Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
  • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
  • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
  • C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
• • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
  • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
  • C10L3/08—Production of synthetic natural gas
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0913—Carbonaceous raw material
  • C10J2300/0916—Biomass
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0953—Gasifying agents
  • C10J2300/0966—Hydrogen
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0953—Gasifying agents
  • C10J2300/0969—Carbon dioxide
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
  • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
  • C10J2300/1656—Conversion of synthesis gas to chemicals
  • C10J2300/1662—Conversion of synthesis gas to chemicals to methane
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
  • C10J2300/1671—Integration of gasification processes with another plant or parts within the plant with the production of electricity
  • C10J2300/1675—Integration of gasification processes with another plant or parts within the plant with the production of electricity making use of a steam turbine
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
  • C10J2300/1687—Integration of gasification processes with another plant or parts within the plant with steam generation
• • 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
  • Y02P20/141—Feedstock
  • Y02P20/145—Feedstock the feedstock being materials of biological origin

Definitions

• the invention relates to a process for producing methane-rich product gas (S ⁇ G, Synthetic Natural Gas), which comprises feeding biomass and/or fossil fuels to a first reactor to form gaseous reaction products and feeding the reaction products from the first reactor to a methanation reactor in which the gaseous reaction product fed thereinto are converted into the methane-rich product gas.
• S ⁇ G Synthetic Natural Gas
• Hydrogen will play an important part in the future sustainable supply of energy.
• Transportation and storage of hydrogen in its free form (H 2 ) is more complicated and will probably require much more energy than transportation and storage of hydrogen chemically stored in the form of methane, for example.
• An additional advantage of the indirect use of hydrogen as a source of energy is that the future (sustainable) supply of energy will still allow use to be made of (parts of) the existing large-scale energy infrastructure such as, for example, the natural-gas grid.
• One of the possible processes for storing hydrogen in chemically bound form is hydrogasification of carbon-containing compounds such as, for example, biomass and waste. Pyrolysis of these compounds in an H 2 atmosphere allows green natural gas to be produced.
• EP-A-0 699 651 discloses that biomass, organic waste or fossil fuels can be converted in a hydrogasification reactor, with the addition of hydrogen, into a gas mixture having a high methane content and with small amounts of carbon dioxide.
• the gas mixture is converted, in a steam reformer, into synthesis gas which, in a third process step, is converted into methanol in the presence of a catalyst known per se, based on Cu/Zn.
• the hydrogen remaining at the final step, after removal of the methanol, is passed to the hydrogasification reactor. This process is suitable only for producing methanol.
• the process according to the invention is characterized in that the first reactor comprises a hydrogasification reactor which is fed with hydrogen, said hydrogen coming from an external source, and in that the product gas (S ⁇ G) has a Wobbe index of between 40 and 45 MJ/m (s.t.p.), preferably between 42 and 45 MJ/m 3 (s.t.p.), and having a methane molar percentage of at least 75%, preferably of at least 80%.
• External source here refers to a source which is not formed by the methanation reactor, but independently of the process for methane production according to the present invention supplies hydrogen to the hydrogasification reactor, such as hydrogen formed by electrolysis of water, steam reforming of light hydrocarbons, hydrogen formed by partial oxidation of heavy hydrocarbons such as oil or coal by means of steam, or hydrogen from industrial processes such as the production of chlorine by means of membrane or diaphragm cells, methanol production, production of acetone, isopropanol or methyl ethyl ketone, or hydrogen from blast furnaces.
• the hydrogasification reactor such as hydrogen formed by electrolysis of water, steam reforming of light hydrocarbons, hydrogen formed by partial oxidation of heavy hydrocarbons such as oil or coal by means of steam, or hydrogen from industrial processes such as the production of chlorine by means of membrane or diaphragm cells, methanol production, production of acetone, isopropanol or methyl ethyl ketone, or hydrogen from blast furnaces.
• Feeding external hydrogen into the hydrogasification reactor proved to make it possible to obtain a product gas having a Wobbe index, a CH4 molar percentage and a calorific value which are very close to the Wobbe index, the C L. percentage and the calorific value of natural gas (for example Groningen natural gas), so that the S ⁇ G formed can be delivered without any problems to consumers via the existing gas grid and can be used in existing facilities.
• natural gas for example Groningen natural gas
• the process according to the invention forms a suitable approach to upgrading biomass and organic waste, using hydrogen, to form S ⁇ G.
• hydrogen can be obtained from fossil sources. A practical application of this is provided by the following example.
• the hydrogen is formed by means of pyrolysis in a plasma reactor, for example via a CB&H process as described in S. Lynum, R. Hildrum, K. Hox, J. Hugdahl: Kvaerner Based Technologies for Environmentally Friendly Energy and Hydrogen Production, Proceedings of the 12th World Hydrogen
• Fig. 1 shows a schematic depiction of the process to form a methane- rich product gas (SNG) according to the present invention
• Fig. 2 shows a schematic depiction of a process according to the invention, in which the hydrogen for hydrogasification is obtained from a plasma process.
• Fig. 1 schematically shows the process stream for forming substitute natural gas (SNG) according to the invention.
• biomass Via a feeder 1, biomass is passed to a dryer 2.
• This biomass can include wood chips, vegetable waste or other organic hydrocarbon sources.
• As well as biomass it is also possible to feed the hydrogasification apparatus 3 with fossil fuels, a drying step not being required in that case.
• CO 2 Via an injection line A', CO 2 is introduced into the biomass feed line 4, in order to inject the biomass at the prevailing operating pressure (for example 30 bar) into the hydrogasification apparatus 3.
• the hydrogasification apparatus Via a feed line 5, the hydrogasification apparatus is fed with hydrogen from an external hydrogen source.
• the hydrogen source may comprise a water electrolysis process or be derived from industrial processes in which hydrogen is formed as a by-product.
• gaseous reaction products are removed from the hydrogasification apparatus, the main constituent being CH t , with CO, H 2 , CO 2 and H 2 O also present.
• the gas mixture is fed, via a heat exchanger 9, to a high-temperature gas purification apparatus 7 to remove solid residue and gaseous impurities from the synthesis gas, for example, H 2 S, HC1, HF, NH 3 .
• the solid residue from the hydrogasification apparatus 3 is removed via a discharge line 8.
• the purified methane-rich gas mixture is fed to a methanation reactor 12, in which the methane-rich gas mixture is converted into substitute natural gas (SNG) which, via a heat exchanger 14 and a water separator 15, is passed to a discharge line 16. Thence, substitute natural gas can be injected into the existing gas grid to be delivered to the end user.
• SNG substitute natural gas
• the heat removed from the methane-rich gas mixture at outlet 6 and in line 10, and the heat removed from the product gas at outlet 13 is supplied, via the heat exchangers 9,11 and 14, to a steam generator 19, the steam generated by which is fed to a steam turbine 20 which drives generator 17 to produce electricity.
• the condensed steam is recycled from the steam turbine 20 via a return line 22 to the inlet of the steam generator 19.
• Part of the low-pressure steam from the steam turbine 20 heats the dryer 2 via a heat exchanger 18.
• the condensed low-pressure steam, having passed the heat exchanger 18, is supplied to the steam generator 19.
• the following reactions take place, inter alia, in the hydrogasification apparatus 3 :
• the synthesis gas formed in the hydrogasification apparatus 3 comprises 29 vol% of methane and 7 vol% of CO, with a carbon conversion of the biomass of 78% and a heat demand of 1.2 MWuVkg of biomass (moisture-free).
• composition C wt% 51.32
• the hydrogasification apparatus 3 was operated at a temperature of 800°C and a pressure of 30 bar. At this setting it is possible, given a specific deviation from the thermodynamic equilibrium, to obtain a carbon conversion of the biomass of 89%, with a hydrogen feed of 75 mol/kg of biomass, the process being autothermal. Since, however, the biomass fed in is not free from moisture, and the hydrogasification apparatus 3 is fed with additional CO 2 , the hydrogen feed in the model was increased from 75 to 100 mol/kg of biomass to render the process autothermal. At this setting, the predicted conversion of carbon from the biomass is 83%.
• the gaseous products from the hydrogasification reactor 3 are cooled in two steps, via heat exchangers 9 and 11, from 850°C to the inlet temperature of the first methanation reactor at 400°C.
• a high- temperature gas purification apparatus 7 can be used to remove solid residue and gaseous contaminants such as H 2 S, HC1, HF, ⁇ H 3 from the synthesis gas.
• the methanation reactor 12 is based on the ICI high-temperature single-pass process as described in the Catalyst Handbook, second Edition, edited by M.V. Twigg, ISBN 1874545359, 1996. This makes use of a series of reactors operating at successively lower outlet temperatures.
• the steam generator 19 generates superheated steam at a pressure of
• the heat derived from the methanation reactor 12 and from the cooling of the methane-rich synthesis gas via heat exchangers 9 and 11 was used in the model to form steam, while the remainder of the heat released during cooling of the methane-rich gas mixture in lines 6 and 10 was used to superheat steam.
• the steam formed was expanded to 0.038 bar in two steps (from 40 to 10 bar in the first step, and from 10 to 0.038 bar in the second step).
• the Wobbe index based on cubic meters at standard temperature and pressure (m 3 [s.t.p.]) at 0°C and 1 atmosphere (MJ/m 3 [S.T.P]), is the ratio of the high calorific value and the square root of the relative density of the gas.
• the Wobbe index is defined according to the following formula:
• HHV is the high heating value in MJ/m (s.t.p.)
• p g and p a ⁇ r are the densities of gas and air, respectively, in kg/m 3 (s.t.p.).
• the Wobbe index is the measure of the amount of energy which is delivered to a burner via an injection Two gases having a different composition but the same Wobbe index provide the same amount of energy, given a predetermined injection direction at the same injection pressure.
• FIG. 2 shows an embodiment of a process in accordance with the present arrangement, in which the hydrogen is formed via a CB&H process as described in R. A. Wijbrans, J.M. van Zutphen, D.H. Recter: "Adding New Hydrogen to the Existing Gas Infrastructure in the Netherlands, Using the Carbon Black & Hydrogen Process, Proceedings of the 12th World Hydrogen Energy Conference", vol. II, pp. 963-968, 1998.
• natural gas is fed, via a feed line 23, to a plasma reactor 24 in which a plasma is generated by electrical energy being supplied, and in which hydrogen and carbon are formed.
• the carbon in the known CB&H process is discharged to be pelleted and packaged and the hydrogen is passed to a compression and injection apparatus 27 in order then to be injected into the natural- gas grid.
• the hydrogen is passed not to compression and injection apparatus 27, but to the hydrogasification process, via the feed line 5.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Combustion & Propulsion (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Processing Of Solid Wastes (AREA)
• Physical Or Chemical Processes And Apparatus (AREA)

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• 1998
  • 1998-10-12 NL NL1010288A patent/NL1010288C2/nl not_active IP Right Cessation
• 1999
  • 1999-10-12 EP EP99949470A patent/EP1127038A1/en not_active Withdrawn
  • 1999-10-12 WO PCT/NL1999/000630 patent/WO2000021911A1/en not_active Application Discontinuation
  • 1999-10-12 CA CA002346970A patent/CA2346970A1/en not_active Abandoned
  • 1999-10-12 JP JP2000575821A patent/JP2002527539A/ja active Pending

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