then, this mixture was introduced into the first reaction zone charged with 0.008 Kg of nickel at the inlet temperature of 510C. The applied pressure and mass velocity on this occasion were equal to those in Example 1 above. Next, the gas mixture flowing out of the first reaction zone was introduced into a fired heater, whereby heat was supplied to the mixture gas at the rate of 12 Kcal per Kg of said gas. The thus heated gas mixture was then introduced into the second reaction zone charged with 0.23 Kg of nickel catalyst and was again subjected to a steam reforming reaction adiabatically so as to attain the outlet temperature of 500C.
  • W /F 0.0401 to 022a wherein W, weight of charged catalyst F weight of supplied hydrocarbon per hour M mean average boiling point of feed hydrocarbons in C,
  • W and F are as defined above, to effect a second adiabatic reforming reaction of said heated reaction mixture to complete reaction of said feed hydrocarbon, thereby to produce a final gaseous product in which the carbon compounds present therein connsist essentially of CH.,, CO and CO said final gaseous product at the exit end of the second reforming reaction zone having a temperature in the range of 350 to 550C, and withdrawing said final gaseous product from said second reforming reaction zone.
  • hydrocarbons having two or more carbon atoms per molecule are selected from the group consisting of the off gas arising from a petroleum oil refinery, LPG, light naphtha, heavy naphtha and kerosene.
  • said first reaction zone consists of at least two reaction chambers j connected in parallel and in which said preheated gaseous mixture is supplied to one of said chambers until i the reaction of said feed hydrocarbon therein becomes less than 20%, then terminatingsupply of said preheated gaseous mixture to said one chamber and supplying it to another reaction chamber.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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US295120A 1971-10-07 1972-10-05 Two-stage steam reforming process of hydrocarbons Expired - Lifetime US3882636A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060008413A1 (en) * 2004-07-08 2006-01-12 Diwakar Garg Catalyst and process for improving the adiabatic steam-reforming of natural gas
US20070284287A1 (en) * 2006-04-27 2007-12-13 Freitag Christian Steam generation in steam reforming processes
US7365102B1 (en) 2007-02-26 2008-04-29 Delphi Technologies, Inc. Process for pre-reforming hydrocarbon fuels
US20100310949A1 (en) * 2009-06-03 2010-12-09 Air Products And Chemicals, Inc. Steam-Hydrocarbon Reforming with Reduced Carbon Dioxide Emissions
EP3018095A1 (en) 2014-11-10 2016-05-11 Air Products And Chemicals, Inc. Steam-hydrocarbon reforming process
WO2024028636A1 (en) 2022-08-02 2024-02-08 Air Products And Chemicals, Inc. Steam-hydrocarbon reforming with reduced carbon dioxide emissions

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5260974A (en) * 1975-11-13 1977-05-19 Daito Denzai Stripping machine for cover of cable
JPS5714025Y2 (ja) * 1976-12-03 1982-03-23
JPS5768712A (en) * 1980-10-13 1982-04-27 Kubota Ltd Apparatus for discharging and selecting dust in threshing machine

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2513022A (en) * 1944-10-05 1950-06-27 Phillips Petroleum Co Manufacture of hydrogen
US3395004A (en) * 1964-01-20 1968-07-30 Exxon Research Engineering Co Low-temperature, high-pressure, catalytic, partial conversion of naphtha hydrocarbons to hydrogen
US3429680A (en) * 1963-10-15 1969-02-25 Japan Gasoline Steam reforming of hydrocarbons
US3433609A (en) * 1964-03-13 1969-03-18 Gas Council Process for the production of gases containing methane from hydrocarbons
US3441395A (en) * 1964-06-08 1969-04-29 Gas Council Production of combustible gases
US3449099A (en) * 1964-02-10 1969-06-10 Exxon Research Engineering Co Process for reacting hydrocarbons and steam using spent catalyst for pretreating
US3450514A (en) * 1964-01-20 1969-06-17 Exxon Research Engineering Co Controlled conversion of light naphtha to town gas
US3467506A (en) * 1964-11-20 1969-09-16 Azote Office Nat Ind Catalytic conversion of liquid petroleum hydrocarbons
US3744981A (en) * 1971-04-26 1973-07-10 Universal Oil Prod Co Steam reforming of hydrocarbons

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2513022A (en) * 1944-10-05 1950-06-27 Phillips Petroleum Co Manufacture of hydrogen
US3429680A (en) * 1963-10-15 1969-02-25 Japan Gasoline Steam reforming of hydrocarbons
US3395004A (en) * 1964-01-20 1968-07-30 Exxon Research Engineering Co Low-temperature, high-pressure, catalytic, partial conversion of naphtha hydrocarbons to hydrogen
US3450514A (en) * 1964-01-20 1969-06-17 Exxon Research Engineering Co Controlled conversion of light naphtha to town gas
US3449099A (en) * 1964-02-10 1969-06-10 Exxon Research Engineering Co Process for reacting hydrocarbons and steam using spent catalyst for pretreating
US3433609A (en) * 1964-03-13 1969-03-18 Gas Council Process for the production of gases containing methane from hydrocarbons
US3441395A (en) * 1964-06-08 1969-04-29 Gas Council Production of combustible gases
US3467506A (en) * 1964-11-20 1969-09-16 Azote Office Nat Ind Catalytic conversion of liquid petroleum hydrocarbons
US3744981A (en) * 1971-04-26 1973-07-10 Universal Oil Prod Co Steam reforming of hydrocarbons

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7622058B2 (en) 2004-07-08 2009-11-24 Air Products And Chemicals, Inc. Catalyst for improving the adiabatic steam reforming of natural gas
US20060008413A1 (en) * 2004-07-08 2006-01-12 Diwakar Garg Catalyst and process for improving the adiabatic steam-reforming of natural gas
US7449167B2 (en) 2004-07-08 2008-11-11 Air Products And Chemicals, Inc. Catalyst and process for improving the adiabatic steam-reforming of natural gas
US20080300130A1 (en) * 2004-07-08 2008-12-04 Air Products And Chemicals, Inc. Catalyst For Improving The Adiabatic Steam Reforming Of Natural Gas
US7572363B2 (en) * 2006-04-27 2009-08-11 Linde Ag Steam generation in steam reforming processes
US20070284287A1 (en) * 2006-04-27 2007-12-13 Freitag Christian Steam generation in steam reforming processes
EP1967490A1 (en) 2007-02-26 2008-09-10 Delphi Technologies, Inc. Process for pre-reforming hydrocarbon fuels
US7365102B1 (en) 2007-02-26 2008-04-29 Delphi Technologies, Inc. Process for pre-reforming hydrocarbon fuels
US20100310949A1 (en) * 2009-06-03 2010-12-09 Air Products And Chemicals, Inc. Steam-Hydrocarbon Reforming with Reduced Carbon Dioxide Emissions
EP2266922A1 (en) 2009-06-03 2010-12-29 Air Products and Chemicals, Inc. Steam-Hydrocarbon Reforming with Reduced Carbon Dioxide Emissions
US8137422B2 (en) 2009-06-03 2012-03-20 Air Products And Chemicals, Inc. Steam-hydrocarbon reforming with reduced carbon dioxide emissions
EP3018095A1 (en) 2014-11-10 2016-05-11 Air Products And Chemicals, Inc. Steam-hydrocarbon reforming process
WO2024028636A1 (en) 2022-08-02 2024-02-08 Air Products And Chemicals, Inc. Steam-hydrocarbon reforming with reduced carbon dioxide emissions

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CA953502A (en) 1974-08-27
JPS518964B2 (ja) 1976-03-23
JPS4843702A (ja) 1973-06-23

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