EP3318619A1 - Method for the production of fuels from gas condensates - Google Patents
Method for the production of fuels from gas condensates Download PDFInfo
- Publication number
- EP3318619A1 EP3318619A1 EP16197027.2A EP16197027A EP3318619A1 EP 3318619 A1 EP3318619 A1 EP 3318619A1 EP 16197027 A EP16197027 A EP 16197027A EP 3318619 A1 EP3318619 A1 EP 3318619A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- gas
- boiling
- reforming
- condensate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Definitions
- the invention relates to a process for converting gas condensates having a boiling range up to about 180 ° C. into fuels, in particular high-octane gasoline fuels, in which condensate originating from the gas recovery is reformed using at least one zeolite catalyst.
- the raw gas that is produced in the natural gas production often also contains heavier hydrocarbons, which can be separated at room temperature under moderate pressure as gas condensate. This is usually accompanied by a drying process.
- Typical ingredients of this natural gas by-product are linear alkanes, cycloalkanes and aromatics.
- the gas condensate is separated in so-called separators, ie containers in which the raw gas produced comes to rest and optionally precipitate the condensable fractions under pressure.
- gas condensate which is similar to the lighter fractions of petroleum distillation, is used as a feedstock for the petrochemical industry, as a fluxing agent for transporting heavy oils in pipelines, or admixed as a blending component to gasoline.
- admixing with gasoline is only possible to a limited extent due to the usually low knocking resistance of the gas condensate.
- the object of the invention is thus to provide a method by which gas condensate from natural gas production can be converted into high-quality products, in particular in fuels for operating engines.
- the process aims to close the existing gap in the production of gas condensate fuels and to remove the previous limitations on their processing in a conventional refinery.
- the method can also be operated at higher pressures;
- the pressures given are to be understood as partial pressures of the completely vaporized starting material.
- gas condensates under the conditions mentioned can be catalytically converted into high-quality fuels with the method according to the invention, which meet the requirements of modern engines to the knock resistance.
- the reforming process according to the invention is carried out at a pressure of 1 to 5 bar, in particular at about 2 bar. It has been shown that the conducts applied usually in the reforming process pressure of more than 20 bar to undesirably high proportions of heavy hydrocarbons (C 11 +) and also leads to products with inadequate knock resistance which, due to their high boiling point no more than gasoline component or as a gasoline fuel to be used.
- process temperature according to the invention is between 380 C ° and 560 C °, preferably between 400 C ° and 470 C ° and in particular between 430 C ° and ⁇ 450 C °. Analyzes have shown that the proportion of hydrocarbons with C 11 + in the product in the specified pressure and temperature regime is optimal.
- LHSV Liquid Hourly Space Velocity
- the process according to the invention is carried out with at least one zeolite catalyst, zeolites based on SiO 2 , Al 2 O 3 and P 2 O 5 being preferably used.
- the process can be carried out in several stages with several catalysts with different power profiles.
- the lighter fractions are converted in particular via isomerization catalysts in higher-boiling products, in which case zeolite catalysts having a Si / Al ratio of 10 to 200, preferably about 30 are used.
- Preference is given to catalysts of MOR, MEL or MFI type.
- aromatization catalysts for higher-boiling fractions are in particular aromatization catalysts in question, which high-boiling fractions of the gas condensate can be converted, inter alia, in gasoline.
- zeolites with an MFI, BEA, TON, MOR, LTL or NTT structure can be used for the aromatization, but an MFI structure is preferred.
- the Si / Al ratio is preferably 2: 1 to 5: 1, in particular 3: 1 to 4: 1.
- the catalysts have cavities, with an average pore size in the range of in particular 0.4 to 1.5 nm and preferably 0.5 to 0.7 nm.
- the zeolites used according to the invention are usually doped with metal ions, the metal content being in the range from 0.1 to 5.0% by weight.
- Preferred metals are Ni, Pd, Pt with a concentration of 0.3 to 0.4 percent by weight and / or one or more metals of the group Zn, Cr, Co, Mg, Ga and Fe, wherein Zn has a weight concentration of 1 to 5 , 0% is preferred.
- the aromatization catalysts are in particular metals from the group Zn, Cr, Co, Mg, Ga, and Fe in question, again preferably Zn, with a weight concentration of 1 to 2.5%, based on the catalyst.
- the inventive method can be carried out in several variants, wherein at the beginning is always a splitting of the condensate into several fractions.
- the gas condensate is split into at least three fractions before the catalytic conversion, a low-boiling fraction, a medium-boiling fraction and at least one high-boiling fraction.
- the low-boiling fraction comprises hydrocarbons up to C 4 or C 5
- the medium-boiling fraction hydrocarbons to C 7 , preferably C 6 to C 7
- a high-boiling fraction to C 10 a high-boiling fraction to C 10 .
- the fraction of hydrocarbons with C 11 + is not subjected to the reforming process.
- At least one of the fractions is thereby fed to a reforming process, a fraction to an optional constituent process and at least one high-boiling fraction of a flavoring.
- a medium-boiling fraction with C 6 and C 7 can be fed directly, without further processing, the repository; it is directly usable as a blending component for gasoline.
- Particularly preferred is a process in which the hydrocarbons are subjected to aromatization to C 5 , the fraction C 6 / C 7 is supplied to the repository and the fraction is subjected to C 8 to C 10 of a separate aromatization.
- a process it is possible to keep the proportion of hydrocarbons with C 11 + below 7.5% by weight and in particular below 5% by weight of the reformed product (see FIG. 1 ).
- nitrogen can be added as the carrier gas. Often it makes sense to add hydrogen.
- Another preferred variant, in particular in the availability of hydrogen is a method in which the hydrocarbons are supplied to C 4 aromatization, which is subjected to C 5 / C 6 fraction to an isomerization and the fraction is converted into a separate flavoring from C 7 becomes. With such a process, it is possible to reduce the proportion of aromatics in the reformed product with constant knock resistance (see FIG. 2 ).
- low-boiling and high-boiling fractions are reformed separately and the reforming products contained are subjected to fractionation.
- light fractions which can not be used directly as fuels gasoline, diesel
- Such a cycle gas procedure can be carried out with the addition of hydrogen in order to increase the yield of desired products in the middle-boiling range.
- hydrogen is basically suitable for reducing coke formation on the catalyst and thus for increasing the service life or cycle time.
- the inventive method can be operated in several other variants in addition to the two variants already described.
- a third variant for example, the gas condensate is split into three fractions, C 1 / C 4 , C 5 / C 10 and C 11 + , of which only the middle fraction is processed in a reforming process to gasoline / diesel / solvent.
- a fourth variant ( FIG. 4 ) the splitting into three fractions C 1 / C 5 , C 6 / C 10 and C 11 + , of which the low-boiling fraction, optionally with the addition of hydrogen is converted into gasoline, the medium-boiling fraction is converted into an aromatic complex and the high-boiling Fractions are used elsewhere.
- This variant is particularly suitable for integration into existing plants, especially in an aromatic complex or within a refinery to increase the yield of aromatics or gasoline.
- the inventive method can always be operated without the use of external hydrogen.
- the zeolite catalysts used are known and widely studied and generally available. They have proven themselves in the conversion of hydrocarbons, but sometimes much more drastic conditions are used. So far, it has not been possible to arrive at the inventively desired low levels of high-boiling hydrocarbons under moderate conditions.
- the catalysts used according to the invention are subject to the usual aging and coking phenomena. They can be regenerated in the usual way. For this purpose, it is useful to provide in the process in the use of fixed bed reactors parallel catalyst beds, which are alternately subjected to regeneration.
- the individual streams are characterized by the carbon numbers of the corresponding hydrocarbons.
- ATM distillation refers to distillation at atmospheric pressure.
- the abbreviation K stands for a compressor, the abbreviation R for a catalytic reactor bed.
- Separators are labeled SEP, stabilizers with STA.
- UOP Reformer is a well-known platinum on alumina reformer developed by Universal Oil Products (UOP).
- the attached table illustrates process results for various pressure (P), temperature (T), and throughput (LHSV) octane ratings (RON) and C 11 + fractions. It can be seen that at moderate temperatures in the range of 430 to 450 ° C and moderate pressures up to 2.0 bar high RON values and low C 11 + contents can be achieved.
- Diagrams 1 to 3 show the dependency of the RON values and C 11 + components as a function of the temperature, the pressure and the throughput. An optimum results for temperatures of 430 to 450 ° C, pressures up to 2.0 bar and throughputs of up to 2.0 / h.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Die Erfindung betrifft ein Verfahren zur Umwandlung von Gaskondensaten mit einem Siedebereich bis etwa 180°C in Kraftstoffe, insbesondere hochoktanige Otto-Kraftstoffe, bei dem aus der Gasgewinnung stammendes Kondensat unter Verwendung mindestens eines Zeolith-Katalysators reformiert wird, bei dem der Reforming-Prozess unter einem Druck von 1 bis 5 bar bei einer Temperatur von 380°C bis 560°C durchgeführt wird.The invention relates to a process for the conversion of gas condensates having a boiling range up to about 180 ° C in fuels, especially high octane gasoline fuels, is reformed from the gas extraction condensate using at least one zeolite catalyst, in which the reforming process under a pressure of 1 to 5 bar at a temperature of 380 ° C to 560 ° C is performed.
Description
Die Erfindung betrifft ein Verfahren zur Umwandlung von Gaskondensaten mit einem Siedebereich bis etwa 180 C° in Kraftstoffe, insbesondere hochoktanige Otto-Kraftstoffe, bei dem aus der Gasgewinnung stammendes Kondensat unter Verwendung mindestens eines Zeolith-Katalysators reformiert wird.The invention relates to a process for converting gas condensates having a boiling range up to about 180 ° C. into fuels, in particular high-octane gasoline fuels, in which condensate originating from the gas recovery is reformed using at least one zeolite catalyst.
Das Rohgas, das bei der Erdgasförderung anfällt, enthält häufig auch schwerere Kohlenwasserstoffe, die bei Raumtemperatur unter mäßigem Druck als Gaskondensat abgeschieden werden können. Dies geht zumeist einher mit einem Trocknungsprozess.The raw gas that is produced in the natural gas production often also contains heavier hydrocarbons, which can be separated at room temperature under moderate pressure as gas condensate. This is usually accompanied by a drying process.
Typische Inhaltsstoffe dieses Erdgasbegleitprodukts sind lineare Alkane, Cycloalkane sowie Aromaten. Vom Rohgas wird das Gaskondensat in sogenannten Separatoren abgetrennt, also Behältern, in denen das geförderte Rohgas zur Ruhe kommt und sich die kondensierbaren Anteile gegebenenfalls unter Druck abscheiden.Typical ingredients of this natural gas by-product are linear alkanes, cycloalkanes and aromatics. From the raw gas, the gas condensate is separated in so-called separators, ie containers in which the raw gas produced comes to rest and optionally precipitate the condensable fractions under pressure.
Üblicherweise wird das Gaskondensat, das den leichteren Fraktionen der Erdöldestillation ähnelt, als Feedstock für die Petrochemische Industrie verwendet, als Fluxmittel für den Transport von schweren Ölen in Pipelines genutzt oder als Blending-Komponente dem Benzin zugemischt. Die Zumischung zum Benzin ist jedoch durch die in der Regel niedrige Klopffestigkeit des Gaskondensates nur eingeschränkt möglich.Typically, gas condensate, which is similar to the lighter fractions of petroleum distillation, is used as a feedstock for the petrochemical industry, as a fluxing agent for transporting heavy oils in pipelines, or admixed as a blending component to gasoline. However, admixing with gasoline is only possible to a limited extent due to the usually low knocking resistance of the gas condensate.
Die starke Zunahme der Erdgasförderung weltweit hat zu einem hohen Anfall von Gaskondensat geführt, der - vom Energiegehalt her gesehen - etwa 10 % der globalen Erdölforderung entspricht.The large increase in natural gas production worldwide has led to a high rate of gas condensate, which, in terms of energy content, accounts for around 10% of global oil demand.
In vielen Ländern mit Erdgas- und Erdölförderung mangelt es an Möglichkeiten zur Verarbeitung der Förderprodukte. Diese Länder müssen Kraftstoffe auf dem Weltmarkt ordern und zu hohen Preisen importieren. Soweit Gaskondensate bei der Förderung anfallen, werden diese entweder exportiert oder thermisch verwertet. Es wäre wünschenswert, dieses anfallende Kondensat vor Ort in hochwertige Kraftstoffe zu überführen.In many countries with natural gas and oil production, there is a lack of possibilities for the processing of production products. These countries have to order fuels on the world market and import them at high prices. As far as gas condensates are incurred in the promotion, they are either exported or thermally recovered. It would be desirable to convert this accumulating condensate on site into high-quality fuels.
Aufgabe der Erfindung ist damit die Bereitstellung eines Verfahrens, mit dem Gaskondensat aus der Erdgasförderung in hochwertige Produkte umgewandelt werden kann, insbesondere in Kraftstoffe zum Betrieb von Motoren. Durch das Verfahren soll die bestehende Lücke zur Produktion von Kraftstoffen aus Gaskondensat geschlossen und die bisherigen Beschränkungen bei ihrer Verarbeitung in einer konventionellen Raffinerie aufgehoben werden.The object of the invention is thus to provide a method by which gas condensate from natural gas production can be converted into high-quality products, in particular in fuels for operating engines. The process aims to close the existing gap in the production of gas condensate fuels and to remove the previous limitations on their processing in a conventional refinery.
Diese Aufgabe wird mit einem Verfahren der eingangs genannten Art gelöst, bei dem das Kondensat einem Reforming-Prozess unter einem Druck von 1 bis 5 bar bei einer Temperatur von 380 C° bis 560 C° zugeführt wird.This object is achieved by a method of the type mentioned, in which the condensate is fed to a reforming process under a pressure of 1 to 5 bar at a temperature of 380 ° C to 560 ° C.
Bei Verwendung eines Kreisgaskompressors und/oder eines Trägergases kann das Verfahren auch bei höheren Drücken betrieben werden; in dem Fall sind die angegebenen Drücke als Partialdrücke des vollständig verdampften Einsatzstoffes zu verstehen.When using a cycle gas compressor and / or a carrier gas, the method can also be operated at higher pressures; In this case, the pressures given are to be understood as partial pressures of the completely vaporized starting material.
Es hat sich gezeigt, dass mit dem erfindungsgemäßen Verfahren Gaskondensate unter den genannten Bedingungen katalytisch in hochwertige Kraftstoffe überführt werden können, die den Anforderungen moderner Motoren an die Klopffestigkeit gerecht werden.It has been found that gas condensates under the conditions mentioned can be catalytically converted into high-quality fuels with the method according to the invention, which meet the requirements of modern engines to the knock resistance.
Das erfindungsgemäße Reforming-Verfahren wird bei einem Druck von 1 bis 5 bar durchgeführt, insbesondere bei etwa 2 bar. Es hat sich gezeigt, dass der üblicherweise im Reforming-Prozess angewandte Druck von mehr als 20 bar zu unerwünscht hohen Anteilen an schweren Kohlenwasserstoffen (C11 +) führt und zudem zu Produkten mit unzureichender Klopffestigkeit führt, die auf Grund ihres hohen Siedepunktes nicht mehr als Benzinkomponente bzw. als Otto-Kraftstoff zu verwenden sind.The reforming process according to the invention is carried out at a pressure of 1 to 5 bar, in particular at about 2 bar. It has been shown that the conducts applied usually in the reforming process pressure of more than 20 bar to undesirably high proportions of heavy hydrocarbons (C 11 +) and also leads to products with inadequate knock resistance which, due to their high boiling point no more than gasoline component or as a gasoline fuel to be used.
Entsprechendes gilt für die Verfahrenstemperatur, die erfindungsgemäß zwischen 380 C° und 560 C° liegt, vorzugsweise zwischen 400 C° und 470 C° und insbesondere zwischen 430 C° und < 450 C°. Analysen haben gezeigt, dass der Anteil an Kohlenwasserstoffen mit C11 + im Produkt in dem angegebenen Druck- und Temperaturregime optimal ist.The same applies to the process temperature according to the invention is between 380 C ° and 560 C °, preferably between 400 C ° and 470 C ° and in particular between 430 C ° and <450 C °. Analyzes have shown that the proportion of hydrocarbons with C 11 + in the product in the specified pressure and temperature regime is optimal.
Wichtig für das Ergebnis ist auch die Verweilzeit, ausgedrückt als LHSV (Liquid Hourly Space Velocity), die in einem Bereich von 0,25 bis 5, vorzugsweise von 1 bis 3 und insbesondere bei etwa 2 liegen sollte.Important for the result is also the residence time, expressed as LHSV (Liquid Hourly Space Velocity), which should be in a range from 0.25 to 5, preferably from 1 to 3 and in particular at about 2.
Das erfindungsgemäße Verfahren wird mit wenigstens einem Zeolith-Katalysator durchgeführt, wobei vorzugsweise Zeolithe auf Basis von SiO2, Al2O3 und P2O5 verwandt werden. Das Verfahren kann dabei in mehreren Stufen mit mehreren Katalysatoren mit unterschiedlichen Leistungsprofilen durchgeführt werden. Die leichteren Fraktionen werden insbesondere über Isomerisierungskatalysatoren in höher siedende Produkte überführt, wobei hier Zeolith-Katalysatoren mit einem Si/Al-Verhältnis von 10 bis 200, vorzugsweise etwa 30, zum Einsatz kommen. Bevorzugt sind Katalysatoren von MOR-, MEL- oder MFI-Typ.The process according to the invention is carried out with at least one zeolite catalyst, zeolites based on SiO 2 , Al 2 O 3 and P 2 O 5 being preferably used. The process can be carried out in several stages with several catalysts with different power profiles. The lighter fractions are converted in particular via isomerization catalysts in higher-boiling products, in which case zeolite catalysts having a Si / Al ratio of 10 to 200, preferably about 30 are used. Preference is given to catalysts of MOR, MEL or MFI type.
Für höher siedende Fraktionen kommen insbesondere Aromatisierungskatalysatoren in Frage, mit denen hochsiedende Anteile des Gaskondensats u.a. in Benzin umgewandelt werden können. Für die Aromatisierung können insbesondere Zeolithe mit einer MFI, BEA, TON, MOR, LTL- oder NTT-Struktur eingesetzt werden, wobei aber eine MFI-Struktur bevorzugt ist. Bei Aromatisierungskatalysatoren beträgt das Si/Al-Verhältnis vorzugsweise 2:1 bis 5:1, insbesondere 3:1 bis 4:1.For higher-boiling fractions are in particular aromatization catalysts in question, which high-boiling fractions of the gas condensate can be converted, inter alia, in gasoline. In particular, zeolites with an MFI, BEA, TON, MOR, LTL or NTT structure can be used for the aromatization, but an MFI structure is preferred. For aromatization catalysts, the Si / Al ratio is preferably 2: 1 to 5: 1, in particular 3: 1 to 4: 1.
Die Katalysatoren weisen Hohlräume auf, bei einer durchschnittlichen Porengröße im Bereich von insbesondere 0,4 bis 1,5 nm und vorzugsweise 0,5 bis 0,7 nm.The catalysts have cavities, with an average pore size in the range of in particular 0.4 to 1.5 nm and preferably 0.5 to 0.7 nm.
Die erfindungsgemäß zum Einsatz kommenden Zeolithe sind üblicherweise mit Metallionen dotiert, wobei der Metallgehalt im Bereich von 0,1 bis 5,0 Gew. - % liegt. Bevorzugte Metalle sind Ni, Pd, Pt mit einer Konzentration von 0,3 bis 0,4 Gewichtsprozent und/oder ein oder mehrere Metalle der Gruppe Zn, Cr, Co, Mg, Ga und Fe, wobei Zn mit einer Gewichtskonzentration von 1 bis 5,0 % bevorzugt ist. Bei den Aromatisierungslkatalysatoren kommen insbesondere Metalle aus der Gruppe Zn, Cr, Co, Mg, Ga, und Fe in Frage, auch hier vorzugsweise Zn, mit einer Gewichtskonzentration von 1 bis 2,5 %, bezogen auf den Katalysator.The zeolites used according to the invention are usually doped with metal ions, the metal content being in the range from 0.1 to 5.0% by weight. Preferred metals are Ni, Pd, Pt with a concentration of 0.3 to 0.4 percent by weight and / or one or more metals of the group Zn, Cr, Co, Mg, Ga and Fe, wherein Zn has a weight concentration of 1 to 5 , 0% is preferred. The aromatization catalysts are in particular metals from the group Zn, Cr, Co, Mg, Ga, and Fe in question, again preferably Zn, with a weight concentration of 1 to 2.5%, based on the catalyst.
Das erfindungsgemäße Verfahren kann in mehreren Varianten durchgeführt werden, wobei am Anfang immer eine Aufspaltung des Kondensats in mehrere Fraktionen steht. Insbesondere wird das Gaskondensat vor der katalytischen Umwandlung in wenigstens drei Fraktionen aufgespalten, eine niedrigsiedende Fraktion, eine mittelsiedende Fraktion und wenigstens eine hochsiedende Fraktion. Die niedrigsiedende Fraktion umfasst Kohlenwasserstoffe bis C4 oder C5, die mittelsiedende Fraktion Kohlenwasserstoffe bis C7, vorzugsweise C6 bis C7, und eine hochsiedende Fraktion bis C10. Die Fraktion der Kohlenwasserstoffe mit C11 + wird dem Reforming-Prozess nicht unterworfen.The inventive method can be carried out in several variants, wherein at the beginning is always a splitting of the condensate into several fractions. In particular, the gas condensate is split into at least three fractions before the catalytic conversion, a low-boiling fraction, a medium-boiling fraction and at least one high-boiling fraction. The low-boiling fraction comprises hydrocarbons up to C 4 or C 5 , the medium-boiling fraction hydrocarbons to C 7 , preferably C 6 to C 7 , and a high-boiling fraction to C 10 . The fraction of hydrocarbons with C 11 + is not subjected to the reforming process.
Wenigstens eine der Fraktionen wird dabei einem Reforming-Prozess zugeführt, eine Fraktion einem optionalen aufbauenden Prozess und zumindest eine hochsiedende Fraktion einer Aromatisierung. Eine mittelsiedende Fraktion mit C6 und C7 kann unmittelbar, ohne weitere Verarbeitung, dem Endlager zugeführt werden; sie ist direkt als Blendkomponente für Benzin verwendbar.At least one of the fractions is thereby fed to a reforming process, a fraction to an optional constituent process and at least one high-boiling fraction of a flavoring. A medium-boiling fraction with C 6 and C 7 can be fed directly, without further processing, the repository; it is directly usable as a blending component for gasoline.
Besonders bevorzugt ist ein Verfahren, bei dem die Kohlenwasserstoffe bis C5 einer Aromatisierung unterworfen werden, die Fraktion C6/C7 dem Endlager zugeführt wird und die Fraktion mit C8 bis C10 einer separaten Aromatisierung unterworfen wird. Mit einem solchen Verfahren ist es möglich, den Anteil an Kohlenwasserstoffen mit C11 + unter 7,5 Gew.- % und insbesondere unter 5 Gew.-% des reformierten Produkts zu halten (siehe
Bei den Reforming-Prozessen kann als Trägergas Stickstoff zugesetzt werden. Häufig ist es auch sinnvoll, Wasserstoff zuzusetzen.In the reforming processes, nitrogen can be added as the carrier gas. Often it makes sense to add hydrogen.
Eine andere bevorzugte Variante, insbesondere bei der Verfügbarkeit von Wasserstoff, ist ein Verfahren, bei dem die Kohlenwasserstoffe bis C4 einer Aromatisierung zugeführt werden, die C5/C6 Fraktion einer Isomerisierung unterworfen wird und die Fraktion ab C7 in einer separaten Aromatisierung umgewandelt wird. Mit einem solchen Verfahren ist es möglich, den Anteil an Aromaten im reformierten Produkt bei gleichbleibender Klopffestigkeit zu reduzieren (siehe
In der Regel werden niedrigsiedende und hochsiedende Fraktionen getrennt reformiert und die dabei enthaltenen Reforming-Produkte einer Fraktionierung unterworfen. Dabei können insbesondere leichte Anteile, die nicht unmittelbar als Kraftstoffe (Benzin, Diesel) verwandt werden können in das Verfahren zurückgeführt werden. Eine solche Kreisgas-Fahrweise kann unter Zusatz von Wasserstoff erfolgen, um die Ausbeute an erwünschten Produkten im mittelsiedenden Bereich zu erhöhen. Zudem ist Wasserstoff grundsätzlich geeignet, die Koksbildung am Katalysator zu vermindern und damit die Standzeit bzw. Zykluszeit, zu verlängern.As a rule, low-boiling and high-boiling fractions are reformed separately and the reforming products contained are subjected to fractionation. In particular, light fractions which can not be used directly as fuels (gasoline, diesel) can be recycled into the process. Such a cycle gas procedure can be carried out with the addition of hydrogen in order to increase the yield of desired products in the middle-boiling range. In addition, hydrogen is basically suitable for reducing coke formation on the catalyst and thus for increasing the service life or cycle time.
Mit verschiedenen Verfahrensvarianten ist es möglich, das Produktspektrum zu verschieben. So kann durchaus neben Benzin in größeren Mengen eine Gasfraktion erzeugt werden, oder aber der Schwerpunkt auf schwerere Kohlenwasserstoffe im Kerosin-/Dieselbereich gelegt werden. Lediglich die C11 +-Fraktion wird in allen Fällen klein gehalten. Die hochsiedenden Anteile, die nicht als Kraftstoffe direkt zu verwerten sind, können beispielsweise Heizöl zugemischt werden oder aber einer separaten Reformierung zugeführt werden, in der dann kurzkettige, niedrigsiedende Produkte entstehen.With different process variants it is possible to shift the product range. Thus, in addition to gasoline in large quantities, a gas fraction can be generated, or the emphasis on heavier hydrocarbons in the kerosene / diesel area are laid. Only the C 11 + fraction is kept small in all cases. The high-boiling components, which can not be used directly as fuels, can for example be mixed with heating oil or else fed to a separate reforming, in which short-chain, low-boiling products are then produced.
Das erfindungsgemäße Verfahren kann neben den beiden bereits beschriebenen Varianten in mehreren weiteren Varianten betrieben werden. In einer dritten Variante (
In einer vierten Variante (
Allen Verfahrensvarianten ist gemeinsam, dass das aufgespaltene Gaskondensat in verschiedenen separaten Strömen gehandhabt und in die gewünschten Endprodukte überführt wird. Eine weitere Gemeinsamkeit besteht darin, dass die C11 +-Fraktion des Gaskondensats nicht dem Reforming-Prozess unterworfen wird. Im Vordergrund steht also immer die Gewinnung von hochwertigen Kraftstoffen, insbesondere von hochoktanigem Otto-Kraftstoff.All process variants have in common that the split gas condensate is handled in different separate streams and converted into the desired end products. Another common feature is that the C 11 + fraction of the gas condensate is not subjected to the reforming process. The focus is therefore always on the production of high-quality fuels, especially high-octane gasoline fuel.
Das erfindungsgemäße Verfahren kann grundsätzlich immer auch ohne die Verwendung von externem Wasserstoff betrieben werden.The inventive method can always be operated without the use of external hydrogen.
Die zum Einsatz kommenden Zeolith-Katalysatoren sind bekannt und vielfach untersucht und allgemein verfügbar. Sie haben sich bei der Umwandlung von Kohlenwasserstoffen bewährt, wobei aber zum Teil sehr viel drastischere Bedingungen zum Einsatz kommen. Bislang war es nicht möglich, zu den erfindungsgemäß gewünschten niedrigen Anteilen an hochsiedenden Kohlenwasserstoffen unter moderaten Bedingungen zu kommen.The zeolite catalysts used are known and widely studied and generally available. They have proven themselves in the conversion of hydrocarbons, but sometimes much more drastic conditions are used. So far, it has not been possible to arrive at the inventively desired low levels of high-boiling hydrocarbons under moderate conditions.
Die erfindungsgemäß eingesetzten Katalysatoren unterliegen den üblichen Alterungs- und Verkokungserscheinungen. Sie können auf übliche Weise regeneriert werden. Hierzu ist es sinnvoll, in dem Verfahren bei der Verwendung von Festbettreaktoren parallel geschaltete Katalysatorbetten vorzusehen, die alternierend der Regenerierung unterworfen werden.The catalysts used according to the invention are subject to the usual aging and coking phenomena. They can be regenerated in the usual way. For this purpose, it is useful to provide in the process in the use of fixed bed reactors parallel catalyst beds, which are alternately subjected to regeneration.
Die Erfindung wird durch die beiliegenden Abbildungen und Tabellen näher erläutert.The invention is further illustrated by the accompanying drawings and tables.
In den Figuren sind die einzelnen Ströme anhand der Kohlenstoffzahlen der entsprechenden Kohlenwasserstoffe charakterisiert. Die Bezeichnung ATM Destillation bezeichnet eine Destillation bei atmosphärischen Druck. Das Kürzel K steht für einen Kompressor, die Kürzel R für ein katalytisches Reaktorbett. Separatoren sind mit SEP bezeichnet, Stabilisatoren mit STA.In the figures, the individual streams are characterized by the carbon numbers of the corresponding hydrocarbons. The term ATM distillation refers to distillation at atmospheric pressure. The abbreviation K stands for a compressor, the abbreviation R for a catalytic reactor bed. Separators are labeled SEP, stabilizers with STA.
Der in
Die im Anhang beigefügte Tabelle veranschaulicht das Verfahrensergebnisse für verschiedene Druck- (P), Temperatur- (T) und Durchsatzbedingungen (LHSV) erhaltenen Oktanzahlen (RON) und C11 +-Anteile. Es zeigt sich, dass bei moderaten Temperaturen im Bereich von 430 bis 450°C und moderaten Drücken bis 2,0 bar hohe RON-Werte und niedrige C11 +-Anteile erzielt werden können.The attached table illustrates process results for various pressure (P), temperature (T), and throughput (LHSV) octane ratings (RON) and C 11 + fractions. It can be seen that at moderate temperatures in the range of 430 to 450 ° C and moderate pressures up to 2.0 bar high RON values and low C 11 + contents can be achieved.
Die Diagramme 1 bis 3 zeigen die Abhängigkeit der RON-Werte und C11 +-Anteile in Abhängigkeit von der Temperatur, dem Druck und dem Durchsatz. Ein Optimum ergibt sich für Temperaturen von 430 bis 450°C, Drücken bis 2,0 bar und Durchsätzen von bis zu 2,0/h.
Claims (17)
der Reforming-Prozess unter einem Druck von 1 bis 5 bar bei einer Temperatur von 380°C bis 560°C durchgeführt wird.A process for the conversion of gas condensates having a boiling range up to about 180 ° C in fuels, particularly in high-oktanigem gasoline fuel, in which originating from the gas recovery condensate reformed using at least one zeolite catalyst, characterized, in that
the reforming process under a pressure of 1 to 5 bar at a temperature of 380 ° C to 560 ° C is performed.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16197027.2A EP3318619A1 (en) | 2016-11-03 | 2016-11-03 | Method for the production of fuels from gas condensates |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16197027.2A EP3318619A1 (en) | 2016-11-03 | 2016-11-03 | Method for the production of fuels from gas condensates |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3318619A1 true EP3318619A1 (en) | 2018-05-09 |
Family
ID=57354107
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16197027.2A Withdrawn EP3318619A1 (en) | 2016-11-03 | 2016-11-03 | Method for the production of fuels from gas condensates |
Country Status (1)
Country | Link |
---|---|
EP (1) | EP3318619A1 (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040182748A1 (en) * | 2002-12-27 | 2004-09-23 | Council Of Scientific And Industrial Research | Process for production of high octane gasoline from straight run light naphtha on Pt containing HZSM - 5 molecular sieve catalyst |
US20110132804A1 (en) * | 2009-12-04 | 2011-06-09 | Saudi Basic Industries Corporation | Increasing octane number of light naphtha using a germanium-zeolite catalyst |
US20120024753A1 (en) * | 2008-06-05 | 2012-02-02 | Chevron U.S.A. Inc. | Multi-stage reforming process to produce high octane gasoline |
US20120024752A1 (en) * | 2010-07-28 | 2012-02-02 | Chevron U.S.A. Inc. | Multi-Stage Hydroprocessing for the Production of High Octane Naphtha |
CA2945839A1 (en) * | 2014-01-28 | 2015-08-06 | Limited Liability Company New Gas Technologies-Synthesis | Catalyst and method for aromatization of c3-c4 gases, light hydrocarbon fractions and aliphatic alcohols, as well as mixtures thereof |
-
2016
- 2016-11-03 EP EP16197027.2A patent/EP3318619A1/en not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040182748A1 (en) * | 2002-12-27 | 2004-09-23 | Council Of Scientific And Industrial Research | Process for production of high octane gasoline from straight run light naphtha on Pt containing HZSM - 5 molecular sieve catalyst |
US20120024753A1 (en) * | 2008-06-05 | 2012-02-02 | Chevron U.S.A. Inc. | Multi-stage reforming process to produce high octane gasoline |
US20110132804A1 (en) * | 2009-12-04 | 2011-06-09 | Saudi Basic Industries Corporation | Increasing octane number of light naphtha using a germanium-zeolite catalyst |
US20120024752A1 (en) * | 2010-07-28 | 2012-02-02 | Chevron U.S.A. Inc. | Multi-Stage Hydroprocessing for the Production of High Octane Naphtha |
CA2945839A1 (en) * | 2014-01-28 | 2015-08-06 | Limited Liability Company New Gas Technologies-Synthesis | Catalyst and method for aromatization of c3-c4 gases, light hydrocarbon fractions and aliphatic alcohols, as well as mixtures thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE69628938T2 (en) | METHOD FOR PRODUCING SYNTHETIC DIESEL FUEL | |
DE2262797A1 (en) | METHOD OF CRACKING UNDER HYDROGEN PRESSURE FOR THE MANUFACTURE OF OLEFINS | |
EP2147082B1 (en) | Method and system for producing synthetic fuels | |
EP0009809B1 (en) | A process for producing olefines | |
EP2130812B1 (en) | Process for producing light olefins from a feed containing triglycerides | |
DE2215665A1 (en) | INTEGRATED PROCESS OF HYDROGEN TREATMENT AND CATALYTIC CLEAVAGE FOR THE PURPOSE OF REFINING SULFURY CRUDE OILS | |
DE2215664A1 (en) | PROCESS FOR MANUFACTURING COCK BASED ON CRUDE OIL THAT TREATED WITH HYDROGEN OR. IS HYDRATED | |
DE112014000972T5 (en) | Improved production of fuels by combined vacuum distillation with solvent deasphalting | |
DE102009046790A1 (en) | Process for the production of hydrocarbons, in particular gasoline, from synthesis gas | |
US10233136B2 (en) | Process for producing benzene from a C5-C12 hydrocarbon mixture | |
DE2164951B2 (en) | Process for the production of gaseous olefins | |
WO2014023417A1 (en) | Method for producing olefins by means of thermal steam cracking in cracking furnaces | |
DE112015004117T5 (en) | METHOD FOR PRODUCING DIESEL FUEL | |
DE112018004190T5 (en) | PRODUCTION OF LIGHT OLEFINES BY AN INTEGRATED STEAM AND HYDROCRACKING PROCESS | |
DE69601346T2 (en) | DESOLFURATION PROCESS FOR CATALYTIC CRACKING GASOLINE | |
EP2688859B1 (en) | Process and plant for preparation of low molecular weight olefins | |
DE2326834A1 (en) | PROCESS FOR PROCESSING HYDROCARBON NAPHTHA INTO A LIQUID PRODUCT WITH A HIGH FLAVORING CONTENT | |
DE2061945C3 (en) | Process for the production of high-octane gasoline | |
WO2007137566A1 (en) | Method for catalytic conversion of organic oxygenated compounds from biomaterials | |
EP3318619A1 (en) | Method for the production of fuels from gas condensates | |
EP0090232A1 (en) | Process for the preparation of olefines from methanol and/or dimethyl ether | |
DE1054624B (en) | Process for the dehydrocyclization and dehydrogenation of starting materials consisting entirely or partially of non-aromatic hydrocarbons | |
DE2134155B2 (en) | Process for the manufacture of high octave unleaded gasoline | |
DE2937376C2 (en) | ||
US9683182B2 (en) | Two-stage diesel aromatics saturation process utilizing intermediate stripping and base metal catalyst |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20181109 |
|
RBV | Designated contracting states (corrected) |
Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20190221 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20190904 |