EP2177590A1 - Verfahren und Vorrichtung zur Verschwelung einer Speisung mit Kohlenwasserstoffen und zur Vergasung des Pyrolysrückstandes - Google Patents

Verfahren und Vorrichtung zur Verschwelung einer Speisung mit Kohlenwasserstoffen und zur Vergasung des Pyrolysrückstandes Download PDF

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Publication number
EP2177590A1
EP2177590A1 EP08166952A EP08166952A EP2177590A1 EP 2177590 A1 EP2177590 A1 EP 2177590A1 EP 08166952 A EP08166952 A EP 08166952A EP 08166952 A EP08166952 A EP 08166952A EP 2177590 A1 EP2177590 A1 EP 2177590A1
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EP
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Prior art keywords
gas
temperature
pyrolysis
residue
hydrocarbons
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EP08166952A
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English (en)
French (fr)
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Resetec Patent Sarl
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Resetec Patent Sarl
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Priority to EP08166952A priority Critical patent/EP2177590A1/de
Publication of EP2177590A1 publication Critical patent/EP2177590A1/de
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    • 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
    • C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60—Processes
    • C10J3/64—Processes with decomposition of the distillation products
    • C10J3/66—Processes with decomposition of the distillation products by introducing them into the gasification zone
    • 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
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/101—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids with water only
    • 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
    • C10J2300/0903—Feed preparation
    • C10J2300/0909—Drying
    • 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
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/094—Char
    • 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
    • C10J2300/0959—Oxygen
    • 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
    • C10J2300/0973—Water
    • 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
    • C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
    • C10J2300/1618—Modification of synthesis gas composition, e.g. to meet some criteria
    • 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
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1846—Partial oxidation, i.e. injection of air or oxygen only
    • 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
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1861—Heat exchange between at least two process streams
    • C10J2300/1884—Heat exchange between at least two process streams with one stream being synthesis 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
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1861—Heat exchange between at least two process streams
    • C10J2300/1892—Heat exchange between at least two process streams with one stream being water/steam

Definitions

  • the invention is directed to a method and an apparatus for processing a feed comprising hydrocarbons.
  • a feed comprising hydrocarbons such as e.g . biomass
  • hydrocarbons such as e.g . biomass
  • the disadvantage of combustion of a feed comprising hydrocarbons is the formation of large amounts of smoke, which smoke is costly to purify. Because of the need of a purification step, an energy conversion efficiency of only 20% is reached using combustion methods, viz . the ratio between the useful energy output of the synthesis gas and the input energy into the process is 0.20.
  • European patent application No. 07115971.9 describes a process in which synthesis gas is produced from a feed comprising hydrocarbons.
  • the hydrocarbons are converted by pyrolysis into synthesis gas, which synthesis gas is quenched by contacting it with water at such a high temperature that at least part of said water is converted into hydrogen and oxygen.
  • the resulting synthesis gas is enriched in hydrogen and oxygen, which adds considerably to its caloric value.
  • the process may further comprise a step, wherein a solid stream of pyrolysis residue is obtained and fed to a process comprising a smelter, which is operated at a temperature that is sufficient to vaporize at least part of the heavy metals present in the feed of said smelter and sufficient to obtain a liquid slag.
  • a smelter which is operated at a temperature that is sufficient to vaporize at least part of the heavy metals present in the feed of said smelter and sufficient to obtain a liquid slag.
  • Object of the present invention is to provide a method for converting a feed comprising hydrocarbons, such as e.g . biomass, into a gaseous product comprising synthesis gas, which method has a high energy conversion efficiency and a high yield of synthesis gas.
  • this object is met by providing a method for pyrolyis of a feed stream comprising hydrocarbons, which method comprises:
  • the method according to the invention has the advantage over the prior art that only little purification is needed before it can be used in combustion engines, gas engines, or gas turbines. Consequently, the method of the invention has an energy conversion efficiency of up to 40% to 50%, which means that 40% to 50% of the theoretical (chemical) energy is converted into work or electricity.
  • the first heating step is conducted in a pyrolysis reactor.
  • a rotating oven such as the one described in EP-A-0 653 478 may be used as a pyrolysis reactor.
  • Heat is provided to the pyrolysis reactor by a heat source, for example a burner that is typically operated using natural gas (in particular during start-up of the process) or synthesis gas produced by the process of the present invention (once the process is operational).
  • the feed comprising hydrocarbons is heated in the pyrolysis reactor to a temperature of preferably 400 - 950 °C, more preferably 700 - 900 °C, even more preferably ca .
  • a gas referred to as a pyrolysis gas and a pyrolysis residue are obtained.
  • the pyrolysis gas comprises hydrocarbons, CO and/or H 2 , and usually also CO 2 and/or H 2 O, and commonly also sulfur compounds, such as sulfur oxides.
  • the pyrolysis residue comprises non-volatile hydrocarbons, solid carbons and any minerals that were present in the feed.
  • the pyrolysis residue can be solid, liquid or partly solid and partly liquid.
  • the second step may be conducted in any suitable kind of gasification oven, such as a rotating oven, a fluid bed reactor, and the like.
  • the temperature of the oven is preferably higher than the temperature used in the pyrolysis reactor and is preferably 800 - 1200 °C, more preferably 1000 - 1100 °C.
  • Such high temperatures may be reached by a burner that is typically operated using natural gas (in particular during start-up of the process) or synthesis gas produced by the process of the present invention (once the process is operational).
  • the solid residue is brought in contact with a gaseous reaction medium in the gasification oven.
  • the gaseous reaction medium may be a gas comprising oxygen and/or water, and is preferably a gas comprising molecular oxygen (O 2 ). Air may be used for this purpose.
  • a gas stream enriched in molecular oxygen or consisting essentially of molecular oxygen is used in order to limit the presence of nitrogen at the high temperature gasification step.
  • the presence of nitrogen in this gasification step generally leads to the formation of nitrogen oxides (NO x ) which is an undesirable pollutant.
  • the pyrolysis residue reacts with the gaseous reaction medium to form a coke gas, which coke gas comprises at least part of the carbon and hydrocarbons of the pyrolysis residue in the form of carbon monoxide (CO) and methane (CH 4 ).
  • coke residue which residue can be liquid, solid or partly liquid and partly solid and mainly comprises minerals that were present in the feed stream. It was found that the coke gas still contained a considerable amount of useful hydrocarbons that could be converted to synthesis gas, thereby increasing the yield of synthesis gas of the method.
  • the method according to the invention is suitable for pyrolysing many different types of biomass.
  • the method is in particular suitable for pyrolysis of organic materials having a relative low mineral content, e.g . organic materials with a mineral content of 8 wt.% or less, preferably a mineral content of 3 wt.% or less.
  • Reason for this is that the amount of coke residue is minimized.
  • the method of the present invention may include a drying step prior to the first step, in which the water content of the feed is reduced.
  • the resulting dried feed preferably comprises less than 20 wt.%, more preferably less than 15 wt.%.
  • the drying step is preferably conducted with waste heat generated in the first and second step.
  • the method of the present invention may further comprise a third step, wherein the pyrolysis gas and coke gas are contacted with oxygen or an oxygen containing gas stream, such as air, and heated with a burner to a temperature of preferably 1200 - 2000 °C, more preferably 1200 - 1600 °C.
  • oxygen or an oxygen containing gas stream such as air
  • the addition of oxygen in this step reduces formation of nitrogen oxide (NO x ).
  • NO x nitrogen oxide
  • Preferably all, or substantially all ( e.g . more than 99 wt.%) of the hydrocarbons present in the pyrolysis and coke gas are converted to synthesis gas in this step.
  • This step may be carried out using a burner, e.g . an Oxy-Fuel Burner, wherein methane is combusted using pure oxygen.
  • the synthesis gas obtained in the third step may be quenched by contacting it with water at a temperature that is sufficiently high to convert at least part of said water into hydrogen and oxygen, thus producing synthesis gas enriched in hydrogen and oxygen.
  • the synthesis gas has a temperature of 1000 - 2000 °C when bringing it in contact with water. Because of this high temperature, at least part of the water is decomposed into H 2 and O 2 when brought in contact with the gas. This process, called thermal dissociation, enriches the synthesis gas with H 2 and O 2 . Such enrichment in H 2 and O 2 adds considerably to the calorific value of the synthesis gas, viz . the amount of heat released during the combustion of a certain volume of the gas is increased.
  • the quality of the synthesis gas is increased by the quenching step.
  • Quenching may be done in a quencher.
  • the temperature in the quencher prior to quenching is at least about 1200 °C, more preferably 1250-2000 °C, even more preferably about 1300-1600 °C, e.g . about 1350 °C.
  • the obtained synthesis gas may be cooled by bringing it in heat-exchanging contact with e.g . boiling water.
  • water is evaporated to steam, which steam can be used for example as a heat source in the pyrolysis reactor, as a heat source in a possible drying step, or for generating electric power.
  • the synthesis gas may further be treated with conventional gas treatments, and purified with for example scrubbers, such as H 2 S scrubbers and/or HCl scrubbers, dust removers, etc .
  • any sulfur compounds, such as H 2 S and dust therefrom, are preferably removed from the synthesis gas.
  • the synthesis gas thus produced can be employed for various applications, including generation of heat and/or work (electricity) and/or as starting material for chemical synthesis. It was found that the coke residue obtained in the second step could be used as fertilizer.
  • FIG. 1 is a schematic representation of an embodiment of the method according to the present invention.
  • solid and/or liquid feed comprising hydrocarbons is fed to dryer (1).
  • the resulting dried feed comprises 10-20 wt.%. water and is fed to pyrolysis reactor (2).
  • a temperature of about 800 °C is provided by using a burner.
  • pyrolysis gas and pyrolysis residue are obtained.
  • the pyrolysis residue is then fed to gasification oven (3), where it is heated in the presence of an oxygen and/or water (steam) containing gas to about 1000 °C, obtaining a coke gas and a coke residue.
  • the pyrolysis gas and the coke gas are fed to converter (4), wherein these gases were heated to about 1400 °C under the addition of an oxygen containing gas.
  • the thus obtained synthesis gas is led to quencher (5), with the temperature of the synthesis gas still being 1400 °C.
  • Water is added in the quencher to the hot synthesis gas and a cooled synthesis gas with a heightened concentration H 2 and O 2 is thus obtained.
  • the gas coming from the quench cooler has a temperature of around 1200 °C.
  • the heat from this gas may be recovered in a recuperation section, e.g. using boiler water, which is converted to steam for further use elsewhere.
  • the synthesis gas coming from the recuperator is then subjected to further cleaning steps (7) to remove sulfur compounds, such as H 2 S, acids such as HCl and dust therefrom.
  • the coke residue containing minerals is pelletized in pelletizer (8) and can be used as artificial fertilizer.
  • the hydrocarbons used in the method of the invention can be of any suitable source.
  • the source of hydrocarbons may be organic feeds such as wood or crops, domestic waste or industrial waste.
  • Organic feeds may for example originate from agriculture and silviculture.
  • non-fermentable biomass in particular olive seeds, oranges or grape skins, is used in the method of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Processing Of Solid Wastes (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP08166952A 2008-10-17 2008-10-17 Verfahren und Vorrichtung zur Verschwelung einer Speisung mit Kohlenwasserstoffen und zur Vergasung des Pyrolysrückstandes Ceased EP2177590A1 (de)

Priority Applications (1)

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EP08166952A EP2177590A1 (de) 2008-10-17 2008-10-17 Verfahren und Vorrichtung zur Verschwelung einer Speisung mit Kohlenwasserstoffen und zur Vergasung des Pyrolysrückstandes

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EP08166952A EP2177590A1 (de) 2008-10-17 2008-10-17 Verfahren und Vorrichtung zur Verschwelung einer Speisung mit Kohlenwasserstoffen und zur Vergasung des Pyrolysrückstandes

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012011800A1 (en) * 2010-07-19 2012-01-26 Rl Finance B.V. System and method for thermal cracking of a hydrocarbons comprising mass
WO2012010223A1 (en) * 2010-07-19 2012-01-26 Rl Finance System and method for thermal conversion of carbon based materials
CN102746901A (zh) * 2012-07-16 2012-10-24 侯小兵 两段式热解气化处理系统
ITTO20120427A1 (it) * 2012-05-14 2013-11-15 Pierluigi Martini Apparato per la gassificazione di sostanze solide carboniose contenute in biomasse vergini e in rifiuti.
GB2599374A (en) * 2020-09-25 2022-04-06 Abundia Biomass To Liquids Ltd Converting biomass to LPG
GB2599371A (en) * 2020-09-25 2022-04-06 Abundia Biomass To Liquids Ltd Converting biomass to diesel
GB2599373A (en) * 2020-09-25 2022-04-06 Abundia Biomass To Liquids Ltd Converting biomass to naphtha
GB2599372A (en) * 2020-09-25 2022-04-06 Abundia Biomass To Liquids Ltd Converting biomass to jet-fuel

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4026272A1 (de) * 1990-08-20 1992-02-27 Kurt Kugler Verfahren und einrichtung zur thermischen behandlung von stoffen nach dem wirbelschichtverfahren
US5347068A (en) * 1991-08-01 1994-09-13 Energiewerke Schwarze Pumpe Aktiengesellschaft Method of simultaneous disposal of solid and liquid wastes
EP0653478A1 (de) 1993-11-15 1995-05-17 Klaus Jungk Verfahren und Anlage zur thermischen Verwertung von Abfallstoffen
DE4446803A1 (de) * 1994-12-24 1996-06-27 Noell Energie & Entsorgung Verfahren und Vorrichtung zur thermischen und stofflichen Verwertung von Rest- und Abfallstoffen
FR2792926A1 (fr) * 1999-04-30 2000-11-03 Air Liquide Procede pour la production d'un gaz de synthese a debit regule dans une unite de traitement de dechets
EP1696177A1 (de) * 2005-02-28 2006-08-30 Drechsler, Daniel Integriertes Mehrbrennstoff- Vergasungsverfahren
WO2008104058A1 (en) * 2007-02-27 2008-09-04 Plasco Energy Group Inc. Gasification system with processed feedstock/char conversion and gas reformulation

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4026272A1 (de) * 1990-08-20 1992-02-27 Kurt Kugler Verfahren und einrichtung zur thermischen behandlung von stoffen nach dem wirbelschichtverfahren
US5347068A (en) * 1991-08-01 1994-09-13 Energiewerke Schwarze Pumpe Aktiengesellschaft Method of simultaneous disposal of solid and liquid wastes
EP0653478A1 (de) 1993-11-15 1995-05-17 Klaus Jungk Verfahren und Anlage zur thermischen Verwertung von Abfallstoffen
DE4446803A1 (de) * 1994-12-24 1996-06-27 Noell Energie & Entsorgung Verfahren und Vorrichtung zur thermischen und stofflichen Verwertung von Rest- und Abfallstoffen
FR2792926A1 (fr) * 1999-04-30 2000-11-03 Air Liquide Procede pour la production d'un gaz de synthese a debit regule dans une unite de traitement de dechets
EP1696177A1 (de) * 2005-02-28 2006-08-30 Drechsler, Daniel Integriertes Mehrbrennstoff- Vergasungsverfahren
WO2008104058A1 (en) * 2007-02-27 2008-09-04 Plasco Energy Group Inc. Gasification system with processed feedstock/char conversion and gas reformulation

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012011800A1 (en) * 2010-07-19 2012-01-26 Rl Finance B.V. System and method for thermal cracking of a hydrocarbons comprising mass
WO2012010223A1 (en) * 2010-07-19 2012-01-26 Rl Finance System and method for thermal conversion of carbon based materials
ITTO20120427A1 (it) * 2012-05-14 2013-11-15 Pierluigi Martini Apparato per la gassificazione di sostanze solide carboniose contenute in biomasse vergini e in rifiuti.
CN102746901A (zh) * 2012-07-16 2012-10-24 侯小兵 两段式热解气化处理系统
GB2599374A (en) * 2020-09-25 2022-04-06 Abundia Biomass To Liquids Ltd Converting biomass to LPG
GB2599371A (en) * 2020-09-25 2022-04-06 Abundia Biomass To Liquids Ltd Converting biomass to diesel
GB2599373A (en) * 2020-09-25 2022-04-06 Abundia Biomass To Liquids Ltd Converting biomass to naphtha
GB2599372A (en) * 2020-09-25 2022-04-06 Abundia Biomass To Liquids Ltd Converting biomass to jet-fuel

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