EP0316234B1 - Verfahren und Einrichtung für die hydrierende Pyrolyse von schweren Kohlenwasserstoffen durch einen Plasmastrahl, insbesondere ein H2/CH4-Plasma - Google Patents

Verfahren und Einrichtung für die hydrierende Pyrolyse von schweren Kohlenwasserstoffen durch einen Plasmastrahl, insbesondere ein H2/CH4-Plasma Download PDF

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Publication number
EP0316234B1
EP0316234B1 EP19880402817 EP88402817A EP0316234B1 EP 0316234 B1 EP0316234 B1 EP 0316234B1 EP 19880402817 EP19880402817 EP 19880402817 EP 88402817 A EP88402817 A EP 88402817A EP 0316234 B1 EP0316234 B1 EP 0316234B1
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EP
European Patent Office
Prior art keywords
hydropyrolysis
hydrocarbons
gas
plasma
injection
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.)
Expired - Lifetime
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EP19880402817
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English (en)
French (fr)
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EP0316234A1 (de
Inventor
Jean-Marie Baronnet
Christian Daumas
Renée Derai
François Pingaud
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGENCE FRANCAISE POUR LA MAITRISE DE L'ENERGIE
Electricite de France SA
Universite de Limoges
Original Assignee
AGENCE FRANCAISE POUR LA MAITRISE DE L'ENERGIE
Electricite de France SA
Universite de Limoges
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Publication of EP0316234B1 publication Critical patent/EP0316234B1/de
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    • 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
    • C10G15/00—Cracking of hydrocarbon oils by electric means, electromagnetic or mechanical vibrations, by particle radiation or with gases superheated in electric arcs
    • C10G15/12—Cracking of hydrocarbon oils by electric means, electromagnetic or mechanical vibrations, by particle radiation or with gases superheated in electric arcs with gases superheated in an electric arc, e.g. plasma

Definitions

  • the present invention relates to a process and an installation for hydropyrolysis of heavy hydrocarbons.
  • hydropyrolysis of hydrocarbons which mainly applies to the cracking of liquid hydrocarbons with a high number of carbons and / or comprising a significant proportion of aromatic constituents, consists in carrying out a thermal cracking in the presence of hydrogen by diluting the hydrocarbons in a phase hydrogenated gas at moderate pressure (a few bars to a few tens of bars).
  • the hydrogen present in excess during this reaction exerts a blocking effect on undesirable polymerization, condensation and aromatization reactions between two molecules of unsaturated hydrocarbons.
  • the reactions involve essentially play free radicals (mainly H., But also CH., CH2., CH3.), A phenomenon characteristic of the hydropyrolysis relative to thermal cracking without hydrogen, the presence and the kinetics of recombination of these radicals free being essential parameters determining the efficiency and the yield of the hydropyrolysis reaction envisaged.
  • Hydropyrolysis cracking applies particularly well to the transformation of heavy residues comprising a high proportion of non-volatile aromatic components as well as a high proportion of residual materials (Ni, V, S) which make direct hydrogenation by catalysis difficult and expensive, in particular due to the rapid degradation of the catalyst due to the residual materials.
  • FR-A-2 542 004 describes in particular a process and a device, assisted by electricity, for cracking by hydropyrolysis, in which an electric arc is produced between an anode and a distant cathode placed opposite, the hydrocarbons being injected in the form of a vortex flow around the arc column.
  • the injection of hydrocarbons is preferably done there tangentially or obliquely against the current of the arc jet, or by vortex sheathing the arc and striking the foot of the anode.
  • the gas generating free radicals is injected radially into the plasma jet.
  • the gas stream is non-vortex at the point of injection of the hydrocarbons, and it is accelerated prior to the injection of the hydrocarbons.
  • the radial injection of the gas generating free radicals does not create any vortex and allows a very fine spraying of the charge ensuring a very superior plasma / hydrocarbon mixture.
  • a convergent-divergent oriented in the axis of the plasma jet, the injection of hydrocarbons being carried out at this convergent-divergent.
  • This convergent-divergent allows to obtain all the advantages mentioned above, ensuring an excellent mixture of the two reactive phases and a cooling of the flow which causes a slowdown of the recombination reactions of free radicals.
  • FIG 1 there is shown schematically a conversion unit implementing the installation of the present invention.
  • This conversion unit comprises a plasma torch 100, which is of a conventional type of plasma projection torch. As can be seen in detail in FIG. 2 which shows the lower part of this torch, it comprises a cathode 101 of the hot cathode type in thoriated tungsten, placed in the axis of a nozzle-anode 102 comprising a channel axial 103 at the outlet of which the plasma jet will be projected, at a temperature between 2000 and 3500 K, for example of the order of 3250 K.
  • This torch 100 is supplied with plasma gas (FIG. 1) by a pipe 110 connected to reserves 120 of hydrogen and argon by means of a series of valves V and sensors of flow rate D, pressure P and temperature T.
  • the plasma torch operates continuously, both with an argon-hydrogen mixture (for example, at around 10% argon) as with pure hydrogen.
  • a direct current generator 130 makes it possible to supply the torch 100 with the desired voltages and intensities, for example in a range going from 300 V / 400 A to 1200 V / 100 A, the output voltage being regulated, for example by semiconductors controlled in phase.
  • the reservoir 360 is pressurized, for example by a gas 362, such as natural gas or methane, to allow the charge to be injected under pressure into the stage 300.
  • a gas 362 such as natural gas or methane
  • the injection of the charge at the location of the throttle of the convergent-divergent creates a suction of liquid allowing a very effective injection, due to the vacuum produced at this location by plasma flow.
  • stage 300 Downstream of stage 300, the mixed constituents react at the outlet of the convergent-divergent in a stage 400 forming an actual reactor, the gaseous and liquid reaction products being collected, separated and analyzed by circuits 500 of conventional type which will not described in detail.
  • a probe 410 also makes it possible to take a sample and measure its temperature at the very heart of the reactor 400.
  • the injection of cold gas (at a temperature close to room temperature) has the effect of lowering the temperature of the plasma set at the anode outlet (where the temperature of the argon / hydrogen mixture or of pure hydrogen is between 2000 and 3500 K, for example of the order of approximately 3250 K as indicated above) at a temperature remaining below approximately 2800 K in the lower part of the chamber 230.
  • the cylinder 250 constituting the wall of the mixing chamber can be formed from an external piece 251 of copper provided with a sleeve 252 formed of a material limiting the transfer of heat to the room. made of copper, for example a 5 mm thick boron nitride sleeve.
  • the stage 300 for injecting the liquid charge essentially comprises a convergent-divergent 310,320 forming a throttle 330 at the level of which the liquid charge is injected.
  • the charge is preferably injected through a plurality of orifices 340 (for example three in number, arranged radially at 120 °), with a radial orientation and perpendicular to the axis nozzle.
  • the homogeneity of the injection of the charge through these orifices is obtained by a distributor interposed between the orifices injection line and supply line for the liquid charge.
  • the holes have for example a diameter of 1.5 mm for a nozzle diameter at the location of the neck of 3 mm and an angle at the top of the diverging point of 16 °.
  • the piece constituting the convergent-divergent can be made of copper, or else of stainless steel to have a higher wall temperature.
  • the depression produced at the constriction of the convergent-divergent and the suction of the resulting charge make it possible to divide and nebulize very finely the injected charge (which correlatively increases the exchange surface), the shape of the convergent- divergent favoring an intimate mixture of hydrocarbons within the plasma rich in free radicals.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Electromagnetism (AREA)
  • General Chemical & Material Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Plasma Technology (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Claims (10)

1. Verfahren für die hydrierende Pyrolyse von schweren Kohlenwasserstoffen, gekennzeichnet durch die Stufen:
- Erzeugung und Ausstoß eines Plasmastrahles unter Druck, hergestellt auf Basis eines Plasmidgases, Erzeuger von freien radikalen H.,
- radiale InJektion eines Erzeugergases für freie Radikale, insbesondere für Radikale H., CH., CH₂. und CH₃., in den so erzeugten Plasmastrahl,
- InJektion, in den resultierenden nicht-wirbelnden Gasstrom an diesem Punkt (330), von hydrierend zu pyrolysierenden Kohlenwasserstoffen, um sie mit dem Erzeugergas für freie Radikale reagieren zu lassen,
- Rückgewinnung der so erhaltenen Produkte der hydrierenden Pyrolyse.
2. Verfahren nach Anspruch 1, bei dem man den Gasstrom vor der InJektion der Kohlenwasserstoffe beschleunigt.
3. Verfahren nach einem der Ansprüche 1 oder 2, bei dem die Temperatur des Plasmastrahles im Punkt (230) der InJektion des Erzeugergases für freie Radikale zwischen etwa 2000 und 3500 K liegt.
4. Verfahren nach einem der Ansprüche 1 bis 3, bei dem das Erzeugergas für freie Radikale Wasserstoff oder eine Mischung aus Wasserstoff und Methan ist.
5. Verfahren nach einem der Ansprüche 1 bis 4, bei dem die hydrierend zu pyrolysierenden Kohlenwasserstoffe in den Gasstrom durch eine Vielzahl von InJektionsöffnungen (340), die umfangsmäßig auf gleichförmige Weise verteilt sind, injiziert werden.
6. Verfahren nach einem der Ansprüche 1 bis 5, bei dem die Temperatur des Gasstromes im Punkt (330) der InJektion der hydrierend zu pyrolysierenden Kohlenwasserstoffe geringer als etwa 2800 K ist.
7. Einrichtung für die hydrierende Pyrolyse von schweren Kohlenwasserstoffen, gekennzeichnet durch:
- einen Plasmabrenner (100), zum Erzeugen und Ausstoßen eines Plasmastrahles unter Druck auf Basis eines Plasmidgases,
- eine Zwischenstufe (200), welche eine Mischkammer (230) aufweist, in die ein Erzeugergas für freie Radikale peripher und radial durch eine Vielzahl von Öffnungspunkten (240) in dem Plasmastrahl injiziert wird, insbesondere für Radikale H., CH., CH₂. und CH₃.,
- Mittel zum Injizieren, in den sich niederdruckseitig ergebenden Gasstrom, der hydrierend zu pyrolysierenden Kohlenwasserstoffe,
- Mittel (400, 500) zum Rückgewinnen, stromabwärts, der Produkte der hydrierenden Pyrolyse.
8. Einrichtung nach Anspruch 7, weiterhin aufweisend:
- stromabwärts der Zwischenstufe einen Diffusor (310, 320), der in der Achse des Plasmastrahles ausgerichtet ist, wobei die Injektion der Kohlenwasserstoffe auf der Höhe dieses Diffusors bewirkt wird.
9. Einrichtung nach Anspruch 8, bei der die hydrierend zu pyrolysierenden Kohlenwasserstoffe auf der Höhe der Drossel (330) des Diffusors injiziert werden.
10. Einrichtung nach einem der Asprüche 8 oder 9, bei der die hydrierend zu pyrolysierenden Kohlenwasserstoffe in den Diffusor durch eine Vielzahl von Öffnungen (340), die umfangsmäßig auf gleichförmige weise verteilt sind, injiziert werden.
EP19880402817 1987-11-10 1988-11-09 Verfahren und Einrichtung für die hydrierende Pyrolyse von schweren Kohlenwasserstoffen durch einen Plasmastrahl, insbesondere ein H2/CH4-Plasma Expired - Lifetime EP0316234B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8715546 1987-11-10
FR8715546A FR2622894B1 (fr) 1987-11-10 1987-11-10 Procede et installation d'hydropyrolyse d'hydrocarbures lourds par jet de plasma,notamment de plasma d'h2/ch4

Publications (2)

Publication Number Publication Date
EP0316234A1 EP0316234A1 (de) 1989-05-17
EP0316234B1 true EP0316234B1 (de) 1992-06-03

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EP19880402817 Expired - Lifetime EP0316234B1 (de) 1987-11-10 1988-11-09 Verfahren und Einrichtung für die hydrierende Pyrolyse von schweren Kohlenwasserstoffen durch einen Plasmastrahl, insbesondere ein H2/CH4-Plasma

Country Status (3)

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EP (1) EP0316234B1 (de)
DE (1) DE3871723T2 (de)
FR (1) FR2622894B1 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2639354B1 (fr) * 1988-11-24 1993-01-22 Gaz De France Procede de craquage d'une charge d'hydrocarbures lourds en hydrocarbures plus legers et dispositif pour la mise en oeuvre de ce procede
NL1010288C2 (nl) * 1998-10-12 2000-04-13 Stichting Energie Werkwijze voor de conversie van waterstof in substituut aardgas.
DE29919142U1 (de) * 1999-10-30 2001-03-08 Agrodyn Hochspannungstechnik G Plasmadüse
CN113247881B (zh) * 2021-05-17 2023-06-20 常州大学 一种甲烷等离子体裂解制备纳米碳的装置及方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2304243A1 (fr) * 1975-03-14 1976-10-08 Inst Teplo I Massoobmena Akade Procede de chauffage de gaz et reacteur plasmochimique a arc electrique pour sa mise en oeuvre
US4144444A (en) * 1975-03-20 1979-03-13 Dementiev Valentin V Method of heating gas and electric arc plasmochemical reactor realizing same
US4010090A (en) * 1975-08-11 1977-03-01 Westinghouse Electric Corporation Process for converting naturally occurring hydrocarbon fuels into gaseous products by an arc heater
FR2542004B1 (fr) * 1983-03-02 1985-06-21 British Petroleum Co Procede de conversion assistee a l'electricite de produits carbones lourds

Also Published As

Publication number Publication date
EP0316234A1 (de) 1989-05-17
FR2622894A1 (fr) 1989-05-12
DE3871723D1 (de) 1992-07-09
DE3871723T2 (de) 1992-12-24
FR2622894B1 (fr) 1990-03-23

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