WO2014072033A1 - Method and device for obtaining synthesis gas from a residual gas containing hydrocarbons - Google Patents

Method and device for obtaining synthesis gas from a residual gas containing hydrocarbons Download PDF

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Publication number
WO2014072033A1
WO2014072033A1 PCT/EP2013/003258 EP2013003258W WO2014072033A1 WO 2014072033 A1 WO2014072033 A1 WO 2014072033A1 EP 2013003258 W EP2013003258 W EP 2013003258W WO 2014072033 A1 WO2014072033 A1 WO 2014072033A1
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soot
pox reactor
reactor
process condensate
decanter
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PCT/EP2013/003258
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German (de)
French (fr)
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Jürgen GLASER
Albrecht Heinzel
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Linde Aktiengesellschaft
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Publication of WO2014072033A1 publication Critical patent/WO2014072033A1/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
    • C01B3/32—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
    • 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
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
    • 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
    • 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
    • C10K3/005—Reducing the tar content by partial oxidation
    • 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
    • C01B2203/04—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
    • 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
    • C01B2203/06—Integration with other chemical processes
    • 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
    • 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
    • C01B2203/1247—Higher hydrocarbons
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/06—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of oil shale and/or or bituminous rocks

Definitions

  • the invention relates to a process for the production of synthesis gas from a substance mixture containing higher boiling hydrocarbons, which is compressed and present in a predominantly higher-boiling hydrocarbons
  • Process condensate and a compressed gas stream is separated, which consists mainly of low-boiling hydrocarbons and is subsequently reacted in a reactor (POX reactor) by partial oxidation, wherein a soot from the POX reactor effluent synthesis gas is subjected to a water scrubbing in which a soot-containing Wastewater arises.
  • a reactor POX reactor
  • the invention relates to a device for carrying out the
  • Hydrocarbons are gaseous under standard conditions.
  • Carbon monoxide and / or hydrogen-containing gas mixtures are important starting materials for the production of a large number of products, such as
  • POX partial oxidation
  • a hydrocarbon-containing use in a reactor at temperatures between 1 300 and 1 500 ° C and pressures up to 150 bar with water vapor and an oxidizing agent to a synthesis crude reacted, which consists to a large extent of hydrogen, carbon monoxide, carbon dioxide and Water exists.
  • the heat required for the reaction is generated by incomplete (partial) oxidation of the hydrocarbons in use.
  • the POX reactor oxygen is added in an amount that is not sufficient for a complete conversion of the hydrocarbons.
  • Solids such as soot and ash or slag, which must be removed from the syngas before it can be treated further. That with one
  • a fine cleaning in which the solids content of Syntheserohgases is typically reduced to about 1 mg / m 3 .
  • the soot removed from the synthesis gas represents 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 costs incurred for separating soot from the wastewater have a decisive influence on the economy of the entire partial oxidation process.
  • Dispersion mixed The soot, which is much better wetted by naphtha than by water, passes almost completely into the naphthaphase.
  • 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 soot-containing naphtha fraction is withdrawn from the decanter and recycled as feed into the POX reactor, while the largely soot-free water fraction is for the most part returned to the quench water loop; a small part is delivered to a wastewater treatment plant.
  • the partial oxidation is suitable for the recovery of hydrocarbon-rich wastes or residues whose material use is otherwise impossible or only possible with great effort, and which can therefore be obtained inexpensively.
  • a cost-effective substance that is suitable for synthesis gas production by means of Partial oxidation is suitable, here is called a residual gas from the oil shale processing.
  • the oil shale is pyrolyzed in a retort process, wherein
  • Hydrocarbons is included. According to the prior art, the
  • Object of the present invention is therefore to provide a method and an apparatus of the type described above, which are suitable to overcome the described disadvantages of the prior art.
  • This object is achieved procedurally according to the invention that at least a portion of the process condensate is mixed with the soot-containing wastewater to absorb soot and separate from the wastewater.
  • the amount of naphtha required for soot removal can at least be reduced in comparison with the prior art; at best, it is possible to completely dispense with the use of expensive naphtha.
  • the amount of naphtha savings depends on the quantity and the quality of the process condensate. For example, if the process condensate has a chemical composition equivalent to that of naphtha and precipitates in an amount sufficient to remove soot, naphtha can be completely replaced with process condensate.
  • Process condensates which consist essentially of hydrocarbons having 4 to 10 carbon atoms and have a boiling range between 35 ° C. and 180 ° C. at atmospheric pressure are particularly suitable for carrying out the process according to the invention.
  • Such compositions are found in process condensates resulting from the compression of retort residual gases resulting from oil shale processing. It is therefore proposed that a retort residual gas be used as a substance mixture containing higher boiling hydrocarbons and the process condensate obtained therefrom be used as a medium for the separation of soot from soot-containing wastewater.
  • the invention relates to a device for obtaining synthesis gas from a mixture containing higher boiling hydrocarbons, with a reactor for carrying out a partial oxidation (POX reactor), a
  • Compressor upstream of the POX reactor for compressing the higher-boiling hydrocarbons-containing mixture
  • a separator arranged downstream of the compressor for the separation of process condensate obtained during compression
  • a decanter arranged downstream of the POX reactor for separating soot from soot-laden wastewater.
  • the separator is connected to the decanter in such a way that process condensate can be mixed with soot-laden wastewater and introduced into the decanter.
  • the decanter is preferably connected to the POX reactor so that a soot-laden hydrocarbon fraction from the decanter can be introduced into the POX reactor.
  • FIG. 1 shows a detail of a device in which synthesis gas is produced from a retort residual gas with the aid of a POX reactor.
  • a retort residual gas containing higher boiling hydrocarbons is fed to the compressor V, where it is compressed to a pressure which is sufficiently high to be able to introduce it into the POX reactor P.
  • Compressor V is followed by a separator A, in which the compressed stream 2 is introduced to condensed in the compression components, which are predominantly higher-boiling hydrocarbons, as
  • Synthesis gas to be implemented The synthesis gas withdrawn via line 6 from the POX reactor P at a temperature of typically more than 1300 ° C. is quenched by water in the quench device Q, wherein at the same time most of the entrained soot and ash particles are washed out and transferred to a first wastewater stream 7 becomes.
  • the only coarsely purified synthesis gas 8 is forwarded from the quench device Q in the water wash W, are removed in the remaining soot and ash particles by means of fresh water 12 from the gas, so that a washed, largely soot and ash-free synthesis crude 9 and a with small amounts of soot and ash laden second waste stream 10 arise.
  • Wastewater stream 10 in the quench device Q serves as quench water, the synthesis crude gas stream 9, which consists mainly of carbon dioxide, carbon monoxide and hydrogen, processed in the separator T to the synthesis gas 1 1.
  • the first waste water stream 7 with process condensate 13, which is supplied from the separator A, is mixed to form a dispersion 14, which is then introduced into the decanter D, where they are in soot-laden
  • Process condensate 15 and a largely soot-free water fraction 16 separates.
  • the soot-laden process condensate 15 is withdrawn from the decanter and returned as a feed into the POX reactor P, while the largely soot-free water fraction 16 is discharged to a wastewater treatment plant (not shown).

Abstract

The invention relates to a method and a device for obtaining synthesis gas (11) from a mixture (1) containing higher boiling point hydrocarbons which is compressed (V) and separated into a process condensate (13) predominantly comprising higher boiling point hydrocarbons and a compressed gas flow (3) which preponderantly contains low boiling point hydrocarbons and is subsequently reacted in a reactor (POX reactor) (P) by partial oxidation, wherein a crude synthesis gas (6) containing soot and flowing out of the POX reactor is subjected to water scrubbing (Q) in which an effluent (7) containing soot is generated. The invention is characterized in that at least a part of the process condensate (13) is mixed with the effluent (7) containing the soot to absorb the soot and separate it from the effluent (7).

Description

Beschreibung  description
Verfahren und Vorrichtung zur Gewinnung von Synthesegas aus einem Process and apparatus for obtaining synthesis gas from a
kohlenwasserstoffhaltigen Restgas  Hydrocarbon-containing residual gas
Die Erfindung betrifft ein Verfahren zur Gewinnung von Synthesegas aus einem höher siedende Kohlenwasserstoffe enthaltenden Stoffgemisch, das dabei verdichtet und in ein vorwiegend aus höher siedenden Kohlenwasserstoffen bestehendes The invention relates to a process for the production of synthesis gas from a substance mixture containing higher boiling hydrocarbons, which is compressed and present in a predominantly higher-boiling hydrocarbons
Prozesskondensat sowie einen verdichteten Gasstrom getrennt wird, der überwiegend aus niedrig siedenden Kohlenwasserstoffen besteht und nachfolgend in einem Reaktor (POX-Reaktor) durch Partielle Oxidation umgesetzt wird, wobei ein rußhaltig aus dem POX-Reaktor abströmendes Syntheserohgas einer Wasserwäsche unterzogen wird, bei der ein rußhaltiges Abwasser entsteht. Process condensate and a compressed gas stream is separated, which consists mainly of low-boiling hydrocarbons and is subsequently reacted in a reactor (POX reactor) by partial oxidation, wherein a soot from the POX reactor effluent synthesis gas is subjected to a water scrubbing in which a soot-containing Wastewater arises.
Weiterhin betrifft die Erfindung eine Vorrichtung zur Durchführung des Furthermore, the invention relates to a device for carrying out the
erfindungsgemäßen Verfahrens. inventive method.
In der vorliegenden Schrift sind unter höher siedenden Kohlenwasserstoffen aus Kohlenstoff und Wasserstoff bestehende Verbindungen zu verstehen, die bei In the present document are to be understood by higher boiling hydrocarbons of carbon and hydrogen existing compounds in
Normbedingungen als Flüssigkeit vorliegen, während niedrig siedende Standard conditions exist as a liquid, while low-boiling
Kohlenwasserstoffe unter Normbedingungen gasförmig sind. Hydrocarbons are gaseous under standard conditions.
Kohlenmonoxid und/oder Wasserstoff enthaltende Gasgemische, sog. Synthesegase, sind wichtige Ausgangsstoffe zur Herstellung einer Vielzahl von Produkten wie 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
Ammoniak, Methanol oder auch synthetischen Kraftstoffen. Ein in der Industrie weit verbreitetes Verfahren, mit dem in Synthesegasanlagen aus Kohlenwasserstoffen Synthesegase erzeugt werden, ist die Partielle Oxidation (POX). Hierbei wird ein kohlenwasserstoffhaltiger Einsatz in einem Reaktor (POX-Reaktor) bei Temperaturen zwischen 1 300 und 1 500°C und Drücken bis zu 150 bar mit Wasserdampf und einem Oxidationsmittel zu einem Syntheserohgas umgesetzt, das zu großen Teilen aus Wasserstoff, Kohlenmonoxid, Kohlendioxid und Wasser besteht. Die für die Reaktion erforderliche Wärme wird durch unvollständige (partielle) Oxidation der im Einsatz befindlichen Kohlenwasserstoffe erzeugt. Hierfür wird dem POX-Reaktor Sauerstoff in einer Menge zugeführt, die für eine vollständige Umsetzung der Kohlenwasserstoffe nicht ausreichend ist. Bei der Partiellen Oxidation entstehen neben gasförmigen Komponenten auch Ammonia, methanol or even synthetic fuels. One method widely used in industry for producing synthesis gases in synthesis gas plants from hydrocarbons is partial oxidation (POX). Here, a hydrocarbon-containing use in a reactor (POX reactor) at temperatures between 1 300 and 1 500 ° C and pressures up to 150 bar with water vapor and an oxidizing agent to a synthesis crude reacted, which consists to a large extent of hydrogen, carbon monoxide, carbon dioxide and Water exists. The heat required for the reaction is generated by incomplete (partial) oxidation of the hydrocarbons in use. For this purpose, the POX reactor oxygen is added in an amount that is not sufficient for a complete conversion of the hydrocarbons. At partial oxidation besides gaseous components also arise
Feststoffe wie Ruß und Asche bzw. Schlacke, die aus dem Syntheserohgas entfernt werden müssen, bevor dieses weiter behandelt werden kann. Das mit einer Solids such as soot and ash or slag, which must be removed from the syngas before it can be treated further. That with one
Temperatur von mehr als 1 300°C aus dem POX-Reaktor austretende Syntheserohgas wird zunächst abgekühlt und anschließend einer Wasserwäsche unterzogen. Erfolgt die Abkühlung des Syntheserohgases in direktem Kontakt mit Wasser (Quenchen), so wird bereits in diesem Verfahrensschritt ein Großteil der Feststoffe aus dem Temperature of more than 1 300 ° C from the POX reactor emerging synthesis crude is first cooled and then subjected to a water wash. If the cooling of the synthesis raw gas in direct contact with water (quenching), so in this process step, a large part of the solids from the
Syntheserohgas ausgewaschen und geht in das zum Quenchen verwendete Wasser über. In der Wasserwäsche erfolgt eine Feinreinigung, bei der der Feststoffgehalt des Syntheserohgases typischerweise auf ca. 1 mg/m3 reduziert wird. Washed out synthesis gas and passes into the water used for quenching. In the water wash a fine cleaning, in which the solids content of Syntheserohgases is typically reduced to about 1 mg / m 3 .
Der aus dem Syntheserohgas 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 synthesis gas represents 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.
Sinnvollerweise wird der Ruß als Einsatz in den POX-Reaktor zurückgeführt und dort zu Kohlenmonoxid umgesetzt. Die für die Rußabtrennung aus dem Abwasser anfallenden Kosten beeinflussen entscheidend die Wirtschaftlichkeit des gesamten Partialoxidationsprozesses.  It makes sense for the soot to be recycled as an insert into the POX reactor and converted there to carbon monoxide. The costs incurred for separating soot from the wastewater have a decisive influence on the economy of the entire partial oxidation process.
Um den bei der Partiellen Oxidation anfallenden Ruß stofflich zu nutzen, wird nach dem Stand der Technik das mit Ruß beladene Abwasser mit Naphtha zu einer In order to use the resulting in the partial oxidation of carbon soot, according to the prior art, the loaded with soot wastewater with naphtha to a
Dispersion vermischt. Der Ruß, der von Naphtha wesentlich besser benetzt wird als von Wasser, geht dabei nahezu vollständig in die 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. Die Ruß enthaltende Naphthafraktion wird aus dem Dekanter abgezogen und als Einsatz in den POX-Reaktor zurückgeführt, während die weitgehend rußfreie Wasserfraktion zum größten Teil in den Quenchwasserkreislauf zurückgeleitet wird; ein kleiner Teil wird an eine Abwasseraufbereitungsanlage abgegeben. Dispersion mixed. The soot, which is much better wetted by naphtha than by water, passes almost completely into the naphthaphase. 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 soot-containing naphtha fraction is withdrawn from the decanter and recycled as feed into the POX reactor, while the largely soot-free water fraction is for the most part returned to the quench water loop; a small part is delivered to a wastewater treatment plant.
Die Partielle Oxidation eignet sich zur Verwertung von kohlenwasserstoffreichen Abfalloder Reststoffen, deren stoffliche Nutzung auf andere Art nicht oder nur mit großem Aufwand möglich ist, und die daher kostengünstig bezogen werden können. Als Beispiel für einen kostengünstigen Stoff, der sich für die Synthesegaserzeugung mittels Partieller Oxidation eignet, sei hier ein Restgas aus der Ölschieferaufbereitung genannt. Der Ölschiefer wird in einem Retorte-Prozess pyrolysiert, wobei The partial oxidation is suitable for the recovery of hydrocarbon-rich wastes or residues whose material use is otherwise impossible or only possible with great effort, and which can therefore be obtained inexpensively. As an example of a cost-effective substance that is suitable for synthesis gas production by means of Partial oxidation is suitable, here is called a residual gas from the oil shale processing. The oil shale is pyrolyzed in a retort process, wherein
kohlenwasserstoffreiche Pyrolysegase entstehen, die anschließend abgekühlt werden. Dabei wird eine aus Kohlenwasserstoffen bestehende Flüssigphase abgeschieden, die ein synthetisches Rohöl darstellt. Übrig bleibt ein Retorte- Restgas, das zu einem Großteil aus kurzkettigen Kohlenwasserstoffen (im Wesentlichen C^ bis C10) besteht, daneben aber auch Verunreinigungen wie z. B. Kohlendioxid, Schwefelwasserstoff, Kohlenoxidsulfid oder Stickstoff enthält. Bei der Verdichtung eines solchen Retorte- Restgases auf den für eine Partielle Oxidation erforderlichen Druck kondensieren höher siedende Kohlenwasserstoffe aus, so dass ein vorwiegend aus höher siedenden Kohlenwasserstoffen (C4 bis Ci0) bestehendes Prozesskondensat sowie eine arise hydrocarbon-rich pyrolysis gases, which are then cooled. In this case, a liquid phase consisting of hydrocarbons is separated, which is a synthetic crude oil. What remains is a retort residual gas, which consists to a large extent of short-chain hydrocarbons (essentially C ^ to C 10 ), but also impurities such. As carbon dioxide, hydrogen sulfide, carbon dioxide sulfide or nitrogen. When compacting such a Retorte- residual gas to the required for a partial oxidation pressure higher boiling hydrocarbons condense, so that a predominantly of higher boiling hydrocarbons (C 4 to C 0) existing process condensate and a
Gasphase entstehen, in der der überwiegende Teil der niedrig siedenden Gas phase arise in which the vast majority of low-boiling
Kohlenwasserstoffe enthalten ist. Nach dem Stand der Technik wird das Hydrocarbons is included. According to the prior art, the
Prozesskondensat gemeinsam mit der Gasphase in den POX-Reaktor eingeleitet, um dort umgesetzt zu werden. Das Retorte-Restgas ist im Vergleich zu Naphtha wesentlich kostengünstiger, so dass sich die Rußrückgewinnung mit Hilfe von Naphtha negativ auf die Wirtschaftlichkeit der Synthesegaserzeugung auswirken würde. Process condensate introduced together with the gas phase in the POX reactor to be implemented there. The retort residual gas is significantly less expensive than naphtha, so that soot recovery using naphtha would negatively impact the economics of syngas production.
Aufgabe der vorliegenden Erfindung ist es daher, ein Verfahren sowie eine Vorrichtung der eingangs beschriebenen Art anzugeben, die geeignet sind, die beschriebenen Nachteile des Standes der Technik zu überwinden. Object of the present invention is therefore to provide a method and an apparatus of the type described above, which are suitable to overcome the described disadvantages of the prior art.
Diese Aufgabe wird verfahrensseitig erfindungsgemäß dadurch gelöst, dass zumindest ein Teil des Prozesskondensats mit dem rußhaltigen Abwasser vermischt wird, um Ruß aufzunehmen und aus dem Abwasser abzutrennen. This object is achieved procedurally according to the invention that at least a portion of the process condensate is mixed with the soot-containing wastewater to absorb soot and separate from the wastewater.
Durch das erfindungsgemäße Verfahren kann die Menge des für die Rußabtrennung benötigten Naphthas im Vergleich zum Stand der Technik zumindest reduziert werden; günstigstenfalls ist es möglich, vollständig auf den Einsatz von teurem Naphtha zu verzichten. Die Höhe der Naphtha-Einsparung hängt dabei von der Menge und der Qualität des Prozesskondensats ab. Weist beispielsweise das Prozesskondensat eine chemische Zusammensetzung auf, die der von Naphtha entspricht, und fällt es in einer für die Rußabtrennung ausreichenden Menge an, kann Naphtha vollständig durch Prozesskondensat ersetzt werden. Falls die chemische Zusammensetzung des Prozesskondensats von der von Naphtha so stark abweicht, dass es alleine nicht für die Rußabtrennung verwendbar ist, kann eine Mischung aus Prozesskondensat und Naphtha eingesetzt werden, was einen lediglich eingeschränkten Naphthabedarf zur Folge hat. Vorzugsweise wird nicht für die Rußabtrennung eingesetztes By means of the process according to the invention, the amount of naphtha required for soot removal can at least be reduced in comparison with the prior art; at best, it is possible to completely dispense with the use of expensive naphtha. The amount of naphtha savings depends on the quantity and the quality of the process condensate. For example, if the process condensate has a chemical composition equivalent to that of naphtha and precipitates in an amount sufficient to remove soot, naphtha can be completely replaced with process condensate. If the chemical composition of the process condensate deviates so much from that of naphtha that it alone is not suitable for the Rußabtrennung is usable, a mixture of process condensate and naphtha can be used, which has a limited naphtha requirement. Preferably, not used for the removal of soot
Prozesskondensat direkt dem POX-Reaktor als Einsatz zugeführt. Process condensate fed directly to the POX reactor as an insert.
Sinnvollerweise wird das mit Ruß beladene Prozesskondensat bzw. die rußbeladene, aus Prozesskondensat und Naphtha gebildete Kohlenwasserstofffraktion zurückgeführt und als Einsatz in den POX-Reaktor eingeleitet, wodurch eine weitgehend vollständige Nutzung des höher siedende Kohlenwasserstoffe enthaltenden Stoffgemisches erreicht wird. It makes sense to load the process condensate laden with soot or the soot-laden hydrocarbon fraction formed from process condensate and naphtha and introduce it as an insert into the POX reactor, thereby achieving a substantially complete utilization of the substance mixture containing higher boiling hydrocarbons.
Besonders geeignet für die Durchführung des erfindungsgemäßen Verfahrens sind Prozesskondensate, die im Wesentlichen aus Kohlenwasserstoffen mit 4 bis 10 Kohlenstoffatomen bestehen und bei atmosphärischem Druck einen Siedebereich zwischen 35°C und 180°C aufweisen. Derartige Zusammensetzungen finden sich in Prozesskondensaten, die bei der Verdichtung von bei der Ölschieferaufbereitung anfallendem Retorte-Restgasen entstehen. Es wird daher vorgeschlagen, dass als höher siedende Kohlenwasserstoffe enthaltendes Stoffgemisch ein Retorte-Restgas eingesetzt und das aus diesem gewonnene Prozesskondensat als Medium für die Abtrennung von Ruß aus rußhaltigem Abwasser verwendet wird. Process condensates which consist essentially of hydrocarbons having 4 to 10 carbon atoms and have a boiling range between 35 ° C. and 180 ° C. at atmospheric pressure are particularly suitable for carrying out the process according to the invention. Such compositions are found in process condensates resulting from the compression of retort residual gases resulting from oil shale processing. It is therefore proposed that a retort residual gas be used as a substance mixture containing higher boiling hydrocarbons and the process condensate obtained therefrom be used as a medium for the separation of soot from soot-containing wastewater.
Weiterhin betrifft die Erfindung eine Vorrichtung zur Gewinnung von Synthesegas aus einem höher siedende Kohlenwasserstoffe enthaltenden Stoffgemisch, mit einem Reaktor zur Durchführung einer Partiellen Oxidation (POX-Reaktor), einem Furthermore, the invention relates to a device for obtaining synthesis gas from a mixture containing higher boiling hydrocarbons, with a reactor for carrying out a partial oxidation (POX reactor), a
stromaufwärts des POX-Reaktors angeordneten Verdichter zur Verdichtung des höher siedende Kohlenwasserstoffe enthaltenden Stoffgemisches, einem stromabwärts des Verdichters angeordneten Abscheider zur Abscheidung von bei der Verdichtung anfallendem Prozesskondensat, sowie einem stromabwärts des POX-Reaktors angeordneten Dekanter zur Abtrennung von Ruß aus rußbeladenem Abwasser. Compressor upstream of the POX reactor for compressing the higher-boiling hydrocarbons-containing mixture, a separator arranged downstream of the compressor for the separation of process condensate obtained during compression, and a decanter arranged downstream of the POX reactor for separating soot from soot-laden wastewater.
Die gestellte Aufgabe wird vorrichtungsseitig erfindungsgemäß dadurch gelöst, dass der Abscheider mit dem Dekanter derart verbunden ist, dass Prozesskondensat mit rußbeladenem Abwasser gemischt und in den Dekanter eingeleitet werden kann. Um Ruß und Kohlenwasserstoffe aus dem Dekanter stofflich nutzen zu können, ist der Dekanter vorzugsweise mit dem POX-Reaktor so verbunden, dass eine rußbeladene Kohlenwasserstofffraktion aus dem Dekanter in den POX-Reaktor eingeleitet werden kann. This object is achieved according to the device device according to the invention in that the separator is connected to the decanter in such a way that process condensate can be mixed with soot-laden wastewater and introduced into the decanter. In order to use carbon black and hydrocarbons from the decanter material, the decanter is preferably connected to the POX reactor so that a soot-laden hydrocarbon fraction from the decanter can be introduced into the POX reactor.
Im Folgenden soll die Erfindung anhand eines in der Figur 1 schematisch dargestellten Ausführungsbeispiels näher erläutert werden. In the following, the invention will be explained in more detail with reference to an exemplary embodiment shown schematically in FIG.
Die Figur 1 zeigt einen Ausschnitt aus einer Einrichtung, in der aus einem Retorte- Restgas mit Hilfe eines POX-Reaktors Synthesegas erzeugt wird. FIG. 1 shows a detail of a device in which synthesis gas is produced from a retort residual gas with the aid of a POX reactor.
Über Leitung 1 wird ein höher siedende Kohlenwasserstoffe enthaltendes Retorte- Restgas dem Verdichter V zugeleitet, wo es auf einen Druck verdichtet wird, der ausreichend hoch ist, um es in den POX-Reaktor P einleiten zu können. Dem Via line 1, a retort residual gas containing higher boiling hydrocarbons is fed to the compressor V, where it is compressed to a pressure which is sufficiently high to be able to introduce it into the POX reactor P. the
Verdichter V ist ein Abscheider A nachgeschaltet, in den der verdichtete Stoffstrom 2 eingeleitet wird, um bei der Verdichtung auskondensierte Komponenten, bei denen es sich vorwiegend um höher siedende Kohlenwasserstoffe handelt, als Compressor V is followed by a separator A, in which the compressed stream 2 is introduced to condensed in the compression components, which are predominantly higher-boiling hydrocarbons, as
Prozesskondensat abzuscheiden, so dass ein weitgehend aus niedrig siedenden Kohlenwasserstoffen bestehender Gasstrom 3 dem POX-Reaktor P als Einsatz zugeführt werden kann, um gemeinsam mit Wasserdampf 4 und Sauerstoff 5 zuSeparate process condensate, so that a largely consisting of low-boiling hydrocarbons gas stream 3 can be fed to the POX reactor P as an application to together with water vapor 4 and oxygen to 5
Synthesegas umgesetzt zu werden. Das über Leitung 6 aus dem POX-Reaktor P mit einer Temperatur von typischerweise mehr als 1300°C abgezogene Syntheserohgas wird in der Quencheinrichtung Q durch Wasser abgekühlt, wobei gleichzeitig der größte Teil an mitgeführten Ruß- und Aschepartikeln ausgewaschen und in einen ersten Abwasserstrom 7 überführt wird. Zur Feinreinigung wird das lediglich grob gereinigte Syntheserohgas 8 aus der Quencheinrichtung Q in die Wasserwäsche W weitergeleitet, in der verbliebene Ruß- und Aschepartikel mittels Frischwassers 12 aus dem Gas entfernt werden, so dass ein gewaschener, weitgehend ruß- und aschefreier Syntheserohgasstrom 9 sowie ein mit geringen Ruß- und Aschemengen beladener zweiter Abwasserstrom 10 entstehen. Während der mit Rußspuren beladene Synthesis gas to be implemented. The synthesis gas withdrawn via line 6 from the POX reactor P at a temperature of typically more than 1300 ° C. is quenched by water in the quench device Q, wherein at the same time most of the entrained soot and ash particles are washed out and transferred to a first wastewater stream 7 becomes. For fine cleaning, the only coarsely purified synthesis gas 8 is forwarded from the quench device Q in the water wash W, are removed in the remaining soot and ash particles by means of fresh water 12 from the gas, so that a washed, largely soot and ash-free synthesis crude 9 and a with small amounts of soot and ash laden second waste stream 10 arise. During the loaded with soot traces
Abwasserstrom 10 in der Quencheinrichtung Q als Quenchwasser dient, wird der Syntheserohgasstrom 9, der vorwiegend aus Kohlendioxid, Kohlenmonoxid und Wasserstoff besteht, in der Trenneinrichtung T zum Synthesegas 1 1 aufbereitet. Zur Abtrennung des Rußes wird der erste Abwasserstrom 7 mit Prozesskondensat 13, das aus dem Abscheider A zugeführt wird, zu einer Dispersion 14 vermischt, die anschließend in den Dekanter D eingeleitet wird, wo sie sich in rußbeladenes Wastewater stream 10 in the quench device Q serves as quench water, the synthesis crude gas stream 9, which consists mainly of carbon dioxide, carbon monoxide and hydrogen, processed in the separator T to the synthesis gas 1 1. To separate off the soot, the first waste water stream 7 with process condensate 13, which is supplied from the separator A, is mixed to form a dispersion 14, which is then introduced into the decanter D, where they are in soot-laden
Prozesskondensat 15 und eine weitgehend rußfreie Wasserfraktion 16 trennt. Das rußbeladene Prozesskondensat 15 wird aus dem Dekanter abgezogen und als Einsatz in den POX-Reaktor P zurückgeführt, während die weitgehend rußfreie Wasserfraktion 16 an eine Abwasseraufbereitungsanlage (nicht dargestellt) abgegeben wird. Process condensate 15 and a largely soot-free water fraction 16 separates. The soot-laden process condensate 15 is withdrawn from the decanter and returned as a feed into the POX reactor P, while the largely soot-free water fraction 16 is discharged to a wastewater treatment plant (not shown).

Claims

Patentansprüche claims
Verfahren zur Gewinnung von Synthesegas (11) aus einem höher siedende Kohlenwasserstoffe enthaltenden Stoffgemisch (1), das dabei verdichtet (V) und in ein vorwiegend aus höher siedenden Kohlenwasserstoffen bestehendes Process for the recovery of synthesis gas (11) from a mixture of substances (1) containing higher boiling hydrocarbons, which compresses (V) and is present in a predominantly higher-boiling hydrocarbon
Prozesskondensat (13) sowie einen verdichteten Gasstrom (2) getrennt wird, der überwiegend aus niedrig siedenden Kohlenwasserstoffen besteht und nachfolgend in einem Reaktor (POX-Reaktor) (P) durch Partielle Oxidation umgesetzt wird, wobei ein rußhaltig aus dem POX-Reaktor abströmendes Syntheserohgas (6) einer Wasserwäsche (Q) unterzogen wird, bei der ein rußhaltiges Abwasser (7) entsteht, dadurch gekennzeichnet, dass zumindest ein Teil des Process condensate (13) and a compressed gas stream (2) is separated, which consists predominantly of low-boiling hydrocarbons and is subsequently reacted in a reactor (POX reactor) (P) by partial oxidation, wherein a soot from the POX reactor effluent synthesis crude (6) a water wash (Q) is subjected, in which a soot - containing wastewater (7) is formed, characterized in that at least a portion of the
Prozesskondensats (13) mit dem rußhaltigen Abwasser (7) vermischt wird, um Ruß aufzunehmen und aus dem Abwasser (7) abzutrennen. Process condensate (13) with the soot-containing wastewater (7) is mixed to receive soot and separated from the wastewater (7).
Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass das mit Ruß beladene Prozesskondensat (15) zurückgeführt und als Einsatz in den POX-Reaktor (P) eingeleitet wird. A method according to claim 1, characterized in that the laden with soot process condensate (15) is recycled and introduced as an insert in the POX reactor (P).
Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass das Prozesskondensat (13) im Wesentlichen aus Kohlenwasserstoffen mit 4 bis 10 Kohlenstoffatomen bestehet und bei atmosphärischem Druck einen Siedebereich zwischen 35°C und 180°C aufweist. Method according to one of claims 1 or 2, characterized in that the process condensate (13) consists essentially of hydrocarbons having 4 to 10 carbon atoms and at atmospheric pressure has a boiling range between 35 ° C and 180 ° C.
Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass es sich bei dem höher siedende Kohlenwasserstoffe enthaltenden Stoffgemisch (1) um ein Retorte-Restgas aus der Ölschieferaufbereitung handelt. Method according to one of claims 1 to 3, characterized in that it is in the higher-boiling hydrocarbons-containing mixture (1) is a retort residual gas from the oil shale preparation.
Vorrichtung zur Gewinnung von Synthesegas (11) aus einem höher siedende Kohlenwasserstoffe enthaltenden Stoffgemisch (1), mit einem Reaktor (P) zur Durchführung einer Partiellen Oxidation (POX-Reaktor), einem stromaufwärts des POX-Reaktors angeordneten Verdichter (V) zur Verdichtung des höher siedende Kohlenwasserstoffe enthaltenden Stoffgemisches (1), einem stromabwärts des Verdichters (V) angeordneten Abscheider (A) zur Abscheidung von bei der Verdichtung anfallendem Prozesskondensat (13) sowie einem stromabwärts des POX-Reaktors (P) angeordneten Dekanter (D) zur Abtrennung von Ruß aus rußbeladenem Abwasser (7), dadurch gekennzeichnet, dass der Abscheider (A) mit dem Dekanter (D) derart verbunden ist, dass Prozesskondensat (13) mit rußbeladenem Abwasser (7) gemischt und in den Dekanter (D) eingeleitet werden kann. Apparatus for recovering synthesis gas (11) from a substance mixture (1) containing higher boiling hydrocarbons, comprising a reactor (P) for carrying out a partial oxidation (POX reactor), a compressor (V) arranged upstream of the POX reactor for compressing the gas higher-boiling hydrocarbon-containing substance mixture (1), a downstream of the compressor (V) arranged separator (A) for separating accumulating in the compression process condensate (13) and a downstream of the POX reactor (P) arranged decanter (D) for the separation of Soot from soot-laden wastewater (7), characterized in that the separator (A) is connected to the decanter (D) such that process condensate (13) with soaked wastewater (7) can be mixed and introduced into the decanter (D).
Vorrichtung nach Anspruch 5, dadurch gekennzeichnet, dass der Dekanter (D) mit dem POX-Reaktor (P) derart verbunden ist, dass eine rußbeladene Apparatus according to claim 5, characterized in that the decanter (D) with the POX reactor (P) is connected such that a soot-laden
Kohlenwasserstofffraktion (15) aus dem Dekanter (D) in den POX-Reaktor (P) eingeleitet werden kann. Hydrocarbon fraction (15) from the decanter (D) in the POX reactor (P) can be initiated.
PCT/EP2013/003258 2012-11-08 2013-10-29 Method and device for obtaining synthesis gas from a residual gas containing hydrocarbons WO2014072033A1 (en)

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US4205963A (en) * 1978-04-28 1980-06-03 Texaco Inc. Process for gas cleaning with reclaimed water and apparatus for water reclamation
US20110068050A1 (en) * 2003-11-27 2011-03-24 Shoufeng Wang Process for distillation and decarbonization of oil shale species using fluidized bed

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