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WO1999055618A1 - Method and apparatus for the production of synthesis gas - Google Patents

Method and apparatus for the production of synthesis gas Download PDF

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Publication number
WO1999055618A1
WO1999055618A1 PCT/NL1999/000256 NL9900256W WO9955618A1 WO 1999055618 A1 WO1999055618 A1 WO 1999055618A1 NL 9900256 W NL9900256 W NL 9900256W WO 9955618 A1 WO9955618 A1 WO 9955618A1
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WO
WIPO (PCT)
Prior art keywords
gasifier
reformer
synthesis gas
biomass
outlet
Prior art date
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PCT/NL1999/000256
Other languages
French (fr)
Inventor
Hubertus Johannes Veringa
Katrien Hemmes
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Stichting Energieonderzoek Centrum Nederland
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Filing date
Publication date
Application filed by Stichting Energieonderzoek Centrum Nederland filed Critical Stichting Energieonderzoek Centrum Nederland
Priority to AU35404/99A priority Critical patent/AU3540499A/en
Priority to JP2000545785A priority patent/JP2002512933A/en
Priority to CA002330302A priority patent/CA2330302A1/en
Priority to EP99917245A priority patent/EP1080034A1/en
Publication of WO1999055618A1 publication Critical patent/WO1999055618A1/en

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Classifications

    • 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
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • 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
    • 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
    • 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
    • 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
    • C10K3/001—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 thermal treatment
    • C10K3/003—Reducing the tar content
    • C10K3/006—Reducing the tar content by steam reforming
    • 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
    • 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
    • C10K3/06—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 mixing with gases
    • 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
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • 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
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0822—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel the fuel containing hydrogen
    • 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
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0866—Methods of heating the process for making hydrogen or synthesis gas by combination of different heating methods
    • 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
    • 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
    • Y02P20/10—Process efficiency
    • 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 method for forming synthesis gas from hydrocarbons, comprising: - feeding a first hydrocarbon and an oxidant to a gasifier and discharging synthesis gas from the gasifier,
  • German patent application DE-A-3, 242.206 discloses an apparatus in which coal in powdered form or a heavy oil fraction are partially oxidized in a gasifier, with the addition of oxygen, at a pressure of between 30 and 100 bar and a temperature of between 1000°C and 1400°C.
  • the hot synthesis gas formed in the process is passed over a water bath to remove soot and slags and is then passed through a tubular reactor in which catalytic steam reforming of LPG takes place at a pressure of between 10 and 40 bar and a temperature of between 750°C and 1000°C.
  • the synthesis gases formed in the gasifier and in the reformer are finally mixed in such a ratio that the desired H 2 /CO ratio is obtained.
  • the known apparatus is relatively complex and is not suitable for gasification of biomass and/or residues, whose partial oxidation does not, owing to the relatively high oxygen content naturally present, afford a suitable synthesis gas. Furthermore, when biomass and/or residues are used as a hydrocarbon source for the gasifier, the temperature achieved may be insufficiently high for driving the flow of heat to the reformer. Finally, the known apparatus, in which the reformer is completely integrated with the gasifier, is inflexible with respect to the operating point to be selected of mass streams fed in and the H /CO ratio of the synthesis gas formed.
  • the method according to the present invention is characterized in that the first hydrocarbon contains biomass and/or residues and in that part of the synthesis gas discharged from the gasifier is combusted, the heat liberated in the process being supplied to the reformer.
  • the avoided fossil CO 2 emission yield, 9co 2 of the process according to the present invention is likewise relatively high: 9co 2 - LHV(H 2 +CO) out /LHV (natural gas) ⁇ n .
  • the production of CO 2 per kg of H 2 + CO produced is small, and the avoided (fossil) CO 2 emission is therefore large.
  • the gasifier and the reformer according to the present invention are not integrated to a large degree, it is possible for the H 2 /CO ratio to be adjusted over a wide range.
  • a reliable process is obtained, since it is possible, in the event of the supply of biomass and/or residues being interrupted, for the 3 steam reformer to be operated separately, with the option of feeding the burner of the reformer with natural gas and gas from the gasifier.
  • the process according to the invention can take place using a relatively simple apparatus, the only measure required being to fit a branch line between the outlet of the gasifier and the reformer.
  • the gasifier delivers a synthesis gas which is rich in CO and relatively low in hydrogen
  • steam reforming gives precisely the opposite result
  • a combination of the two gas streams provides a mixed gas whose composition can be controlled by selecting the ratio between the input of fossil hydrocarbons and biomass. This allows the quality of the syngas of the biomass gasification to be increased and the H 2 /CO ratio of the mixed gas to be freely adjusted.
  • the hydrogen/carbon monoxide ratio of the mixed gas is between 0.7 and 5, preferably between 2 and 3. At these values, the mixed gas is suitable for a large number of downstream processes, such as admixture into the gas grid, secondary energy generation, generation of heat and/or power, and production of organic compounds as starting materials for the processing industry.
  • An apparatus in which the method according to the present invention can be implemented advantageously comprises, for example, a gasifier whose bed material is circulated, for the biomass and/or the residues, to which the steam reformer for the fossil hydrocarbon, preferably natural gas, is connected via a branch line.
  • a gasifier whose bed material is circulated, for the biomass and/or the residues, to which the steam reformer for the fossil hydrocarbon, preferably natural gas, is connected via a branch line.
  • Figure 1 shows a schematic depiction of the combined biomass/residues gasification and hydrocarbon reforming
  • Figure 2 shows a schematic depiction of the syngas composition according to the present invention
  • Figures 3 and 4 respectively, show the energy streams and mass streams of a syngas production process according to the present invention.
  • Figure 1 shows a gasifier 1 with a first inlet 2 for biomass and/or residues, and a second inlet 3 for an oxidant such as, for example, oxygen.
  • the apparatus also comprises a reformer 4 with a first inlet 5 for the supply of fossil hydrocarbons and a steam supply 6.
  • the outlet 8 of the gasifier 1 is connected to the reformer 4 by means of a branch line 7.
  • the outlet 8 of the gasifier is further connected to a purification apparatus 10 such as, for example, a scrubber to remove cyclic hydrocarbons and other contaminants such as H 2 S, HC1. alkali metals, tarry materials and dust from the syngas.
  • a purification apparatus 10 such as, for example, a scrubber to remove cyclic hydrocarbons and other contaminants such as H 2 S, HC1. alkali metals, tarry materials and dust from the syngas.
  • the outlet 9 of the 4 reformer 4 " can be connected to the outlet 12 of the purification apparatus 10 to form ' a mixed gas which can be fed to a CO 2 separator 13.
  • the outlet 14 of the CO 2 separator 13 is connected to a gas separation apparatus 15 for adjusting the composition of the product gas.
  • the gas coming from the gas separation apparatus 15 can be fed to the gas grid, can be used for production of energy, or can, for example, be used as process gas, where CO and H 2 can be reacted together catalytically to produce economically interesting hydrocarbons according to known and proven conversion technologies. It is also possible for the synthesis gas available from the outlet 9 of the reformer 4 to be fed, in its entirety or in part, to the gas grid via line 16.
  • the waste heat of the gases formed at the outlet of the gasifier 1 and the reformer 4 is returned, via heat exchangers 17 and 18, to the gasifier 1 and the reformer 4, respectively.
  • the process in the apparatus according to the present invention is determined by the following reactions: In the gasifier 1, the reaction taking place is: biomass + O 2 ⁇ CO + H 2 + C0 2 + H 2 O + C x H y .
  • the choice of gasification system provides the additional freedom to adjust the relative composition of the gas components.
  • hydrocarbons (C x H y ) may form part of the gas components.
  • the shift reaction CO + H 2 O ⁇ -> CO 2 + H 2 occurs. Since the gasifier 1 is operated autothermally, CO 2 and H 2 O are formed therein. If the oxidant used is ambient air, the synthesis gas at the outlet 8 of the gasifier may also comprise nitrogen. In the reformer 4, CO 2 is formed as a result of the shift reaction taking place to a significant degree. For a number of applications or downstream conversion routes of the process gas, the presence of minor components need not be a disadvantage. If the presence of minor components is not disadvantageous, a relatively coarse removal technique in, for example, purification apparatus 10 may be sufficient. To lower the nitrogen content in the product of the biomass gasifier 1 , it would be possible to use pure oxygen, rather than air, in the gasification.
  • the water can likewise be removed in a simple manner from the process gas.
  • the "gasifier 1 and the reformer 4 are operated at temperatures of between 750° ' C and 1000°C, for example about 800°C-900°C.
  • the gasifier 1 can, for example, be formed by a gasifier having an external burner, such as is manufactured by Manufacturing Technology Conversion International, with a temperature of 850°C and a pressure of 1 bar.
  • the reformer 4 comprises a steam reformer known per se having a burner which, for example, is operated at a pressure of 1 bar and a temperature of 1200°C, the pressure in the reformer 4 being 1 bar and the temperature being 815°C.
  • the burner of the reformer is fed with synthesis gas coming from the gasifier.
  • Figure 2 in the form of a graph, shows how varying the ratio of the quantity of methane fed to the reformer 4 via the inlet 5 and the quantity of biomass fed to the gasifier 1 via the inlet 2 allows the composition of the mixed gas formed after combining the synthesis gases from outlets 9 and 12 to be varied.
  • the gasifier 1 delivers a synthesis gas which mainly comprises CO
  • the steam reformer 4 comprises synthesis gas mainly containing H 2
  • the H 2 /CO ratio can be adjusted by selecting the ratio between the input of natural gas and of biomass.
  • the H 2 /CO ratio is around 2-3 mol/mol. This ratio is particularly beneficial for forming organic compounds, including liquid hydrocarbons.
  • Figures 3 and 4 respectively show the energy and mass streams of the process according to the present invention for an H /CO ratio of 3.16.
  • the figures in brackets give percentages for an energy or mass yield of the synthesis gas formed in total.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
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  • Physics & Mathematics (AREA)
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  • Hydrogen, Water And Hydrids (AREA)
  • Industrial Gases (AREA)

Abstract

The invention relates to a method and an apparatus for forming synthesis gas from biomass and/or residues. In a biomass gasifier and/or residues gasifier, synthesis gas is formed, part of which is combusted, the combustion heat being transferred to a reformer. In the reformer, a fossil hydrocarbon is converted into synthesis gas which is mixed with the synthesis gas formed in the gasifier. The method and apparatus according to the invention afford a high cold-gas yield, and the production of CO2 per kilogram of synthesis gas (H2 and CO) produced is low. Owing to the low degree fo integration of the gasifier and the reformer, the H2/CO ratio can be adjusted over a wide range. The apparatus according to the invention is relatively simple and reliable, given that the only connection between the reformer and the outlet of the gasifier is via a branch line. Coupling the gasifier and the reformer according to the invention permits a gradual transition from the use of fossil fuel to a more sustainable hydrocarbon source. Moreover, the quality of the synthesis gas formed in the biomass gasifier can be improved by mixing with the synthesis gas from the reformer, and control of the feed streams allows a variable syngas composition (H2/CO ratio) to be achieved.

Description

METHOD AND APPARATUS FOR THE PRODUCTION OF SYNTHESIS GAS
The invention relates to a method for forming synthesis gas from hydrocarbons, comprising: - feeding a first hydrocarbon and an oxidant to a gasifier and discharging synthesis gas from the gasifier,
- feeding a second, fossil hydrocarbon and steam to a reformer and discharging synthesis gas from the reformer, and
- mixing the synthesis gases formed in the gasifier and in the reformer. The production of synthesis gas from fossil fuels such as coal and natural gas, with the addition of steam and an oxidant such as air, to form hydrogen and carbon monoxide (synthesis gas) is generally known. This steam reforming affords a relatively pure synthesis gas which, because of the shift reaction, also contains CO2.
German patent application DE-A-3, 242.206 discloses an apparatus in which coal in powdered form or a heavy oil fraction are partially oxidized in a gasifier, with the addition of oxygen, at a pressure of between 30 and 100 bar and a temperature of between 1000°C and 1400°C. The hot synthesis gas formed in the process is passed over a water bath to remove soot and slags and is then passed through a tubular reactor in which catalytic steam reforming of LPG takes place at a pressure of between 10 and 40 bar and a temperature of between 750°C and 1000°C. The synthesis gases formed in the gasifier and in the reformer are finally mixed in such a ratio that the desired H2/CO ratio is obtained.
The known apparatus is relatively complex and is not suitable for gasification of biomass and/or residues, whose partial oxidation does not, owing to the relatively high oxygen content naturally present, afford a suitable synthesis gas. Furthermore, when biomass and/or residues are used as a hydrocarbon source for the gasifier, the temperature achieved may be insufficiently high for driving the flow of heat to the reformer. Finally, the known apparatus, in which the reformer is completely integrated with the gasifier, is inflexible with respect to the operating point to be selected of mass streams fed in and the H /CO ratio of the synthesis gas formed.
Within the scope of developing sustainable energy sources which involve a reduction in C02 emission, and also with a view to the exhaustion of the fossil hydrocarbon sources, gasification of biomass and hydrocarbon-containing residue 2 streams is "Of great importance. On the basis of maximum use of the available sources and cultivation in the Netherlands, the estimated extent of the potential use of biomass and residue streams is 165 PJ (165 1015 J) per year, with a total energy consumption which in the Netherlands today is about 3000 PJ per year. A gradual transition towards a substantial use of sustainable energy is desirable, preference being given to technologies which are able to provide electricity as well as heat and a raw material for the process industry or transport sector, without requiring drastic adjustments to the infrastructure.
Within this scope it is an object of the present invention to provide a method and apparatus for forming synthesis gas from biomass and/or residues, in which a gradual transition of the use of fossil hydrocarbons towards sustainable hydrocarbon sources is possible. It is also an objective of the present invention to provide a method and apparatus in which it is possible for a synthesis gas of relatively high quality to be formed, on an industrial scale, from residues and/or biomass and in which the composition (the H2/CO ratio) of the synthesis gas can be adjusted over a wide range in a simple manner. It is a further objective of the present invention to form a synthesis gas in an exoenergetically efficient manner, from biomass and/or residues, in which the production of CO2 per kg of synthesis gas formed is as small as possible.
To this end, the method according to the present invention is characterized in that the first hydrocarbon contains biomass and/or residues and in that part of the synthesis gas discharged from the gasifier is combusted, the heat liberated in the process being supplied to the reformer.
The invention is based on the insight that the heat required for steam reforming is obtained not by combustion of the biomass and/or residues, but by combustion of some of the synthesis gas formed in the gasifier, so that a high cold-gas yield c of the synthesis gas is obtained, based on H2 and CO; c = LHV(H2+CO)0ut/LHV (biomass + natural gas)ιn, where LHV is the lower heating value. The avoided fossil CO2 emission yield, 9co2, of the process according to the present invention is likewise relatively high: 9co2 - LHV(H2+CO)out/LHV (natural gas)ιn. In other words, the production of CO2 per kg of H2 + CO produced is small, and the avoided (fossil) CO2 emission is therefore large. Moreover, given the fact that the gasifier and the reformer according to the present invention are not integrated to a large degree, it is possible for the H2/CO ratio to be adjusted over a wide range. At the same time, a reliable process is obtained, since it is possible, in the event of the supply of biomass and/or residues being interrupted, for the 3 steam reformer to be operated separately, with the option of feeding the burner of the reformer with natural gas and gas from the gasifier. Finally, the process according to the invention can take place using a relatively simple apparatus, the only measure required being to fit a branch line between the outlet of the gasifier and the reformer. As the gasifier delivers a synthesis gas which is rich in CO and relatively low in hydrogen, whereas steam reforming gives precisely the opposite result, a combination of the two gas streams provides a mixed gas whose composition can be controlled by selecting the ratio between the input of fossil hydrocarbons and biomass. This allows the quality of the syngas of the biomass gasification to be increased and the H2/CO ratio of the mixed gas to be freely adjusted. The hydrogen/carbon monoxide ratio of the mixed gas is between 0.7 and 5, preferably between 2 and 3. At these values, the mixed gas is suitable for a large number of downstream processes, such as admixture into the gas grid, secondary energy generation, generation of heat and/or power, and production of organic compounds as starting materials for the processing industry. An apparatus in which the method according to the present invention can be implemented advantageously comprises, for example, a gasifier whose bed material is circulated, for the biomass and/or the residues, to which the steam reformer for the fossil hydrocarbon, preferably natural gas, is connected via a branch line.
The invention will be explained in more detail with reference to the appended drawing, in which:
Figure 1 shows a schematic depiction of the combined biomass/residues gasification and hydrocarbon reforming,
Figure 2 shows a schematic depiction of the syngas composition according to the present invention, and Figures 3 and 4, respectively, show the energy streams and mass streams of a syngas production process according to the present invention.
Figure 1 shows a gasifier 1 with a first inlet 2 for biomass and/or residues, and a second inlet 3 for an oxidant such as, for example, oxygen. The apparatus also comprises a reformer 4 with a first inlet 5 for the supply of fossil hydrocarbons and a steam supply 6. The outlet 8 of the gasifier 1 is connected to the reformer 4 by means of a branch line 7. The outlet 8 of the gasifier is further connected to a purification apparatus 10 such as, for example, a scrubber to remove cyclic hydrocarbons and other contaminants such as H2S, HC1. alkali metals, tarry materials and dust from the syngas. The outlet 9 of the 4 reformer 4" can be connected to the outlet 12 of the purification apparatus 10 to form' a mixed gas which can be fed to a CO2 separator 13. The outlet 14 of the CO2 separator 13 is connected to a gas separation apparatus 15 for adjusting the composition of the product gas. The gas coming from the gas separation apparatus 15 can be fed to the gas grid, can be used for production of energy, or can, for example, be used as process gas, where CO and H2 can be reacted together catalytically to produce economically interesting hydrocarbons according to known and proven conversion technologies. It is also possible for the synthesis gas available from the outlet 9 of the reformer 4 to be fed, in its entirety or in part, to the gas grid via line 16. The waste heat of the gases formed at the outlet of the gasifier 1 and the reformer 4 is returned, via heat exchangers 17 and 18, to the gasifier 1 and the reformer 4, respectively. The process in the apparatus according to the present invention is determined by the following reactions: In the gasifier 1, the reaction taking place is: biomass + O2 → CO + H2 + C02 + H2O + CxHy. The choice of gasification system provides the additional freedom to adjust the relative composition of the gas components. In addition, hydrocarbons (CxHy) may form part of the gas components.
In the steam reformer 4, the following reaction takes place, natural gas being fed in via the first inlet 5, steam being supplied via the steam supply 6, and thermal energy being supplied via an internal or external heat exchanger heated by combustion of the synthesis gas coming from the gasifier 1 and supplied via branch lines 7: CH4 + H2O <-> CO + 3H2.
In addition, the shift reaction CO + H2O <-> CO2 + H2 occurs. Since the gasifier 1 is operated autothermally, CO2 and H2O are formed therein. If the oxidant used is ambient air, the synthesis gas at the outlet 8 of the gasifier may also comprise nitrogen. In the reformer 4, CO2 is formed as a result of the shift reaction taking place to a significant degree. For a number of applications or downstream conversion routes of the process gas, the presence of minor components need not be a disadvantage. If the presence of minor components is not disadvantageous, a relatively coarse removal technique in, for example, purification apparatus 10 may be sufficient. To lower the nitrogen content in the product of the biomass gasifier 1 , it would be possible to use pure oxygen, rather than air, in the gasification. In the purification apparatus, the water can likewise be removed in a simple manner from the process gas. 5 The "gasifier 1 and the reformer 4 are operated at temperatures of between 750°'C and 1000°C, for example about 800°C-900°C. The gasifier 1 can, for example, be formed by a gasifier having an external burner, such as is manufactured by Manufacturing Technology Conversion International, with a temperature of 850°C and a pressure of 1 bar. The reformer 4 comprises a steam reformer known per se having a burner which, for example, is operated at a pressure of 1 bar and a temperature of 1200°C, the pressure in the reformer 4 being 1 bar and the temperature being 815°C. The burner of the reformer is fed with synthesis gas coming from the gasifier.
Figure 2, in the form of a graph, shows how varying the ratio of the quantity of methane fed to the reformer 4 via the inlet 5 and the quantity of biomass fed to the gasifier 1 via the inlet 2 allows the composition of the mixed gas formed after combining the synthesis gases from outlets 9 and 12 to be varied. As the gasifier 1 delivers a synthesis gas which mainly comprises CO, whereas the steam reformer 4 comprises synthesis gas mainly containing H2, the H2/CO ratio can be adjusted by selecting the ratio between the input of natural gas and of biomass. In an advantageous embodiment, the H2/CO ratio is around 2-3 mol/mol. This ratio is particularly beneficial for forming organic compounds, including liquid hydrocarbons.
Figures 3 and 4 respectively show the energy and mass streams of the process according to the present invention for an H /CO ratio of 3.16. The figures in brackets give percentages for an energy or mass yield of the synthesis gas formed in total.

Claims

6 Claims
1. Method for forming synthesis gas from hydrocarbons, comprising:
- feeding a first hydrocarbon and an oxidant to a gasifier and discharging synthesis gas from the gasifier,
- feeding a second, fossil hydrocarbon and steam to a reformer and discharging synthesis gas from the reformer, and
- mixing the synthesis gases formed in the gasifier and in the reformer, characterized in that the first hydrocarbon contains biomass and/or residues and in that part of the synthesis gas discharged from the gasifier is combusted, the heat liberated in the process being supplied to the reformer.
2. Method according to Claim 1, characterized in that part of the synthesis discharged from the gasifier is fed to a burner of the reformer.
3. Method according to Claim 1 or 2, characterized in that between 10 and 70 wt%, preferably between 30 and 50 wt%, of the synthesis gas formed in the gasifier is combusted.
4. Method according to Claim 1, 2 or 3, characterized in that the fossil hydrocarbon comprises natural gas.
5. Method according to Claim 1 , 2, 3 or 4, characterized in that the mixing ratio of the synthesis gases is set such that the mixing gas has a hydrogen/carbon monoxide ratio of between 0.7 and 5, preferably of between 2 and 3.
6. Method according to any one of the preceding claims, characterized in that the biomass and/or the residues are gasified autothermally.
7. Method according to any one of the preceding claims, characterized in that part of the heat generated by combustion of the synthesis gas is used to form steam for the reformer and/or to provide for other heat requirements.
8. Apparatus for forming synthesis gas, comprising a gasifier (1) for biomass and/or residues having a first inlet (2) for the biomass and/or the residues, a second inlet (3) for an oxidant and a first outlet (8) for synthesis gas, a reformer (4) having a first inlet (5) for fossil hydrocarbons, a steam supply (6) and a second outlet (9) for synthesis gas, said second outlet (9) being connected to the first outlet (8), and also a branch line (7), connected to the first outlet (8) for feeding part of the synthesis gas formed in the gasifier to a burner which is thermally coupled to the reformer (4). 7
9. " Apparatus according to Claim 8, characterized in that the synthesis gas formed in the gasifier (1) and/or in the reformer (4) is passed via a heat exchanger (17, 18), said heat exchanger being thermally coupled to the gasifier (1) and/or the reformer
(4).
10. Apparatus according to Claim 8 or 9, characterized in that the bed material of the gasifier (1) circulates, within the gasification system.
11. Apparatus according to Claim 8, 9 or 10, characterized in that outlet (8) of the gasifier (1) is connected, via a purification apparatus (10), to the outlet (9) of the reformer (4).
PCT/NL1999/000256 1998-04-29 1999-04-29 Method and apparatus for the production of synthesis gas WO1999055618A1 (en)

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CA002330302A CA2330302A1 (en) 1998-04-29 1999-04-29 Method and apparatus for the production of synthesis gas
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JP2002512933A (en) 2002-05-08

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