US20090151254A1 - Process for pyrolysis of glycerol-containing feedstocks - Google Patents

Process for pyrolysis of glycerol-containing feedstocks Download PDF

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Publication number
US20090151254A1
US20090151254A1 US12/333,498 US33349808A US2009151254A1 US 20090151254 A1 US20090151254 A1 US 20090151254A1 US 33349808 A US33349808 A US 33349808A US 2009151254 A1 US2009151254 A1 US 2009151254A1
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Prior art keywords
glycerol
feedstock
pyrolysis
thermal drying
water
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Abandoned
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US12/333,498
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English (en)
Inventor
Hubertus Winkler
Frank Wiessner
Hans-Jorg Zander
Axel Behrens
Wibke Korn
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Linde GmbH
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Linde GmbH
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Assigned to LINDE AKTIENGESELLSCHAFT reassignment LINDE AKTIENGESELLSCHAFT ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BEHRENS, AXEL, KORN, WIBKE, ZANDER, HANS JORG, WIESSNER, FRANK, WINKLER, HUBERTUS
Publication of US20090151254A1 publication Critical patent/US20090151254A1/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • 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
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • 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
    • 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
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • 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
    • C01B2203/1217—Alcohols
    • 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
    • C01B2203/1258—Pre-treatment of the feed
    • 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
    • C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas

Definitions

  • the invention relates to a process for producing a hydrogen-containing product gas (product gas) from a glycerol-containing feedstock as well as a device for implementing the process.
  • Biodiesel is a standardized fuel that is obtained from, e.g., rapeseed oil but also from other plant oils and fats.
  • Plant oils and fats consist of triglycerides, i.e., fatty acid tri-esters of glycerol. This structure causes plant oils and fats to be viscous to solid at normal ambient temperatures, i.e., to have a much higher viscosity than the fuels for which a commercially available diesel engine is designed. Plant oils and fats behave differently in the injection process, and also the combustion proceeds less cleanly.
  • Biodiesel is produced from plant oils and fats by the replacement of glycerol by methanol. Its viscosity corresponds to that of commercially available diesel fuel, which is why it can be easily consumed even in unmodified diesel engines.
  • the glycerol that is separated from the plant oils and fats in the biodiesel production is not obtained in pure form but rather accumulates as a portion of the mixture of materials, which contain larger amounts of contaminants in addition to glycerol.
  • a mixture of materials is, for example, so-called crude glycerol, which has a glycerol content of 80-85%, but in addition also contains water, salts e.g. potassium salts, and organic contaminants (e.g., fatty acids or methanol) as well as residues from the production process in still larger amounts.
  • the crude glycerol is purified in expensive process steps by vacuum distillation, deodorizing and filtration, to the extent that it is sufficient for the strict requirements of the European Pharmacopeia and can be sold to the pharmaceutical industry with a purity of at least 99.5% as a pharmaceutical glycerol.
  • the entire amount of glycerol that accumulates in the biodiesel production can be used in this way. With the foreseeable expansion of the biodiesel production, this will be increasingly more difficult in the future, however, so that other ways of using crude glycerol must be sought.
  • This object is achieved according to the process side of the invention in that a product gas is produced from the glycerol-containing feedstock by separation of undesirable substances and pyrolysis of glycerol.
  • pyrolysis is defined as the thermal decomposition of glycerol in volatile molecules, whereby the decomposition is carried out with the exclusion of oxygen and water or—deviating from the usual definition—in the presence of oxygen and/or water.
  • the invention is based on the experience that when glycerol-containing feedstocks, such as, for example, crude glycerol, are put to direct use by gasification, problems arise—which cannot be overcome or can be overcome only at great expense—owing to the high proportion of contaminants that are present in the feedstocks. Thus, salts lead to corrosion of system parts. Also, organic contaminants are controlled only with difficulty and can result in deposits and the formation of carbon black.
  • glycerol-containing feedstocks such as, for example, crude glycerol
  • One embodiment of the process according to the invention calls for the separation of undesirable substances—already present in the feedstock and/or produced in the implementation of the process according to the invention—and the pyrolysis of glycerol to be implemented simultaneously in one process step.
  • Another embodiment of the process according to the invention calls for a product gas to be obtained from the feedstock in at least two successive process steps, whereby in each of the process steps, undesirable substances are separated and/or glycerol is reacted by pyrolysis.
  • the feedstock according to the invention is preferably subjected to a distillation and/or a thermal drying and/or a filtering on activated carbon and/or a membrane and/or chromatography and/or an ion exchange and/or an ion exclusion and/or a precipitation.
  • the water or steam content in the glycerol-containing fraction that was recovered by separating undesirable substances from the feedstock is set at a value by adding or removing water or steam, which makes it possible to implement a subsequent pyrolysis without the formation of carbon black and with simultaneously minimum energy input.
  • Another embodiment of the process according to the invention calls for the water required for pyrolysis to be fed in more than one step (in a stepped process), whereby the water is fed before and/or during pyrolysis at a suitable location. If pyrolysis is implemented in several successive steps (pyrolysis steps), it is useful for water to be added in each case before a pyrolysis step.
  • water is preferably fed in the form of steam, whereby the steam is sprayed into the glycerol-containing fraction or the glycerol-containing fraction is sprayed into the steam.
  • a portion of the energy required for the subsequent pyrolysis is already introduced with the steam, which results in a reduced heating expense in the pyrolysis reactor and in a reduction of the equipment cost for the pyrolysis reactor.
  • the process according to the invention is suitable in particular for producing a product gas under increased pressure.
  • an expensive compression of the product gas can be eliminated.
  • thermal drying is defined as the feedstock being introduced into a thermal drying system and being subjected there to a thermal treatment.
  • Volatile components such as water and glycerol
  • Volatile components are evaporated and form a gas fraction possibly with other gaseous substances, while solids, such as, for example, salts, are converted into a largely anhydrous solid fraction.
  • Solid and gas fractions are then separated to a large extent from the thermal drying system, which is equipped for this purpose with a suitable system for separating dust and gas, such as, for example, a gravity separator and/or a cyclone and/or a filtering system and/or a water scrubber.
  • glycerol is thermally decomposed, i.e., pyrolyzed into a gas containing hydrogen. Further developing the process according to the invention, it is therefore proposed that the thermal drying of the feedstock be implemented at temperatures in which at least part of the glycerol contained in the feedstock is pyrolyzed. Depending on how much of the glycerol is pyrolyzed in the thermal drying, the gas fraction is subjected to further pyrolysis downstream of the thermal drying.
  • An advantageous embodiment of the process according to the invention calls for the heat that is required for thermal drying of the feedstock to be removed from the hot product gas.
  • fluidized-bed granulators and/or fluidized-bed dryers and/or drum dryers and/or fluid-bed dryers and/or suspension dryers and/or paste dryers are used for thermal drying of the feedstock.
  • Variants of the process according to the invention call for the pyrolysis to be implemented while water and/or steam and/or an oxidizing agent are being fed in, whereby the oxidizing agent is air or oxygen-enriched air or oxygen.
  • the application of oxygen during the pyrolysis step refers to another reaction option.
  • the glycerol will react partly with the oxygen to steam and CO/CO 2 .
  • the benefit is the internally generated heat which is used for the pyrolysis of the remaining glycerol. This results in decreased operating costs owing to an improved heat transfer/balance.
  • This variant will lower the requirement of energy from the externally applied heat (usually methane) but will use some of the glycerol and the applied oxygen to form CO/CO 2 .
  • an aqueous mixture in which the separated substances are present in dissolved and/or suspended form and whose material cannot be used without additional treatment, can accumulate when the process according to the invention is implemented.
  • the waste water represents a waste that has to be shipped to a hazardous waste site at a dump. To keep dumping costs low, an attempt is made to keep the volume of waste to be dumped as small as possible.
  • An embodiment of the process according to the invention therefore calls for the waste water to be subjected to a treatment in which the volume of waste to be deposited is reduced.
  • the waste water is preferably subjected to drying in a thermal drying system, whereby a largely anhydrous solid fraction and a gas fraction are produced. In the most advantageous case, the thus obtained solid fraction can be used economically (e.g., as fertilizer), so that the volume of waste to be dumped drops to zero.
  • An advantageous embodiment of the process according to the invention therefore calls for the heat that is required for thermal drying of waste water to be removed from hot product gas. Based on the heat that is released from the hot product gas to the waste water, volatile components pass from the waste water into the gas phase, by which a gas fraction and a largely anhydrous solid fraction—which is present, for example, as a granulate or powder depending on the drying process that is used—are produced.
  • the hot gas stream that is used for thermal drying of waste water is a part of the product gas, and its heat is transferred in direct heat exchange to the waste water to be dried, thus a further development of the process according to the invention calls for the gas fraction that is produced during drying to preferably be subjected to a water scrubbing system of a water scrubber and then be recycled before pyrolysis.
  • the charged scrubber water is drawn off from the water-scrubber system and mixed in with glycerol-containing feedstock.
  • fluidized-bed granulators and/or fluidized-bed dryers and/or drum dryers and/or fluid-bed dryers and/or suspension dryers and/or paste dryers are preferably used.
  • the invention also relates to a device for implementing the process according to the invention.
  • this object is achieved in that it comprises a pyrolysis system in which a product gas can be produced from the feedstock by separation of contaminants and pyrolysis of the glycerol contained in the feedstock.
  • a preferred embodiment of the device according to the invention calls for the pyrolysis system to consist of a thermal drying system, in which a gas-free and largely anhydrous solid fraction can be produced from the feedstock, whereby based on the temperatures prevailing in the thermal drying system, glycerol that is present in the gas fraction is at least partially pyrolyzed.
  • the thermal drying system comprises a suitable system for separating dust from the gas fraction, so that a largely dust-free product gas can be produced.
  • the thermal drying system is a fluidized-bed granulator and/or a fluidized-bed dryer and/or a drum dryer and/or a fluid-bed dryer and/or a suspension dryer and/or a paste dryer.
  • Such thermal drying systems have been known to one skilled in the art for many years and are available on the market.
  • the pyrolysis system comprises a purification system and a downstream pyrolysis reactor, whereby a prolysis feedstock, which can be reacted into product gas in the pyrolysis reactor by pyrolysis, can be produced in the purification system from the feedstock by separation of contaminants.
  • the purification system is preferably designed as a vacuum distillation system and/or a thermal drying system and/or a filtering system with activated carbon or membrane and/or a chromatography system and/or an ion exchanger and/or an ion exclusion system and/or a precipitating and separating system.
  • a suitable embodiment of the device according to the invention calls for a suitable system with which the water or the steam content of the glycerol-containing fraction—obtained by separation of undesirable substances from the feedstock—can be adjusted preferably to a value that is advantageous for implementing a subsequent pyrolysis by adding or removing water or steam.
  • Another embodiment of the device according to the invention calls for a suitable system with which the water that is required for pyrolysis can be fed to a suitable location in front of the pyrolysis reactor and/or in the pyrolysis reactor in more than one step (in a stepped process). If the pyrolysis is implemented in several pyrolysis reactors that are arranged in series, water can be fed in each case in front of a pyrolysis reactor in a useful way.
  • the device according to the invention preferably comprises a system for mixing steam with the glycerol-containing fraction (mixer), whereby steam can be injected into the glycerol-containing fraction or the glycerol-containing fraction can be injected into the steam.
  • a nozzle via which the glycerol-containing fraction is sprayed as a fine mist into the greatly turbulent steam—is provided, for example, at a suitable location. A portion of the energy required for the subsequent pyrolysis is already introduced with the steam, which results in a reduced heat demand in the pyrolysis reactor and in a reduction of the equipment cost for the pyrolysis reactor.
  • an advantageous variant of the device according to the invention calls for a system for reducing the water content of an aqueous mixture (waste water) whose material cannot be further used and that accumulates when the glycerol-containing feedstock is purified.
  • this system is a thermal drying system, such as, for example, a fluidized-bed granulator and/or a fluidized-bed dryer and/or a drum dryer and/or a fluid-bed dryer and/or a suspension dryer and/or a paste dryer.
  • thermal drying systems have been known to one skilled in the art for years and are available on the market, by such companies as GEA Barr-Rosin, ALL GAIER and FIMA, for example.
  • the thermal drying system is designed so that a largely anhydrous solid fraction and a largely dust-free gas fraction can be produced from the waste water.
  • the thermal drying system is a system in which energy can be fed to the waste water to be dried in direct contact with hot product gas; thus, an advantageous embodiment of the device according to the invention calls for a water scrubbing system into which the dust-charged gas stream that exits from the thermal drying system can be introduced and freed from dust there by water scrubbing before it is recycled and fed to the pyrolysis reactor as feedstock.
  • the charged scrubbing water can be removed from the water scrubber and mixed in with the crude glycerol.
  • This embodiment relates to a unit for producing a product gas, whereby crude glycerol from the biodiesel production is used as a feedstock.
  • the crude glycerol is introduced into the vacuum distillation system V, where it is separated into two streams 2 and 3 .
  • the stream 2 which consists almost exclusively of evaporated glycerol, is sent to the pyrolysis reactor P as a feedstock and is converted there to a hydrogen-containing product gas, which is drawn off via line 4 from the pyrolysis reactor P.
  • Stream 3 from the vacuum distillation system V which consists primarily of water and salts, as well as residues from the biodiesel production, is sent to the granulator G and dried there by means of a part 5 of the hot hydrogen-containing product gas 4 .
  • the salts and other solids contained in stream 3 are converted into a granulate and drawn off via line 6 from the granulator G.
  • a stream which consists primarily of gases and vapors, but in addition also contains solids in dust form, is fed to the water scrubbing system W and purified there.
  • a part of the charged scrubber water from the water scrubbing system W is drawn off via line 8 and introduced together with the crude glycerol via line 1 into the vacuum distillation system V, while the other part 9 is mixed with fresh water 10 and is recycled as scrubbing water in the water scrubber system W.
  • a stream that consists largely of product gas and steam is drawn off from the water scrubber system W and fed together with the glycerol stream 2 to the pyrolysis reactor P.
  • the crude glycerol is heated up to a temperature high enough to evaporate glycerol, and hence separate it from the impurities, and simultaneously crack the glycerol molecules in a pyrolysis reaction.
  • the first step of the two-step process is a purification step, in which glycerol is mainly evaporated, in order to separate it from impurities. Whether pyrolysis takes place in the purification step depends on the applied temperature within the purification. If the temperature is high enough, the pyrolysis of glycerol starts in the purification step.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
US12/333,498 2007-12-13 2008-12-12 Process for pyrolysis of glycerol-containing feedstocks Abandoned US20090151254A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007060166A DE102007060166A1 (de) 2007-12-13 2007-12-13 Verfahren zur Pyrolyse von Glycerin enthaltenden Einsatzstoffen
DE102007060166.4 2007-12-13

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110220848A1 (en) * 2010-03-09 2011-09-15 Linde Aktiengesellschaft Gasification of crude glycerol
WO2014158037A1 (en) 2013-03-27 2014-10-02 Enriquez Erwin P Process for producing carbon from poly-alcohols and the products therefor

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010053290A1 (de) 2010-12-02 2012-06-06 Linde Ag Verfahren und Vorrichtung zur Erzeugung von Wasserstoff aus Glycerin

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110220848A1 (en) * 2010-03-09 2011-09-15 Linde Aktiengesellschaft Gasification of crude glycerol
WO2014158037A1 (en) 2013-03-27 2014-10-02 Enriquez Erwin P Process for producing carbon from poly-alcohols and the products therefor

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