WO1997037930A1 - Production d'un gaz de synthese a partir d'une charge premiere hydrocarbonee - Google Patents

Production d'un gaz de synthese a partir d'une charge premiere hydrocarbonee Download PDF

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WO1997037930A1
WO1997037930A1 PCT/GB1997/000900 GB9700900W WO9737930A1 WO 1997037930 A1 WO1997037930 A1 WO 1997037930A1 GB 9700900 W GB9700900 W GB 9700900W WO 9737930 A1 WO9737930 A1 WO 9737930A1
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temperature
catalyst
synthesis gas
range
gas
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PCT/GB1997/000900
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Stephen Bruce John Scott
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Bg Plc
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Priority to JP9535945A priority Critical patent/JP2000508286A/ja
Priority to AU22991/97A priority patent/AU713494B2/en
Priority to EP97915555A priority patent/EP0891295A1/fr
Publication of WO1997037930A1 publication Critical patent/WO1997037930A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/007—Mixed salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • 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
    • 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
    • C01B3/40—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 characterised by the catalyst
    • 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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/061—Methanol production
    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0872—Methods of cooling
    • C01B2203/0883—Methods of cooling by indirect heat exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1276—Mixing of different feed components
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • This invention relates to the production of synthesis gas from hydrocarbonaceous feedstock, more particularly from methane- containing feedstock, such as natural gas.
  • the invention also relates to the synthesis of products, such as methanol, hydrogen, synthetic crude oil and ammonia from the synthesis gas.
  • 'synthesis gas means a mixture essentially of hydrogen and carbon monoxide, which may also contain carbon dioxide and/or steam and/or methane.
  • One known method of producing synthesis gas comprises passing a mixture of steam and a methane-containing feedstock over a catalyst under conditions to cause steam reformation and the production of synthesis gas.
  • An object of the present invention is to employ partial oxidation of methane at relatively low temperatures to produce synthesis gas.
  • the invention provides a method of producing synthesis gas from a reactant gas mixture comprising methane, oxygen and optionally, steam and/or carbon dioxide, wherein the method comprises partially oxidising the methane by bringing the reactant gas mixture at a temperature in the range from 100°C to 950°C and at a pressure of up to 150 bar into contact with a first solid catalyst, which initiates the reaction, and conducting the reaction under substantially adiabatic conditions to produce the synthesis gas, the catalyst having been made by a method comprising intimately mixing a Feitknecht compound having the general formula:
  • Me 3+ is substantially completely Al 3+ or substantially Al 3+ and Cr 3+ ,
  • a 2 is either a single divalent anion or two monovalent anions.
  • x/y lies between 1.5/1 and 4/1
  • z/ (x+y) lies in the range 0.05 to 0.2
  • n/ (x+y) lies in the range 0.25 to 1.0, with a non-calcined alumino-silicate clay mineral and, at the same time and/or subsequently but prior to calcination, with at least one added stabilising additive for reducing silicon- species loss comprising an alkaline earth and/or rare earth metal compound, and, optionally, an alkali metal compound, and thereafter calcining the resulting mixture and subjecting the catalyst material to a reducing process to activate the catalyst .
  • the Feitnecht compound is formed by a co-precipitation comprising the bringing together of a mixed solution of water soluble salts of nickel and aluminium, and optionally chromium, and a precipitant solution.
  • the mixed salt solution may, for example, be a mixed nitrate solution.
  • the precipitant solution may be an alkaline solution such as sodium carbonate, bicarbonate or hydroxide; or potassium carbonate bicarbonate or hydroxide; or ammonium hydroxide or bicarbonate; or urea.
  • the Feitnecht compount may be co-precipitated in the presence of the clay mineral and the stabilising additive mixed in subsequent to the co-precipitation.
  • the Feitnecht compound may be co-precipitated in the absence of the clay mineral and the clay mineral and stabilising additive mixed in subsequent to the co-precipitation.
  • the resulting intimate mixture may be mixed with a cement binder prior to calcination of the mixture.
  • a cement binder may be added to the mixture after calcination.
  • the cement binder may be a high alumina cement binder. The presence of the cement binder further strengthens and gives stability to the catalyst.
  • the clay mineral may be a layer-structured phyllosilicate and/or pseudo-layer-structured, such as a smectite - for example, bentonite.
  • the bentonite for example, also further strengthens and gives stability to the catalyst.
  • Applicants UK patent specification no. 2222963 is directed to catalysts and catalyst precursors, and the method of preparing catalysts and catalyst precursors, employed in the present invention.
  • the synthesis gas may be produced at a temperature in the range from 500°C to 1000°C and at a pressure in the range from 1 to 40 bar.
  • the synthesis gas may, for example, be produced at a temperature in the range from about 500°C to about 900°C and at a pressure in the range from about l to about 10 bar. At these temperatures and pressures relatively good methane conversion occurs, i.e. there is relatively low methane slippage, and the resulting synthesis gas would, typically be used in fuel cells in which the resulting synthesis gas so produced, for example, would proceed to a shift reactor and then on for further processing without further reforming or compression of the synthesis gas being required. Such further processing may involve one or more techniques which are familiar to persons skilled in the art and are designed to remove carbon monoxide from the gas, such techniques, for example, including membrane separation, reverse methanation and selective oxidation.
  • the synthesis gas may instead, for example, be produced at a temperature in the range from about 700°C to about 1000°C and at a pressure in the range from about 5 to about 40 bar. Again, at these temperatures and pressures relatively good methane conversion occurs and the synthesis gas can be fed straight to a process operating at a medium pressure to produce a chemical product from such synthesis gas, without the synthesis gas being further reformed or compressed.
  • the synthesis gas may alternatively, for example, be produced at a temperature in the range from about 700°C to 1000°C and at a pressure in the range from about 25 to about 100 bar. Synthesis gas obtained at these temperatures and pressures may be employed in a process to obtain a second synthesis gas in order to overcome the problem described below.
  • Another object of the present invention is to produce synthesis gas at a relatively high temperature and pressure without the assistance of a make-up compressor or like gas compressing means, suitable for direct use in a high pressure downstream synthesis process.
  • the invention also provides a method of producing a second synthesis gas at relatively high temperature and pressure, the method comprising utilising as feed gas a first synthesis gas produced by the method as defined above at a temperature in the range from 700°C to 1000°C and at a pressure in the range from 25 to 100 bar, and comprising carbon monoxide, carbon dioxide, hydrogen, steam and unreacted methane, and without having been subjected to a compression stage subsequent to its production, the present method comprising adding oxygen to the first synthesis gas and causing partial oxidation of hitherto unreacted methane, by passing the reactant mixture of first synthesis gas and oxygen at a temperature in the range from 600°C to 900°C and at a pressure in the range from 25 to 100 bar over a solid catalyst, and conducting the further partial oxidation under substantially adiabatic conditions to produce the second synthesis gas at a relatively high temperature and pressure.
  • the above method thus involves two stages; the first being an initial partial oxidation stage, and the second being a further partial oxidation stage. It is envisaged that both stages in the above defined two stage or two step partial oxidation process can be carried out in adiabatic reactors which are of relatively simple design and relatively inexpensive to build and operate. In addition, metallurgical problems which constrain, for example, conventional fired tubular reformers can be removed and so the outlet temperature of the reactor can be increased substantially. This means that the pressure within the reactor can be increased without increasing methane slippage.
  • the resulting synthesis gas can be produced at high pressures to match those used in various current commercial processes, e.g. methanol manufacture and ammonia production, avoiding the use of expensive and energy intensive make-up gas compressors.
  • each of the methane-containing gas e.g. natural gas, the oxygen-containing gas (e.g. air) and, optionally, steam and/or carbon dioxide may pass to a mixer whereafter the gas mixture is passed to and heated in a common pre-heater.
  • the individual feed streams may pass to individual pre-heaters before being passed to a mixer to produce a mixture which ensures that the different gases are co-fed to the reactor. It will be appreciated that the residence time in the pre-heater must be kept shorter than the time which would result in auto-ignition of the reactant gas mixture.
  • the pre-heat temperature may be in the range from 100°C to 500°C, typically 200°C to 300°C. Advantages stem from being able to employ such low pre-heat temperatures. On the one hand the required size of the pre-heater can be reduced with an accompanying reduction in cost. At the same time, the time required for auto-ignition of the reactant mixture is increased. Applicants investigations have shown that highly active and very robust steam reforming catalysts have to be used in order for the reaction to be initiated and sustained at these low temperatures . Examples of suitable catalysts are set out below.
  • the 'cold' feed streams may be at ambient temperature and at a pressure of approximately 83 bar, whilst the heated gas mixture about to be passed over the catalyst may be at about 300°C and at a pressure of about 82 bar.
  • the product gas or synthesis gas emerging from the reaction zone containing the catalyst may be at a temperature of about 800°C and at a pressure of approximately 80.5 bar.
  • high space velocities will be employed - in the order of 50,000hr " ' (GHSV) - to give residence times of 0.1 to 10 seconds in the reactor containing the catalyst and 0.2 to 60 seconds for the passage through mixer, pre-heater(s) and reactor.
  • the residence time is such that the reactant gases are contacted with the catalyst for sufficient time to be brought to thermodynamic equilibrium at the outlet temperature or temperature of the synthesis gas emerging from the reaction zone.
  • reaction comprises the following three steps which may or may not happen simultaneously:
  • steam/methane and/or carbon dioxide/methane and oxygen/methane ratios can be varied within wide limits depending on the synthesis gas composition required at the outlet from the reaction zone.
  • the steam to methane and/or C0 2 to methane ratio can be varied from 0 to 10 depending on the outlet composition required.
  • the oxygen to methane ratio can be varied from 1 to 0.2.
  • a catalyst used in a method according to the invention is a catalyst used in a method according to the invention.
  • a solution containing 25.4kg of anhydrous sodium carbonate in 80 litres of deionised water was heated to 75°C.
  • 35.2kg of nickel nitrate hexahydrate, 13.6kg of aluminium nitrate nonahydrate and 1.6kg of chromium nitrate hexahydrate were dissolved in 80 litres of deionised water and heated to 75°C.
  • the precursor was precipitated by slow addition of the carbonates solution to the nitrates solution at a constant temperature of 75°C, both solutions being vigorously stirred throughout. After precipitation an aqueous slurry containing 1.7kg of kaolin and 0.8kg of magnesium oxide was added to the solution with stirring.
  • the slurry was filtered and the filter cake reslurried with 140 litres of deionised water at 60°C. The process of reslurrying followed by filtration was continued until the filtrate contained less than lOOppm by weight of sodium.
  • the resulting material was dried at 125°C and then calcined at 450°C for two hours to give the calcined precursor.
  • the calcined precursor was ground to pass a 850 micron sieve, then mixed with 4.95kg of Secar 71 high alumina cement, supplied by Larfarge, as a binder to improve strength. This powder was further blended with 2% by weight of graphite and then pelleted.
  • the pelleted catalyst was steamed at atmospheric pressure at 240°C for 16 hours and then soaked at room temperature in deionised water for over 12 hours. The pellets were dried at 125°C and then dipped in a solution containing 2% by weight of potassium hydroxide.
  • the composition of the final catalyst precursor is given in Table 1.
  • compositions analysted by inductively coupled plasma emission spectroscopy. Error in silicon content + or - 0.1 wt% .
  • reaction feed (10% methane, 49% carbon dioxide and 41% air GHSV 9,500) was introduced into the tube and the temperature raised incrementally to 300°C.
  • Catalysts 1 and 2 were able to initiate and maintain the reaction when the temperature reached 150°C.
  • Catalyst 3 did not initiate the reaction until the temperature reached 380°C.
  • the unreduced version of catalyst 1, i.e. catalyst 4 did not initiate the reaction below 400°C.
  • catalysts 1 and 2 can initiate the reaction at very low temperatures, even with very dilute feed gas compositions. This enables reduction in the size of the feed gas pre-heater and the start-up heaters as the catalyst bed need only reach a relatively low temperature for the reaction to be initiated. This in turn would reduce start up times and capital and operational costs.
  • the lower pre-heat temperature would also increase the safety of the system because the reactant mixture would be below its auto- ignition temperature and therefore residence times within the pre-heater and reactor inlet manifolds would not be so critical. This in turn increases the flexibility of any plant by increasing the operational turn-down ratio.
  • catalysts 1 and 2 can bring the reaction to equilibrium at very high space velocities. This means that these catalysts are stable and active for extended periods of time under the most arduous conditions. As catalyst 3 is deactivated under these conditions, this demonstrated that catalysts 1 and 2 would be the preferred catalysts as a commercial reactor utilising these two of the four catalysts tested could be smaller and cheaper for the same duty. Experiment 4 also demonstrated that the process is catalysed heterogeneously and that 'empty tube' gas phase reactions are not solely responsible for the occurrence of the reactions under these conditions.
  • a feed gas containing by mole 31.3% steam, 60% N 2 , 11.4% CH 4 and 8.5% 0 2 was passed over a 70g bed of catalyst 1 at 20 bar (GHSV 30,000 dry) .
  • the temperature of the feed gas was 300°C and the temperature of the gaseous mixture emerging from the bed (i.e. outlet temperature) was 750°C.
  • the composition by mole of the emerging gas mixture was: H 2 27.6%, C0 2 8.2%, N 2 51.6%, CO 4.48% and CH 4 7.59%. This was calculated to be at the thermodynamic equilibrium with the 'outlet' temperature. The run lasted more than 200 hours with no significant deactivation of the catalyst.
  • catalyst 1 can carry out catalytic partial oxidation in the presence of steam, that the increase in partial pressure of steam (and the decrease in partial pressure of C0 2 ) does not cause deactivation problems or physical collapse of the catalyst, and that the catalyst can bring the reactant gases to equilibrium under these conditions.
  • the reactants are pre- mixed whilst cold and co-fed to the pre-heater, the temperature of which may be below or just above the adiabatic auto-ignition temperature.
  • the adiabatic auto-ignition temperature is defined as the temperature at which in an adiabatic enclosure the self heating effect of the reaction mixture will eventually lead to ignition. Ignition is defined as thermal runaway. Reaction mixtures below the adiabatic auto-thermal ignition temperature may exhibit self heating, but this will never lead to ignition. It is therefore considered vitally important that the residence times through the pre-heater and on to the catalyst bed are kept to a minimum. Studies indicate that times in the order of 1 to 10 seconds are safe depending on the gas mixture in use.
  • the outlet H 2 to CO ratio can be varied from 0.25:1 to 8:1. This can be achieved by varying the 0 2 concentration in the feed gas mixture without either carbon deposition nor excessive outlet temperature.
  • 1.5-2:1 would be used for manufacturing, for example, synthetic fuels or methanol, whilst >6:1 could be used for fuel processing for fuel cells.
  • the reactant gases are contacted with the catalyst for sufficient time to be brought to thermodynamic equilibrium at the outlet temperature. Because the exothermic combustion reactions (grouped under reaction - equation (2) - see above) are faster than the reforming reactions (equations (3) and (4) above) , the temperature profile in the reactor passes through a peak or hot spot. It is important that the reactor is engineered so that this hot spot is minimised and kept below 950°C (preferably 900°C) . It is important that there is sufficient catalyst in the reactor to bring the gases to equilibrium after the hot spot. Although it is possible to operate the reactor away from equilibrium i.e.
  • the reactor could readily be constructed. to operate over a wide range of pressures (1 to 100 bar or more) and could be fed with either oxygen or air as the oxidant .
  • catalyst 1 was able to initiate and maintain the partial oxidation reaction at very low pressures (down to 1 bar) , even though the residence time was greatly reduced.
  • catalyst 1 was also effective at high pressures (up to 70 bar) in the presence of steam in initiating and maintaining reforming activity whilst retaining good physical condition.
  • catalysts 1 and 2 have submitted catalysts 1 and 2 to tests for many thousands of hours under reaction conditions where the partial pressure of super-heated steam was much higher than the highest pressure to be used in the partial oxidation process to which the present invention relates . These tests demonstrated that catalysts 1 and 2 are capable of performing the partial oxidation reaction at the highest pressures and temperatures claimed by the Applicants in relation to the present invention.
  • Reference numeral 1 indicates a reactor in which 'low' temperature partial oxidation as illustrated above occurs .
  • the synthesis gas emerging from reactor 1 passes to reactor 2 which is also fed with oxygen.
  • Reactor 2 may be a known 'high' temperature partial oxidation reactor such as that, for example, described in European patent application no. 89300704.7 (published under the number EP 0329292 A2) and identified therein by the reference number 46. That reactor comprises a large refractory lined pressure vessel, a burner and a high temperature reforming catalyst.
  • the incoming partially reformed synthesis gas is combusted with the oxidising stream at the burner head and the resulting mixture is then passed over the catalyst (typically Chromium on alumina) which brings the reactants to thermodynamic equilibrium with respect to reaction equations (2), (3) and (4) above at a temperature higher than that in reactor l.
  • the methane slippage from this reactor is typically less than 5%.
  • the partially oxidised/reformed gases leaving reactor 1 are mixed with more oxygen in the burner assembly (not shown) in reactor 2.
  • the further partially oxidised product gases which are now further reformed and comprise a mixture of carbon monoxide, carbon dioxide, hydrogen, steam and a reduced amount of unreacted methane. No higher hydrocarbons are present.
  • These product gases emerge from reactor 2 and typically pass through a series of heat exchangers before passing, without being subjected to compression operations, to further reactors to undergo further processing to produce, for example, methanol.
  • heat exchanger 3 which is one of the series mentioned above, is used to pre-heat the feed natural gas, oxygen and steam and/or carbon dioxide before they are introduced into the reactor 1.
  • the further partially oxidised product gases or the "fully reformed" gas, i.e. the further synthesis gas or make ⁇ up gas reach the synthesis loop, they may pass through one or more purification/scrubbing stages. It may, for example, be desirable to remove some of the carbon dioxide present in the make-up gas, prior to the gas being passed to the synthesis loop. It is envisaged that such removed carbon dioxide could be recycled and used as part of the carbon dioxide feed to the reactor 1.
  • the initial feed gas mixture supplied may be at a pressure of from 50 to 100 bar.
  • the individual components prior to forming the feed gas mixture may be
  • inlet composition at the second stage corresponds to the outlet composition at the first stage except that further oxygen is added.
  • plants for converting the natural gas into other products and incorporating the relatively inexpensive first and second stage catalytic partial oxidation reactors referred to above for carrying out the methods according to this invention could encourage utilisation of hitherto unused natural gas fields .
  • Another advantage is that the methods according to this invention can be conducted in partial oxidation reactors which are small and light weight, making them ideally suited for operation where space and weight are at a premium, such as in situations which require synthesis gas manufacture offshore or in a remote location.
  • the cost of infrastructure required to support such partial oxidation reactors and associated equipment can easily exceed the cost of the process equipment itself.
  • the units or equipment can be substantially completed or assembled before shipping to the site as 'modules' . This greatly reduces the work which has to be done in the remote location and generally increases the ease with which the units and equipment can be transported both to and from the remote location.

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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de production d'un gaz de synthèse (essentiellement un mélange d'hydrogène et de monoxyde de carbone) à partir d'un mélange de méthane et d'oxygène. Ledit procédé consiste à oxyder partiellement le méthane par mise en contact dumélange de gaz reactant à une température relativement basse (entre 100 °C et 950°C) et à une pression pouvant atteindre 15 bar, avec un catalyseur défini, constitué d'un composé de Feitknecht nickel-aluminium et d'un minéral argileux aluminosilicate. Le gaz de synthèse obtenu peut être mélangé à nouveau à de l'oxygène et être partiellement oxydé sans passer par une étape de compression intermédiaire de façon à produire un second gaz de synthèse pouvant être utilisé directement dans un procédé en aval à haute pression pour la production d'un produit chimique, tel qu'un méthanol.
PCT/GB1997/000900 1996-04-04 1997-04-01 Production d'un gaz de synthese a partir d'une charge premiere hydrocarbonee WO1997037930A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP9535945A JP2000508286A (ja) 1996-04-04 1997-04-01 炭化水素系供給原料からの合成ガスの製造
AU22991/97A AU713494B2 (en) 1996-04-04 1997-04-01 Production of synthesis gas from hydrocarbonaceous feedstock
EP97915555A EP0891295A1 (fr) 1996-04-04 1997-04-01 Production d'un gaz de synthese a partir d'une charge premiere hydrocarbonee

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9607231.9 1996-04-04
GB9607231A GB2311790A (en) 1996-04-04 1996-04-04 Production of synthesis gas from hydrocarbonaceous feedstock

Publications (1)

Publication Number Publication Date
WO1997037930A1 true WO1997037930A1 (fr) 1997-10-16

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PCT/GB1997/000900 WO1997037930A1 (fr) 1996-04-04 1997-04-01 Production d'un gaz de synthese a partir d'une charge premiere hydrocarbonee

Country Status (11)

Country Link
EP (1) EP0891295A1 (fr)
JP (1) JP2000508286A (fr)
AR (1) AR006538A1 (fr)
AU (1) AU713494B2 (fr)
CA (1) CA2250893A1 (fr)
GB (1) GB2311790A (fr)
ID (1) ID17322A (fr)
RU (1) RU2161120C2 (fr)
TN (1) TNSN97062A1 (fr)
WO (1) WO1997037930A1 (fr)
ZA (1) ZA972890B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999015459A1 (fr) * 1997-09-22 1999-04-01 Amoco Corporation Procede de preparation et d'utilisation de catalyseurs au nickel
JP2001348207A (ja) * 2000-03-02 2001-12-18 Boc Group Inc:The 炭化水素を部分酸化して水素と一酸化炭素を製造する方法

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NO316440B1 (no) † 2000-05-18 2004-01-26 Statoil Asa Hydrotalcitt-basert materiale med forbedret styrke, anvendelse og fremgangsmåte derav, og katalysator omfattende dette materialet
EP1188713A3 (fr) * 2000-09-18 2003-06-25 Haldor Topsoe A/S Production de gaz de synthèse contenant de l'hydrogène et du monoxyde de carbone par oxydation partielle
FR2820416B1 (fr) * 2001-02-07 2003-12-05 Cie D Etudes Des Technologies Procede et dispositif pour la production d'hydrogene par oxydation partielle de carburants hydrocarbones
GB0127517D0 (en) * 2001-11-16 2002-01-09 Statoil Asa Catalysts
US7427388B2 (en) 2004-03-19 2008-09-23 Air Products And Chemicals, Inc. Process for improving prereforming and reforming of natural gas containing higher hydrocarbons along with methane
US7510793B2 (en) 2004-08-05 2009-03-31 Rolls-Royce Fuel Cell Systems (Us) Inc. Post-reformer treatment of reformate gas
JP4781704B2 (ja) * 2005-03-31 2011-09-28 大阪瓦斯株式会社 水素含有ガスの製造方法及び装置
JP4838526B2 (ja) * 2005-03-31 2011-12-14 大阪瓦斯株式会社 合成ガスの製造方法及び装置
JP4886416B2 (ja) * 2006-08-04 2012-02-29 株式会社東芝 一酸化炭素低減装置、一酸化炭素低減方法、水素製造装置および燃料電池発電システム
JP5009109B2 (ja) * 2007-09-13 2012-08-22 関西電力株式会社 炭化水素の部分酸化触媒、それを用いた水素含有ガスの製造方法及び装置
JP5324265B2 (ja) * 2009-03-11 2013-10-23 関西電力株式会社 炭化水素の部分酸化触媒、それを用いた水素含有ガスの製造方法及び装置
JP7417920B2 (ja) * 2019-09-19 2024-01-19 国立大学法人北海道大学 軽質炭化水素の部分酸化触媒ならびに該触媒による一酸化炭素と水素の製造方法

Citations (3)

* Cited by examiner, † Cited by third party
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GB2222963A (en) * 1988-09-23 1990-03-28 British Gas Plc Methanation catalysts comprising feitknecht compounds
WO1994014700A1 (fr) * 1992-12-21 1994-07-07 Amoco Corporation Procede de preparation de gaz synthetique a l'aide de catalyseurs contenant du nickel
GB2274284A (en) * 1992-12-23 1994-07-20 Snam Progetti Catalytic process for producing synthesis gas

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2222963A (en) * 1988-09-23 1990-03-28 British Gas Plc Methanation catalysts comprising feitknecht compounds
WO1994014700A1 (fr) * 1992-12-21 1994-07-07 Amoco Corporation Procede de preparation de gaz synthetique a l'aide de catalyseurs contenant du nickel
GB2274284A (en) * 1992-12-23 1994-07-20 Snam Progetti Catalytic process for producing synthesis gas

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999015459A1 (fr) * 1997-09-22 1999-04-01 Amoco Corporation Procede de preparation et d'utilisation de catalyseurs au nickel
JP2001348207A (ja) * 2000-03-02 2001-12-18 Boc Group Inc:The 炭化水素を部分酸化して水素と一酸化炭素を製造する方法

Also Published As

Publication number Publication date
ID17322A (id) 1997-12-18
AU2299197A (en) 1997-10-29
RU2161120C2 (ru) 2000-12-27
AU713494B2 (en) 1999-12-02
AR006538A1 (es) 1999-09-08
CA2250893A1 (fr) 1997-10-16
TNSN97062A1 (fr) 1999-12-31
GB9607231D0 (en) 1996-06-12
EP0891295A1 (fr) 1999-01-20
GB2311790A (en) 1997-10-08
JP2000508286A (ja) 2000-07-04
ZA972890B (en) 1998-04-16

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