WO2009027007A2 - Method and apparatus for the production of syngas from heavy oil - Google Patents
Method and apparatus for the production of syngas from heavy oil Download PDFInfo
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- WO2009027007A2 WO2009027007A2 PCT/EP2008/006439 EP2008006439W WO2009027007A2 WO 2009027007 A2 WO2009027007 A2 WO 2009027007A2 EP 2008006439 W EP2008006439 W EP 2008006439W WO 2009027007 A2 WO2009027007 A2 WO 2009027007A2
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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
- C01B3/32—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
- C01B3/36—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 oxygen or mixtures containing oxygen as gasifying agents
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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
- 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
- C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
- C01B2203/0255—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a non-catalytic partial oxidation step
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- 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
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/049—Composition of the impurity the impurity being carbon
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0872—Methods of cooling
- C01B2203/0877—Methods of cooling by direct injection of fluid
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1252—Cyclic or aromatic hydrocarbons
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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
- 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 method for producing a carbon monoxide and hydrogen-containing gas (synthesis gas) by partial oxidation of a higher-boiling hydrocarbons (heavy oil) containing insert in one
- the invention relates to a device for carrying out the method.
- Carbon monoxide and / or hydrogen-containing gas mixtures are important starting materials for the production of a large number of products, such as ammonia, methanol or even synthetic fuels.
- a process widely used in industry for producing synthesis gases or their precursors from hydrocarbons in synthesis gas plants is partial oxidation.
- the heat required for the reaction is generated by incomplete (partial) oxidation of the hydrocarbons in use.
- the POX reactor is supplied with oxygen in an amount which is insufficient for complete conversion of the hydrocarbons.
- the soot removed from the gasification product is a valuable raw material, which is why it is separated from the wastewater produced by quenching and / or water scrubbing and fed to a material and / or energetic use.
- soot makes sense for the soot to be recycled as an insert into the POX reactor and converted there to carbon monoxide.
- the economy of the use of soot depends crucially on how high the effort for the separation of the soot from the wastewater and possibly its treatment to a feedstock.
- soot-laden wastewater is mixed with naphtha to form a dispersion. While the majority of the ash contained in the wastewater remains in the water phase, the soot, which is wetted by naphtha much better than water, almost completely in the
- the soot-containing naphtha fraction is first withdrawn from the decanter and mixed with heavy oil. From the mixture of substances thus produced, the naphtha is subsequently separated by distillation and stripping. The remaining mixture of heavy oil and carbon black is diluted with fresh heavy oil and recycled as an insert into the reactor of the heavy oil POX.
- the soot-free water fraction from the decanter is depressurized, with light hydrocarbons dissolved in the water going into the gas phase. Both these light hydrocarbons as well as the distilled and the stripped naphtha are liquefied by cooling, stored and later re-loaded with soot Wastewater mixed. Because of the large expenditure on equipment and energy, this process is only used in large plants (> 50,000 m N 3 / h synthesis gas).
- naphtha is available as a hydrocarbon-containing feed, even smaller amounts of synthesis gas can be produced economically by partial oxidation in a so-called naphtha POX.
- wastewater laden with soot also accumulates here, from which, according to the state of the art, the soot is separated off and returned to the POX reactor as an insert, the outlay for soot recirculation is, however, significantly lower in a heavy oil POX.
- a dispersion is produced according to the prior art from the soot-laden wastewater and naphtha, which is introduced into a decanter and there separated into a soot-containing naphtha fraction and a largely soot-free water fraction.
- the naphtha fraction containing carbon black withdrawn from the decanter is then recycled as an insert into the reactor of the naphtha POX without further treatment, while the soot-free water fraction is discharged to a wastewater treatment plant.
- the object of the present invention is therefore to provide a method of the type mentioned above and an apparatus for carrying out the method, which allow synthesis gases from heavy oil-containing inserts to produce more economically than is possible in the prior art.
- the stated object is achieved according to the method according to the invention that the anhydrous naphtha / carbon black mixture is fed to the POX reactor together with heavy oil as an insert.
- the cost-effectiveness of the process according to the invention depends crucially on the level of naphtha content in the hydrocarbon-containing feed to the POX reactor.
- a preferred embodiment of The method according to the invention therefore envisages mixing the soot removal wastewater laden with soot only with the minimum amount of naphtha required in terms of process technology.
- minimum amount of naphtha is that naphtha to understand that is just sufficient to reduce the soot in the largely soot-free water fraction to a maximum allowable residual concentration, which is typically less than 200Gew.-ppm.
- the invention relates to a device for producing a carbon monoxide and hydrogen-containing gas (synthesis gas), comprising a gasification device (POX reactor) for recovering a gasification product by partial oxidation of a higher boiling hydrocarbons (heavy oil) containing insert, a means for cooling and washing the in the POX reactor recoverable gasification product, a first mixing device for mixing incurred in the synthesis gas production, soot-laden wastewater with naphtha and a separator for separating the dispersion produced in the first mixing device into a substantially soot-free water fraction and an anhydrous naphtha / carbon black mixture.
- a gasification device POX reactor
- a gasification device for recovering a gasification product by partial oxidation of a higher boiling hydrocarbons (heavy oil) containing insert
- a means for cooling and washing the in the POX reactor recoverable gasification product a first mixing device for mixing incurred in the synthesis gas production, soot-laden wastewater with naphtha and a separator for
- the stated object is achieved in that it comprises a second mixing device into which heavy oil and the naphtha / carbon black mixture produced in the separator can be introduced and from which a heavy oil, naphtha and carbon black containing mixture as an insert to the POX reactor is removable ,
- the separating device is a decanter.
- the device according to the invention expediently comprises a control device via which the mixing device always loads the soot removal from the soot laden with soot Wastewater of the heavy oil POX required minimum amount of naphtha can be fed.
- the invention is particularly suitable to replace the expensive feedstock naphtha to a large extent by considerably cheaper heavy oil in existing synthesis gas plants in which a synthesis gas is produced by partial oxidation of naphtha.
- a complex conversion of the system is not necessary for this purpose, since existing plant parts can be used virtually unchanged.
- Hydrocarbons produced by partial oxidation synthesis gas cooling and scrubbing with water, a synthesis gas containing hydrogen and carbon monoxide Hydrocarbons produced by partial oxidation synthesis gas cooling and scrubbing with water, a synthesis gas containing hydrogen and carbon monoxide.
- Partial oxidation is converted into a mainly hydrogen and carbon monoxide, but also carbon black-containing gasification product 4.
- the gasification product 4 is cooled and freed from soot, whereby a loaded with soot wastewater 5 and the soot-free synthesis gas 6 are generated.
- the loaded with soot wastewater 5 is then introduced into the mixing device M1 and mixed with naphtha 7, which is simultaneously supplied volume-controlled via the control element a, to form a dispersion.
- the soot from the wastewater which is much better wetted by naphtha than water, goes into the naphthaphase, while in the wastewater 5 contained ash remains in the water phase.
- the mixing device M1 is always supplied only the minimum amount of naphtha, which is required to bring the soot content in the water phase below a predetermined limit.
- the dispersion is withdrawn from the mixing device M1 and introduced into the separator D.
- the separating device D is a decanter, then after a residence time of typically 2 to 5 minutes from the top of the decanter a largely anhydrous naphtha / soot mixture 9 and over its bottom a substantially soot-free Water fraction 10 deducted.
- the naphtha / soot mixture 9 is returned before the POX reactor R, mixed in the mixer M2 with heavy oil 11 and fed via line 1, as part of the insert, the POX reactor R.
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Abstract
Description
Beschreibung description
Verfahren und Vorrichtung zur Erzeugung von Synthesegas aus SchwerölProcess and apparatus for producing synthesis gas from heavy oil
Die Erfindung betrifft ein Verfahren zur Erzeugung eines Kohlenmonoxid und Wasserstoff enthaltenden Gases (Synthesegas) durch Partielle Oxidation eines höher siedende Kohlenwasserstoffe (Schweröl) enthaltenden Einsatzes in einerThe invention relates to a method for producing a carbon monoxide and hydrogen-containing gas (synthesis gas) by partial oxidation of a higher-boiling hydrocarbons (heavy oil) containing insert in one
Vergasungseinrichtung (POX-Reaktor) und der Abkühlung und Wäsche des im POX- Reaktor gewonnenen Vergasungsproduktes, wobei anfallendes, mit Ruß beladenes Abwasser mit Naphtha vermischt und anschließend in eine Trenneinrichtung eingeleitet wird, aus der eine weitgehend rußfreie Wasserfraktion und ein wasserfreies Naphtha/Ruß-Gemisch getrennt abgezogen werden.Gasification device (POX reactor) and the cooling and scrubbing of the gasification product obtained in the POX reactor, whereby resulting wastewater laden with soot is mixed with naphtha and then introduced into a separation device from which a largely soot-free water fraction and anhydrous naphtha / soot Mixture be withdrawn separately.
Weiterhin betrifft die Erfindung eine Vorrichtung zur Durchführung des Verfahrens.Furthermore, the invention relates to a device for carrying out the method.
Kohlenmonoxid und/oder Wasserstoff enthaltende Gasgemische, sog. Synthesegase, sind wichtige Ausgangsstoffe zur Herstellung einer Vielzahl von Produkten, wie Ammoniak, Methanol oder auch synthetische Kraftstoffe. Ein in der Industrie weit verbreitetes Verfahren, mit dem aus Kohlenwasserstoffen in Synthesegasanlagen Synthesegase bzw. deren Vorstufen erzeugt werden, ist die Partielle Oxidation. Hierbei wird ein i. AIIg. vorgewärmter kohlenwasserstoffhaltiger Einsatz in einem Reaktor (POX-Reaktor) bei Temperaturen zwischen 1 300 und 1 5000C und Drücken bis zu 100 bar mit Wasserdampf und einem Oxidationsmittel zu einem Vergasungsprodukt umgesetzt, das zu großen Teilen aus Wasserstoff (H2), Kohlenmonoxid (CO), Kohlendioxid (CO2) und Wasser besteht. Die für die Reaktion erforderliche Wärme wird durch unvollständige (partielle) Oxidation der im Einsatz befindlichen Kohlenwasserstoffe erzeugt. Dem POX-Reaktor wird hierzu Sauerstoff in einer Menge zugeführt, die für eine vollständige Umsetzung der Kohlenwasserstoffe nicht ausreichend ist.Carbon monoxide and / or hydrogen-containing gas mixtures, so-called synthesis gases, are important starting materials for the production of a large number of products, such as ammonia, methanol or even synthetic fuels. A process widely used in industry for producing synthesis gases or their precursors from hydrocarbons in synthesis gas plants is partial oxidation. Here is an i. AIIg. preheated hydrocarbonaceous use in a reactor (POX reactor) at temperatures between 1 300 and 1 500 0 C and pressures up to 100 bar reacted with water vapor and an oxidizing agent to a gasification product consisting to a large extent of hydrogen (H 2 ), carbon monoxide ( CO), carbon dioxide (CO 2 ) and water. The heat required for the reaction is generated by incomplete (partial) oxidation of the hydrocarbons in use. For this purpose, the POX reactor is supplied with oxygen in an amount which is insufficient for complete conversion of the hydrocarbons.
Bei der Partiellen Oxidation entstehen neben gasförmigen Komponenten auch Feststoffe, wie Ruß und Asche, die aus dem Vergasungsprodukt entfernt werden müssen, bevor es weiter aufbereitet werden kann. Das mit einer Temperatur von mehr als 1 3000C aus dem POX-Reaktor austretende Vergasungsprodukt wird nach dem Stand der Technik zunächst abgekühlt und anschließend einer Wasserwäsche unterzogen. Erfolgt die Abkühlung in direktem Kontakt mit Wasser (Quenchen), so wird bereits in diesem Verfahrensschritt ein Großteil der Feststoffe aus dem Vergasungsprodukt ausgewaschen und geht in das zum quenchen verwendete Wasser (Quenchwasser) über. In der Wasserwäsche erfolgt eine Feinreinigung, bei der ein Synthesegas erzeugt wird, das einen Feststoffgehalt aufweist, der typischer Weise unterhalb von 1 mg/m3 liegt.In the case of partial oxidation, in addition to gaseous components, solids such as soot and ash, which must be removed from the gasification product before it can be further processed, are formed. The exiting with a temperature of more than 1300 0 C in the POX reactor gasification product will according to the prior art is first cooled, and then a water wash subjected. If the cooling takes place in direct contact with water (quenching), a large part of the solids is already washed out of the gasification product in this process step and passes into the water used for quenching (quench water). In the water wash a fine cleaning is carried out, in which a synthesis gas is produced, which has a solids content, which is typically below 1 mg / m 3 .
Der aus dem Vergasungsprodukt entfernte Ruß stellt einen wertvollen Rohstoff dar, weshalb er aus dem durch Quenchen und/oder Wasserwäsche erzeugten Abwasser abgetrennt und einer stofflichen und/oder energetischen Nutzung zugeführt wird.The soot removed from the gasification product is a valuable raw material, which is why it is separated from the wastewater produced by quenching and / or water scrubbing and fed to a material and / or energetic use.
Sinnvoller Weise wird der Ruß als Einsatz in den POX-Reaktor zurückgeführt und dort zu Kohlenmonoxid umgesetzt. Die Wirtschaftlichkeit der Rußnutzung hängt entscheidend davon ab, wie hoch der Aufwand für die Abtrennung des Rußes aus dem Abwasser und ggf. seiner Aufbereitung zu einem Einsatzstoff ist.It makes sense for the soot to be recycled as an insert into the POX reactor and converted there to carbon monoxide. The economy of the use of soot depends crucially on how high the effort for the separation of the soot from the wastewater and possibly its treatment to a feedstock.
In einer Synthesegasanlage, in der Schweröl durch Partielle Oxidation vergast wird (Schweröl-POX), wird nach dem Stand der Technik mit Ruß beladenes Abwasser mit Naphtha zu einer Dispersion vermischt. Während der überwiegende Teil der im Abwasser enthaltenen Asche in der Wasserphase verbleibt, geht der Ruß, der von Naphtha wesentlich besser benetz wird, als von Wasser, nahezu vollständig in dieIn a synthesis gas plant, in which heavy oil is gasified by partial oxidation (heavy oil POX), according to the prior art soot-laden wastewater is mixed with naphtha to form a dispersion. While the majority of the ash contained in the wastewater remains in the water phase, the soot, which is wetted by naphtha much better than water, almost completely in the
Naphthaphase über. Die Dispersion wird anschließend in einen Dekanter eingeleitet, in der es sich in eine Ruß enthaltende Naphthafraktion und eine weitgehend rußfreie Wasserfraktion trennt. Das im Vergleich zu Schweröl teuere Naphtha wird zurückgewonnen und erneut für die Rußabtrennung eingesetzt.Naphthaphase over. The dispersion is then introduced into a decanter in which it separates into a soot-containing naphtha fraction and a substantially soot-free water fraction. The expensive in comparison to heavy oil naphtha is recovered and used again for the separation of soot.
Zur Rückgewinnung des Naphthas wird zunächst die Ruß enthaltende Naphthafraktion aus dem Dekanter abgezogen und mit Schweröl vermischt. Aus dem so erzeugten Stoffgemisch wird das Naphtha anschließend durch Destillation und Strippung abgetrennt. Das verbleibende Gemisch aus Schweröl und Ruß wird mit frischem Schweröl verdünnt und als Einsatz in den Reaktor der Schweröl-POX zurückgeführt. Die rußfreie Wasserfraktion aus dem Dekanter wird entspannt, wobei im Wasser gelöste leichte Kohlenwasserstoffe in die Gasphase übergehen. Sowohl diese leichten Kohlenwasserstoffe als auch das abdestillierte und das abgestrippte Naphtha werden durch Abkühlung verflüssigt, zwischengelagert und später erneut mit Ruß beladenem Abwasser gemischt. Wegen des großen apparativen und energetischen Aufwands wird dieses Verfahren nur in Großanlagen (> 50000 mN 3/h Synthesegas) angewandt.To recover the naphtha, the soot-containing naphtha fraction is first withdrawn from the decanter and mixed with heavy oil. From the mixture of substances thus produced, the naphtha is subsequently separated by distillation and stripping. The remaining mixture of heavy oil and carbon black is diluted with fresh heavy oil and recycled as an insert into the reactor of the heavy oil POX. The soot-free water fraction from the decanter is depressurized, with light hydrocarbons dissolved in the water going into the gas phase. Both these light hydrocarbons as well as the distilled and the stripped naphtha are liquefied by cooling, stored and later re-loaded with soot Wastewater mixed. Because of the large expenditure on equipment and energy, this process is only used in large plants (> 50,000 m N 3 / h synthesis gas).
Steht Naphtha als kohlenwasserstoffhaltiger Einsatz zur Verfügung, können auch geringere Synthesegasmengen wirtschaftlich durch Partielle Oxidation in einer sog. Naphtha-POX erzeugt werden. Zwar fällt auch hier, genauso wie in einer Schweröl- POX, mit Ruß beladenes Abwasser an, aus dem nach dem Stand der Technik der Ruß abgetrennt und als Einsatz in den POX-Reaktor zurückgeführt wird, allerdings ist der Aufwand für die Rußrückführung deutlich geringer als in einer Schweröl-POX. Auch in einer Naphtha-POX wird nach dem Stand der Technik aus dem mit Ruß beladenen Abwasser und Naphtha eine Dispersion erzeugt, die in einen Dekanter eingeleitet und dort in eine Ruß enthaltende Naphthafraktion und eine weitgehend rußfreie Wasserfraktion getrennt wird. Die aus dem Dekanter abgezogene Ruß enthaltende Naphthafraktion wird jedoch anschließend ohne weitere Aufbereitung als Einsatz in den Reaktor der Naphtha-POX zurückgeführt, während die rußfreie Wasserfraktion an eine Abwasseraufbereitungsanlage abgegeben wird.If naphtha is available as a hydrocarbon-containing feed, even smaller amounts of synthesis gas can be produced economically by partial oxidation in a so-called naphtha POX. Although, as in a heavy oil POX, wastewater laden with soot also accumulates here, from which, according to the state of the art, the soot is separated off and returned to the POX reactor as an insert, the outlay for soot recirculation is, however, significantly lower in a heavy oil POX. Also in a naphtha POX, a dispersion is produced according to the prior art from the soot-laden wastewater and naphtha, which is introduced into a decanter and there separated into a soot-containing naphtha fraction and a largely soot-free water fraction. However, the naphtha fraction containing carbon black withdrawn from the decanter is then recycled as an insert into the reactor of the naphtha POX without further treatment, while the soot-free water fraction is discharged to a wastewater treatment plant.
Die Preise für Naphtha und Schweröl entwickeln sich bereits seit einigen Jahren immer stärker auseinander, so dass es immer schwieriger wird, kleinere Synthesegasmengen durch die Vergasung von Naphtha zu wirtschaftlich vertretbaren Kosten zu erzeugen.The prices for naphtha and heavy oil have been developing more and more for several years, so that it is becoming increasingly difficult to produce smaller quantities of synthesis gas by the gasification of naphtha at economically reasonable cost.
Aufgabe der vorliegenden Erfindung ist es daher ein Verfahren der eingangs genannten Art sowie eine Vorrichtung zur Durchführung des Verfahrens anzugeben, die es erlauben, Synthesegase aus Schweröl enthaltenden Einsätzen wirtschaftlicher zu erzeugen, als dies nach dem Stand der Technik möglich ist.The object of the present invention is therefore to provide a method of the type mentioned above and an apparatus for carrying out the method, which allow synthesis gases from heavy oil-containing inserts to produce more economically than is possible in the prior art.
Die gestellte Aufgabe wird verfahrensseitig erfindungsgemäß dadurch gelöst, dass das wasserfreie Naphtha/Ruß-Gemisch dem POX-Reaktor zusammen mit Schweröl als Einsatz zugeführt wird.The stated object is achieved according to the method according to the invention that the anhydrous naphtha / carbon black mixture is fed to the POX reactor together with heavy oil as an insert.
Die Wirtschaftlichkeit des erfindungsgemäßen Verfahrens hängt entscheidend von der Höhe des Naphthaanteils im kohlenwasserstoffhaltigen Einsatz zum POX-Reaktor ab. Je weniger teueres Naphtha über das wasserfreie Naphtha/Ruß-Gemisch in den kohlenwasserstoffhaltigen Einsatz eingebracht wird, desto höher kann der Anteil des preiswerteren Schweröls liegen. Eine bevorzugte Ausgestaltung des erfindungsgemäßen Verfahrens sieht daher vor, zur Rußabtrennung das mit Ruß beladene Abwasser nur mit der prozesstechnisch erforderliche Mindestmenge an Naphtha zu vermischen. Unter der prozesstechnisch erforderlichen Mindestmenge an Naphtha ist dabei diejenige Naphthamenge zu verstehen, die gerade ausreicht den Ruß in der weitgehend rußfreien Wasserfraktion bis auf eine maximal zulässige Restkonzentration, die typischer Weise kleiner ist als 200Gew.-ppm, zu reduzieren.The cost-effectiveness of the process according to the invention depends crucially on the level of naphtha content in the hydrocarbon-containing feed to the POX reactor. The less expensive naphtha is introduced via the anhydrous naphtha / carbon black mixture in the hydrocarbon-containing use, the higher the proportion of cheaper heavy oil can be. A preferred embodiment of The method according to the invention therefore envisages mixing the soot removal wastewater laden with soot only with the minimum amount of naphtha required in terms of process technology. Under the process technically required minimum amount of naphtha is that naphtha to understand that is just sufficient to reduce the soot in the largely soot-free water fraction to a maximum allowable residual concentration, which is typically less than 200Gew.-ppm.
Um die Rußabtrennung aus dem Ruß enthaltenden Abwasser auch bei schwankenden Betriebsverhältnissen stets mit der prozesstechnisch erforderliche-Mindestmenge an Naphtha durchführen zu können, sieht eine Ausgestaltung des erfindungsgemäßen Verfahrens vor, dass Naphtha mit geregeltem Massenstrom in die Mischeinrichtung eingeleitet wird, wobei der Sollwert (die prozesstechnisch erforderliche Mindestmenge für einen aktuellen Betriebszustand) für den Naphthastrom aus Menge und Rußbeladung des der Mischeinrichtung zugeführten mit Ruß beladenen Abwassers berechnet wird, wozu die prozessrelevanten Werte kontinuierlich gemessen werden.In order to carry out the removal of soot from the soot-containing wastewater even with fluctuating operating conditions always with the process technology required minimum amount of naphtha, provides an embodiment of the method according to the invention that naphtha is introduced with controlled mass flow into the mixing device, the setpoint (the process technology required minimum amount for a current operating state) is calculated for the naphtha from the amount and soot loading of the soot-laden waste water fed to the mixing device, for which the process-relevant values are continuously measured.
Weiterhin betrifft die Erfindung eine Vorrichtung zur Erzeugung eines Kohlenmonoxid und Wasserstoff enthaltenden Gases (Synthesegas), umfassend eine Vergasungseinrichtung (POX-Reaktor) zur Gewinnung eines Vergasungsproduktes durch Partielle Oxidation eines höher siedende Kohlenwasserstoffe (Schweröl) enthaltenden Einsatzes, eine Einrichtung zur Abkühlung und Wäsche des im POX- Reaktor gewinnbaren Vergasungsproduktes, eine erste Mischeinrichtung zur Mischung von bei der Synthesegaserzeugung anfallendem, rußbeladenem Abwasser mit Naphtha sowie eine Trenneinrichtung zur Trennung der in der ersten Mischeinrichtung erzeugbaren Dispersion in eine weitgehend rußfreie Wasserfraktion und ein wasserfreies Naphtha/Ruß-Gemisch.Furthermore, the invention relates to a device for producing a carbon monoxide and hydrogen-containing gas (synthesis gas), comprising a gasification device (POX reactor) for recovering a gasification product by partial oxidation of a higher boiling hydrocarbons (heavy oil) containing insert, a means for cooling and washing the in the POX reactor recoverable gasification product, a first mixing device for mixing incurred in the synthesis gas production, soot-laden wastewater with naphtha and a separator for separating the dispersion produced in the first mixing device into a substantially soot-free water fraction and an anhydrous naphtha / carbon black mixture.
Vorrichtungsseitig wird die gestellte Aufgabe dadurch gelöst, dass sie eine zweite Mischeinrichtung umfasst, in die Schweröl und das in der Trenneinrichtung erzeugte Naphtha/Ruß-Gemisch einleitbar sind und aus der ein Schweröl, Naphtha und Ruß enthaltendes Stoffgemisch als Einsatz zum POX-Reaktor abziehbar ist.On the device side, the stated object is achieved in that it comprises a second mixing device into which heavy oil and the naphtha / carbon black mixture produced in the separator can be introduced and from which a heavy oil, naphtha and carbon black containing mixture as an insert to the POX reactor is removable ,
Eine vorteilhafte Weiterbildung der erfindungsgemäßen Vorrichtung sieht vor, dass es sich bei der Trenneinrichtung um einen Dekanter handelt. Um auch bei schwankenden Betriebsverhältnissen das Naphtha stets mit der für die Rußabtrennung aus dem mit Ruß beladenen Abwasser erforderlichen Mindestmenge der Mischeinrichtung zuführen zu können, umfasst die erfindungsgemäße Vorrichtung zweckmäßiger Weise eine Regeleinrichtung, über die der Mischeinrichtung stets die für die Rußabtrennung aus dem mit Ruß beladenen Abwasser der Schweröl-POX erforderliche Mindestmenge an Naphtha zuführbar ist.An advantageous development of the device according to the invention provides that the separating device is a decanter. In order to always be able to supply the naphtha with the minimum amount of mixing device required for soot removal from the wastewater laden with soot, the device according to the invention expediently comprises a control device via which the mixing device always loads the soot removal from the soot laden with soot Wastewater of the heavy oil POX required minimum amount of naphtha can be fed.
Die Erfindung ist besonders dazu geeignet, in bestehenden Synthesegasanlagen, in welchen ein Synthesegas durch Partielle Oxidation von Naphtha erzeugt wird, den teueren Einsatzstoff Naphtha zu einem großen Teil durch erheblich billigeres Schweröl zu ersetzen. Ein aufwendiger Umbau der Anlage ist hierzu nicht nötig, da bereits vorhandene Anlagenteile praktisch unverändert weiter verwendet werden können.The invention is particularly suitable to replace the expensive feedstock naphtha to a large extent by considerably cheaper heavy oil in existing synthesis gas plants in which a synthesis gas is produced by partial oxidation of naphtha. A complex conversion of the system is not necessary for this purpose, since existing plant parts can be used virtually unchanged.
Im Folgenden soll die Erfindung anhand eines in der Figur schematisch dargestellten Ausführungsbeispiels näher erläutert werden, in welchem aus höher siedendenIn the following, the invention will be explained in more detail with reference to an embodiment schematically illustrated in the figure, in which from higher boiling
Kohlenwasserstoffen durch Partielle Oxidation Synthesegaskühlung und Wäsche mit Wasser ein Wasserstoff und Kohlenmonoxid enthaltendes Synthesegas erzeugt wird.Hydrocarbons produced by partial oxidation synthesis gas cooling and scrubbing with water, a synthesis gas containing hydrogen and carbon monoxide.
Über die Leitung 1 wird dem POX-Reaktor R ein höher siedende Kohlenwasserstoffe enthaltender Einsatz 1 zugeführt, der mit Sauerstoff 2 und Wasserdampf 3 durchVia the line 1, the POX reactor R, a higher-boiling hydrocarbons containing insert 1 is supplied with the oxygen 2 and water vapor 3 by
Partielle Oxidation zu einem vor allem Wasserstoff und Kohlenmonoxid, aber auch Ruß enthaltenden Vergasungsprodukt 4 umgesetzt wird. In der Abkühl- und Wascheinrichtung W wird das Vergasungsprodukt 4 abgekühlt und von Ruß befreit, wobei ein mit Ruß beladenes Abwasser 5 sowie das rußfreie Synthesegas 6 erzeugt werden. Das mit Ruß beladene Abwasser 5 wird anschließend in die Mischeinrichtung M1 eingeleitet und mit Naphtha 7, das gleichzeitig über das Regelorgan a mengengeregelt zugeführt wird, zu einer Dispersion vermischt. Der Ruß aus dem Abwasser, der wesentlich besser von Naphtha als von Wasser benetz wird, geht in die Naphthaphase über, während im Abwasser 5 enthaltene Asche in der Wasserphase verbleibt. Der Mischeinrichtung M1 wird stets nur die Mindestmenge an Naphtha zugeführt, die erforderlich ist, um den Rußgehalt in der Wasserphase unter einen vorgegebenen Grenzwert zu bringen. Über Leitung 8 wird die Dispersion aus der Mischeinrichtung M1 abgezogen und in die Trenneinrichtung D eingeleitet. Handelt es sich bei der Trenneinrichtung D um einen Dekanter, so wird nach einer Verweilzeit von typischerweise 2 bis 5 Minuten vom Kopf des Dekanters ein weitgehend wasserfreies Naphtha/Ruß-Gemisch 9 und über dessen Boden eine weitgehend rußfreie Wasserfraktion 10 abgezogen. Das Naphtha/Ruß-Gemisch 9 wird vor den POX- Reaktor R zurückgeführt, in der Mischeinrichtung M2 mit Schweröl 11 gemischt und über Leitung 1 , als Teil des Einsatzes, dem POX-Reaktor R zugeführt. Partial oxidation is converted into a mainly hydrogen and carbon monoxide, but also carbon black-containing gasification product 4. In the cooling and washing device W, the gasification product 4 is cooled and freed from soot, whereby a loaded with soot wastewater 5 and the soot-free synthesis gas 6 are generated. The loaded with soot wastewater 5 is then introduced into the mixing device M1 and mixed with naphtha 7, which is simultaneously supplied volume-controlled via the control element a, to form a dispersion. The soot from the wastewater, which is much better wetted by naphtha than water, goes into the naphthaphase, while in the wastewater 5 contained ash remains in the water phase. The mixing device M1 is always supplied only the minimum amount of naphtha, which is required to bring the soot content in the water phase below a predetermined limit. Via line 8, the dispersion is withdrawn from the mixing device M1 and introduced into the separator D. If the separating device D is a decanter, then after a residence time of typically 2 to 5 minutes from the top of the decanter a largely anhydrous naphtha / soot mixture 9 and over its bottom a substantially soot-free Water fraction 10 deducted. The naphtha / soot mixture 9 is returned before the POX reactor R, mixed in the mixer M2 with heavy oil 11 and fed via line 1, as part of the insert, the POX reactor R.
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102007040092.8 | 2007-08-24 | ||
| DE200710040092 DE102007040092A1 (en) | 2007-08-24 | 2007-08-24 | Process and apparatus for producing synthesis gas from heavy oil |
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| Publication Number | Publication Date |
|---|---|
| WO2009027007A2 true WO2009027007A2 (en) | 2009-03-05 |
| WO2009027007A3 WO2009027007A3 (en) | 2009-04-30 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2008/006439 Ceased WO2009027007A2 (en) | 2007-08-24 | 2008-08-05 | Method and apparatus for the production of syngas from heavy oil |
Country Status (3)
| Country | Link |
|---|---|
| DE (1) | DE102007040092A1 (en) |
| TW (1) | TW200927645A (en) |
| WO (1) | WO2009027007A2 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2992906A (en) * | 1958-05-29 | 1961-07-18 | Texaco Inc | Carbon recovery method |
| GB1579070A (en) * | 1977-11-02 | 1980-11-12 | Ased | Process for recovering the soot formed during the production of synthesis gas by partial oxidation of hydrocarbonaceous materials |
| US4205962A (en) * | 1978-04-28 | 1980-06-03 | Texaco Inc. | Process for gas cleaning with reclaimed water |
| WO2000029514A1 (en) * | 1998-11-16 | 2000-05-25 | Texaco Development Corporation | Removal of soot in a gasification system |
-
2007
- 2007-08-24 DE DE200710040092 patent/DE102007040092A1/en not_active Withdrawn
-
2008
- 2008-08-05 WO PCT/EP2008/006439 patent/WO2009027007A2/en not_active Ceased
- 2008-08-22 TW TW97132231A patent/TW200927645A/en unknown
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| Publication number | Publication date |
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| DE102007040092A1 (en) | 2009-02-26 |
| WO2009027007A3 (en) | 2009-04-30 |
| TW200927645A (en) | 2009-07-01 |
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