WO2000013786A1 - Dispositif a plasma provenant de decharges electriques mobiles et ses applications pour transformer des matieres carbonees - Google Patents

Dispositif a plasma provenant de decharges electriques mobiles et ses applications pour transformer des matieres carbonees Download PDF

Info

Publication number
WO2000013786A1
WO2000013786A1 PCT/US1999/020204 US9920204W WO0013786A1 WO 2000013786 A1 WO2000013786 A1 WO 2000013786A1 US 9920204 W US9920204 W US 9920204W WO 0013786 A1 WO0013786 A1 WO 0013786A1
Authority
WO
WIPO (PCT)
Prior art keywords
plasma
wherem
discharges
conversion
carbon
Prior art date
Application number
PCT/US1999/020204
Other languages
English (en)
Other versions
WO2000013786A9 (fr
Inventor
Piotr Czernichowski
Albin Czernichowski
Original Assignee
Laxarco Holding Limited
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Laxarco Holding Limited filed Critical Laxarco Holding Limited
Priority to AU63842/99A priority Critical patent/AU6384299A/en
Publication of WO2000013786A1 publication Critical patent/WO2000013786A1/fr
Publication of WO2000013786A9 publication Critical patent/WO2000013786A9/fr

Links

Classifications

    • 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
    • C01B3/342—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 with the aid of electrical means, electromagnetic or mechanical vibrations, or particle radiations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • 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
    • C10G15/08—Cracking of hydrocarbon oils by electric means, electromagnetic or mechanical vibrations, by particle radiation or with gases superheated in electric arcs by electric means or by electromagnetic or mechanical vibrations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B01J2219/0807—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
    • B01J2219/0809—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes employing two or more electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B01J2219/0807—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
    • B01J2219/0816—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes involving moving electrodes
    • B01J2219/0818—Rotating electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B01J2219/0807—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
    • B01J2219/0824—Details relating to the shape of the electrodes
    • B01J2219/0826—Details relating to the shape of the electrodes essentially linear
    • B01J2219/0828—Wires
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B01J2219/0807—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
    • B01J2219/0824—Details relating to the shape of the electrodes
    • B01J2219/0832—Details relating to the shape of the electrodes essentially toroidal
    • B01J2219/0833—Details relating to the shape of the electrodes essentially toroidal forming part of a full circle
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0875—Gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0877—Liquid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0879—Solid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0892—Materials to be treated involving catalytically active material

Definitions

  • TITLE DEVICE WITH PLASMA FROM MOBILE ELECTRIC DISCHARGES AND ITS APPLICATIONS TO CONVERT CARBON MATTER
  • the invention relates generally to the conversion of carbon substances and more particularly to the use of fixed and mobile electrodes to stretch discharges and create an off equihbnum plasma for stimulating conversion reactions
  • the invention compnses a method and system for converting carbon substances in plasma-chemical reactors based on mobile electric discharges
  • the discharges cause high activation of the medium by unusual species (with respect to the traditional conditions of conversions) onginating from the matter in which these discharges develop
  • electrons, atoms, ions and molecular radicals such as H, OH, O, 0 2 , H + , 0 + , 0 2 + 0 2 , H0 2 , CH 3 , CH 2 , CH, C 2 and many others are detected
  • H, OH, O, 0 2 , H + , 0 + , 0 2 + 0 2 , H0 2 , CH 3 , CH 2 , CH, C 2 and many others are detected Most of these species may exist in their electronic or vibratory excited states with a rather long lifetime They are also known to be extremely chemically active
  • a device compnses one or more fixed electrodes and one or more mobile electrodes Discharges established between the fixed electrodes and the mobile electrodes generate an off equihbnum plasma by very rapidly stretching the discharges between the electrodes and thereby causing the off equihbnum plasma to sweep the gas passing through the reactor in order to stimulate chemical conversions
  • the flow of the matter activated by the plasma may be brought into contact with a metal or ceramic body placed near discharges This body becomes active in the presence of the catalytic species onginating from the plasma and thus participates in the continuation of the conversion
  • Fig 1 is an illustration of a toothed mobile electrode used in one embodiment
  • Fig 2 is an illustration of a multiple-stage reactor using mobile disk electrodes
  • Fig 3 is an illustration of a mobile electrode composing a circular brush
  • Fig 4a is an illustration of an embodiment using an inductor to alter the phase of the terminal voltage with respect to the discharge current and voltage
  • Fig 4b is a graph of the terminal voltage, discharge current and discharge voltage for the embodiment illustrated in Fig 4a While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example m the drawings and will herein be described in detail It should be understood, however, that the drawing and detailed description thereto are not intended to limit the invention to the particular form disclosed, but on the contrary, the mtention is to cover all modifications, equivalents and alternatives falling within the spirit and scope of the present invention as defined by the appended claims
  • the system descnbed herein proposes a device with high voltage mobile discharges, as well as its application for the conversion of hydrocarbons and/or carbon dioxide and/or carbon monoxide
  • Reaction (4) or (4a) of the "dry" reforming can also be considered as an upgrading conversion of C0 2 , a gas suspected of causing the greenhouse effect; of course, that will depend on the main objective of the industrial operation considered.
  • Partial oxidation of very heavy HCs can also be carried out in order to convert them to lighter liquid hydrocarbons. Therefore, this would consist of slightly oxidizing cracking with high added value.
  • HC conversion according to endothermic reactions (1) through (2b) and (4) through (5) would require a supply of preferably "clean" energy, not connected with any external combustion which is not economic and is highly polluting
  • the best way to help these reactions would be to have electnc arcs and/or discharges directly in the medium to be converted, imposing permanent distribution of energy in the larger volume to be treated
  • the transfer of energy of electnc ongin to the gas mixture would occur by direct transfer of the energy to the molecules This would entail excitation, lonization and dissociation phenomena and also Joule effect, considering the mixture partially ionized as a gaseous electnc conductor
  • the gas mixture having become a conductor after lonization (itself due to dielect ⁇ c breakdown, hence to pre-ionization) between electrodes brought to different potentials, would be considered as an elect ⁇ c resistance and, at the same time, as a sort of electrolyte in gaseous phase the plasma
  • Plasma is defined as a state of matter and, therefore, cannot be taken as a c ⁇ te ⁇ on of simila ⁇ ty for different, previously known processes
  • plasma is a gaseous medium in which particles are partially oxidized
  • the main physical macroscopic quantity - temperature - is the same for all the components this is thermodynamic equihbnum
  • Chemists prefer plasmas which do not respect the thermodynamic equilibrium conditions. For example, it is sufficient to act on the free electrons. It is also possible to act on the rotation or vibration properties of certain molecules. In terms of energy, that breaks again the balance of energy exchange between the plasma and the medium surrounding it. This state is called “out of thermodynamic equilibrium” or simply “non-equilibrium”. These plasmas are sometimes called “low temperature” plasmas, although the concept of temperature can no longer be used! There are several methods for generating these plasmas: microwaves, electron beams, flame fronts, etc. However, at industrial scale, the generators of such transposable plasmas are rare and fit only a well-defined application. This is the reason why these plasmas are not used much in chemistry.
  • GlidArc-I already enabled a chemist to envision the distribution of an energy supply directly in the gas mixture, without, for example, resorting to catalysts.
  • a chemist could also distribute the energy directly rather than in thermal form or in chemical form. He could also intervene on the flow still charged with active species from the arc or discharge zone to have these substances react with the feed to be converted or reconverted in a post-plasma zone. Nevertheless, some difficulties were determined in the last few years, hence our research to bypass them. Thus, we have succeeded in perfecting a totally new device with mobile arcs, GlidArc-II.
  • KERKER wrote in general on production tests of synthesis gas at Huls [Hergori von Reduktionsgas oder Synthesegas mit Lichtbogenplasmadan", Elektro-warme international B, Industnelle Elektrowarme, vol 45 (3-4), 155-61 (1987)].
  • the illustrations mdicate a very powerful (1 through 9 MW) traditional tubular arc reactor used at this plant since 1939 to produce acetylene This time, a natural gas steam reforming project is involved, to produce 99.9% pure hydrogen at a very competitive cost with respect to electrolysis (but still more expensive than for hydrogen from traditional steam reforming or partial oxidation methods)
  • reaction 5 HC reformmg with carbon dioxide (reaction 4 or 4a), one smgle simultaneous HC conversion operation by steam reforming accompamed by reforming with carbon dioxide, m the presence of the mverse shift of part of the hydrogen (reaction 5)
  • the new device is based on elect ⁇ c discharges which explode on at least two electrodes, of which at least one is mobile
  • the electrodes are arranged so as to form a mobile structure which can be divergent, but this arrangement is only optional
  • the gas circulates almost mdependently with respect to the structure of the electrodes, for example along one of the electrodes, or perpendicular to the movement of the mobile electrode, or also otherwise
  • the gas flow can also participate m the displacement of the roots of the discharge which, for example, moves rapidly along one of the electrodes
  • the electrodes involved are anywhere at a minimum distance, regardless of their geometnc arrangement That is where electnc breakdown occurs, if the voltage applied to the electrodes exceeds the dielectnc breakdown Immediately after this breakdown, a small volume of plasma, formed between the electrodes, is dnven by the movement of one electrode with respect to the other This dnving is possibly aided by a gas flow
  • the displacement speed of the discharge depends mostly on the mechamcal displacement speed of one (or two
  • the second phase of the life of the discharge that of thermal and electnc non-equihbnum dunng which up to 80% of the energy is mjected, is of special mterest in order to stimulate a chemical reaction
  • the active discharges thus created m the GhdArc-II device, can sweep almost the entire gas flow without the need for accelerating this gas flow in the vicinity of the electrodes
  • the displacement speed of the mobile discharge is then mdependent of the flow-rate and speed of the gas
  • Figure 1 represents a method of execution of the device according to one embodiment
  • a high voltage and low intensity (a few Amperes) discharge is established between end 2 of a stationary electrode 1 and a pomt 4' of a second electrode 3
  • the voltage applied between electrodes 1 and 3 is that of the secondary 6" of the transformer (voltage amplifier) 6 whose primary 6' is connected at 8 with the network
  • the discharge 7 is thus stretched over a great length and sweeps the peripheral zone of mobile electrode 3
  • the power begins to decrease and the discharge enters its thermal non- equilibrium phase
  • the discharge dies down; then it is pruned aga between the stationary electrode 1 and the 4' part nearest electrode 3; then the cycle begins again.
  • the zone affected by the diffused discharge may extend on more than 2 rad between points 4' and 4".
  • FIG. 2 shows the diagram of a reactor with 4 identical stages
  • Each stage includes a disk d and 3 stationary electrodes offset by 120°, identified as r, s and t, each electrode bemg connected to a three-phase transformer phase, the disk bemg connected to the neutral pomt of the transformer This turning disk may also be connected to the ground, which eliminates the problem of elect ⁇ c insulation of this movmg part.
  • the gas is introduced, for example, m k in the lower part of the reactor and extracted in /.
  • the rotating motion of the mobile electrode can be provided by an electnc motor or a compressed gas motor, or even by the gas to be processed
  • the turning electrode may consist of a stack of identical disks d] through d4, be a conductor brush (see Fig. 3) or even be hehcoidal m shape. It is understood that these representations are given only as examples and that other methods of execution may be proposed, particularly 6- or 12-phase electncal supplies.
  • the mtenor part of the body of the reactor can be srmply cyhndncal or equipped with baffles in order to guide the gas flow, for example, vortically.
  • each tummg electrode can be equipped with blades which can very thoroughly stir the gas to be processed.
  • blades which can very thoroughly stir the gas to be processed.
  • Another solution consists of applymg stationary electrodes with an elongated shape which allows the discharge bases to move rapidly on these electrodes Although it is still possible, it is not necessary to resort to a coolmg system for the stationary electrodes, since the intensities used are limited and, as a rule, are lower than 10 A.
  • the reactor is supplied by controlled flows (by mass flow meters) of gas taken from cylmders
  • the reactor supply m compound initially liquid at ambient or higher temperature may also be provided by a dosmg pump
  • the constant flow of said liquid controlled by a valve and a flow meter, can thus be evaporated m an oven, to be then mjected mto the reactor, whether or not bemg previously mixed with another process fluid
  • the incoming fluids are mixed far from the injection spray tip, m the injection tip itself or in its vicinity They can be preheated together or separately by means of a temperature controlled resistance oven
  • This last method would be preferable for an industrial reactor, m order to prevent an early 0 2 + HC combustion at the time of preheating
  • Another subject of this application consists of dividing a GhdArc-II mobile discharge reactor in some compartments By addmg (for certain tests) a more or less perforated separation, for example m the form of gnllwork, we thus create a
  • a pressure gauge shows the pressure mside the reactor, this pressure is established and controlled by a manual valve placed at the reactor exit
  • the products leavmg the reactor are first cooled in an air- heat exchanger When they leave the exchanger, the gases and vapors are directed to a tee-piece which serves to send them either to analysis or to the exhaust chimney
  • the liquids deposit m a cooled flask and in an absorbent matter, then the dry gases are sucked mto a syringe
  • the reactor was not thermally msulated (hence the high losses of energy).
  • the stationary and mobile electrodes are made of stainless steel; no post-plasma compartments.
  • the temperature of the incoming gases was always equal to 22°C
  • This table (as well as the followmg tables) is divided horizontally mto three parts. The first part shows the nature and quantity of the fluids mjected mto the reactor, the specific energy (SE) mjected mto the plasma (the real electnc power of GhdArc-II related to the normal hourly flow of all the incoming gases and vapors, as well as the temperature of the fluid leavmg the reactor, which is equal to the temperature read inside the last plasma compartment (but not m contact with the mobile discharges).
  • SE specific energy
  • each table shows the volumes (m standard liters) of dry products of the process leavmg the reactor after mjection of 1 kWh of electnc energy in the GhdArc-II plasma under experimental conditions.
  • these values mdicate an actual energy cost (EC) m electncity of the process at laboratory scale.
  • This section shows also the energy cost of a unit mass of CO (other products considered “free") or of unit volume of synthesis gas (other products also considered “free”) with a given H 2 /CO ratio.
  • the third part of each table shows the other results of calculations based on the experimental data: the overall rate of conversion of carbon of HC ongm and possibly of CO, ongm, the conversion rates of different hydrocarbons present in the NG, as well as the relative conversion selectivities of carbon present m the HC and possibly of C0 2 ongm towards vanous products.
  • the matenal balances were facilitated by the absence of coke, soot, tar or other pyrolytic compounds m our products (within limits not to exceed 1% expressed m mass of converted carbon).
  • the dry reformmg process assisted by mobile discharges can then be applied, regardless of which natural gas (or other mixture of hydrocarbons) is to be converted.
  • natural gas or other mixture of hydrocarbons
  • a "clean" energy source solar, hydraulic, nuclear, etc.
  • “free” energy source exhaust gas from thermal engmes, etc.
  • Table 2 summarizes tests 31 through 34 of natural gas steam reformmg. This time, the NG earned by the steam, enters preheated at a higher temperature than before. The conversion took place under atmosphenc pressure.
  • the stationary and mobile electrodes are made of stainless steel; no post-plasma compartments.
  • Table 3 summarizes tests 11 through 15 of NG reformmg with an H,0/CO, mixture
  • the three reagents are mjected at 22°C and then H 2 0 is in fog form
  • the conversion takes place under atmosphenc pressure
  • the reactor was not thermally msulated, hence the high energy losses
  • the stationary and mobile electrodes are made of stainless steel, no post-plasma compartments
  • the gas first came m contact with the mobile discharges between the Ni electrodes (first stage), then it passed through the chip zone to take agam the second discharge zone followed by a second Ni chip zone
  • the internal walls of the reactor were lmed with a double layer of refractory felt m order to reduce the thermal losses of the device and to operate at the highest possible temperature
  • Other inert bodies, such as large fragments of ceramic bnck or copper chips could also be placed mstead of Ni chips for some comparative tests
  • Table 5 summarizes 51 through 59 NG reformmg tests m a NG/N 2 /0 2 system, without any water vapor added Whenever we used the term "added” we emphasize the external provenance of this reagent which may appear m any case (but m a very small quantity) as product of the (5), (7) and/or (8) reactions
  • the partial oxidation of a NG with oxygen-ennched air (for example, of membrane provenance) is much less expensive and less dangerous than oxidation with pure oxygen of cryogenic ongm
  • the reagents are mjected through the same nozzle at 28°C The conversion takes place under atmosphenc pressure
  • the reactor is thermally msulated by refractory waddmg to reduce the large losses of energy (except for test 51)
  • the stationary and mobile electrodes are made of stainless steel, no post-plasma compartments
  • ballast up to 40% by volume
  • This ballast can be comparable to the inert nitrogen ballast, although a fraction of C0 2 may participate actively, via reactions (4), (4a) and (5), m the production of CO, which mcreases the content of valuable product.
  • test 58a For a pressure higher than 2 bars (test 58a) and other parameters significantly near those of test 58, we observe all the slightly improved performances (from 10 to 30%). However, when the pressure is agam increased to 6 bars at the time of preliminary tests, we observe an increasing amount of soot, especially for 0 2 NG ratios ⁇ 0.5
  • This post-plasma zone at a temperature lower than 1100°C can be partially filled with a solid metal or ceramic matter which, m contact with a flow of products of treatment of the hydrocarbon feed with plasma, becomes active and participates m a total or almost total conversion of the HCs mto SG with more or less co-generated ethylene and acetylene.
  • HCs such as CH 4 , C 2 H 6 , C 3 H 8 and C 4 H, 0 mto synthesis gas and also, partially, mto valuable products: C 2 H 4 and C 2 H 2 , without usmg traditional catalysts.
  • a broad range of ratios of the two oxidizers (0 2 and H 2 0) with respect to the NGs may be used. Our examples are given for 0 2 /NG values between 0 06 and 0.97 and H 2 0/HC between 0 and 2 5, but it is evident that we can further expand at will these two terminals from zero to infinity, smce our mobile discharges can be generated m pure water vapor as well as m pure oxygen. Thus, all the H 2 0/0 2 /NG mixtures can be converted m the reactor descnbed herem Accordmg to need, we can in this manner obtain synthesis gas with an H 2 /CO ratio near 2 for the
  • the selectivities of NG pyrolysis towards acetylene, ethylene and soot mdicate that reaction (2b) of the complete pyrolysis is m the minonty. This is surpnsmg at this low level ( ⁇ 300°C) of average temperatures of the outgomg gases.
  • the methane entermg the active discharge is treated at certainly much higher "temperature” (smce this concept is reserved for the complete thermodynamic equihbnum), but the products of this plasma pyrolysis are soon abandoned at relatively low temperature, smce the mobile discharge is no longer present
  • the sulfur and metal contents m the residues may attam very high values, makmg it much more difficult to treat and upgrade the products
  • the metals (V, Na) are undesirable poisons for the traditional hydro-treatment catalysts and render the hydrogen processes inoperative
  • HCs These fogs ongmated from preheating (up to 370°C) of liquid hydrocarbons (such as gasoil or n-C 16 ) driven with a process gas (dosed by flow meter) by means of a dosing pump through a tubular oven heated by electnc resistance
  • the liquid would evaporate partially m the oven, thus forming a mixture of gas/vapors/droplets which entered through the upper part of the reactor to undergo four stages of the mobile discharge Part of the liquid would be thrown on the inner walls of the reactor by centntugal force from rotation of the central disks dnving the rotation of the gas (and of the fog) filling the reactor
  • a liquid film thus would flow slowly on the walls while bemg m contact with the post-discharge gas containing multiple active radicals
  • the products of the conversion exited through the lower part of the reactor where they were separated m a trap at 0°C mto liquids and gas/vapors for qualitative and quantitative analysis
  • Tests with pure n-C, 6 (Hexadecane or otherwise Cetane) simulating a heavy feed were performed m the presence of vanous plasma-forming gases: H 2 and/or N 2 , N 2 /H 2 0, N 2 /0 2 , CH 4 / N 2 /0 2 or C0 2 /N 2 /0 2 m different proportions.
  • the presence of oxygen seemed puzzlmg, but we envisioned a process m which part of the heavy hydrocarbons (considered a waste to be upgraded) would be converted in place mto Hydrogen used to hydrogenate the other part of the load.
  • the n-C, 6 flow rate would vary between 0.16 and 0.50 kg/h, the flow rate of the incoming plasma-forming gas between 1 4 and 2.4 m 3 (n)/h, the electnc power of the reactor between 0.7 and 2.0 kW.
  • the most important vanable of this set was found to be the plasma-forming gas. It should be noted that, regardless of which plasma-forming gas, the same type of "useful" light product is always observed m the liquid recovered: the alpha-olefins centered on C ⁇ (between C 6 and C 15 ).
  • H 2 or NH radicals plays a positive role
  • the role of the hydrogen plasma at low temperature seems to be limited, perhaps when an additional medium intervenes in the system
  • This analysis seems to be remforced by our experiments conducted as a function of the gas volume and of the nature of the gas in which the role of the hydrogen plasma alone m the conversion phenomenon seems to remam relatively low
  • the first conclusions which we draw from this are that the hydrogen plasma (at low temperature) hardly acts on liquid HCs (fine droplets) and that the experimented reduction conditions do not appear to be very favorable towards obtaimng major conversion of heavy HCs mto light liquid fractions
  • the subject of this application is then a process which makes oxidation and partial cracking of hydrocarbons possible, in the active presence of water vapor and/or of carbon dioxide and/or of oxygen, without need for the intervention of other reagents or catalysts, as well as without the formation of soot, coke or tar which would hinder the proper operation of the reactor.
  • the tests demonstrate clearly the feasibility of steam reforming, "dry" reforming with carbon dioxide, simultaneous reforming with an H,0/CO, mixture or partial oxidation with oxygen, all accompanied by hydrocarbon non-catalytic cracking. This partial oxidation and steam reforming are also accompanied by reforming with carbon dioxide (if it is already present in the NG or is created by the over-oxidation parasite reactions).
  • the necessary reagents are extremely simple water and/or C0 2 and/or 0 2 •
  • the unit is very compact and, therefore, can be transported and installed near the storage, emission or extraction site of the products to be treated (for example, offshore oil platforms to convert associated gases)
  • the GhdArc-II reactors have no thermal inertia and, therefore, can respond very quickly to control signals • Extrapolation to large volumes will be easy.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Electromagnetism (AREA)
  • General Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Toxicology (AREA)
  • Mechanical Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

L'invention concerne un procédé et un système utilisant du plasma provenant de décharges électriques mobiles pour transformer une substance carbonée. Le procédé et le système (R) utilisent du plasma provenant de décharges (7) électriques mobiles pour transformer des substances carbonées telles que des hydrocarbures légers, des hydrocarbures lourds ou des résidus provenant du raffinage de ceux-ci, du CO2 ou du CO en produits tels que des gaz contenant CO et/ou H2 et/ou C2H4 et C2H2 et/ou des combustibles carbonés liquides. Les transformations sont basées sur une oxydation et/ou un craquage de la matière en présence de vapeur d'eau et d'un gaz tel que CO2, O2, N2, H2, seul ou mélangé. Le système produit un plasma déséquilibré en étendant très rapidement les décharges (7) produites entre au moins une électrode fixe (r, s, t) et au moins une électrode mobile (d). Le plasma déséquilibré balaie le gaz traversant le réacteur afin d'activer des transformations chimiques. L'écoulement de matières activées par le plasma entrant par (k) peut être soumis à une ou à plusieurs étapes (d1, d2, d3, d4) de décharge, et peut être mis en contact avec un corps métallique ou céramique placé à proximité des décharges avant de sortir par (l). Ce corps devient actif en présence des espèces catalytiques provenant du plasma, et contribue ainsi à la poursuite de la transformation.
PCT/US1999/020204 1998-09-03 1999-09-01 Dispositif a plasma provenant de decharges electriques mobiles et ses applications pour transformer des matieres carbonees WO2000013786A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU63842/99A AU6384299A (en) 1998-09-03 1999-09-01 Device with plasma from mobile electric discharges and its applications to convert carbon matter

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR98/11172 1998-09-03
FR9811172A FR2786409B1 (fr) 1998-09-03 1998-09-03 Dispositif a plasma de decharges electriques mobiles et ses applications pour convertir une matiere carbonee

Publications (2)

Publication Number Publication Date
WO2000013786A1 true WO2000013786A1 (fr) 2000-03-16
WO2000013786A9 WO2000013786A9 (fr) 2000-08-10

Family

ID=9530198

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/020204 WO2000013786A1 (fr) 1998-09-03 1999-09-01 Dispositif a plasma provenant de decharges electriques mobiles et ses applications pour transformer des matieres carbonees

Country Status (3)

Country Link
AU (1) AU6384299A (fr)
FR (1) FR2786409B1 (fr)
WO (1) WO2000013786A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6356457B1 (en) 1999-06-07 2002-03-12 Sun Microsystems, Inc. Circuit card support mechanism and method
WO2003055795A1 (fr) * 2001-12-21 2003-07-10 Siemens Aktiengesellschaft Procede et dispositif de traitement ou de transformation de combustibles gazeux
DE102006061188A1 (de) * 2006-12-22 2008-06-26 J. Eberspächer GmbH & Co. KG Verfahren zur Herstellung von Wasserstoff aus Wasserstoffverbindungen der Elemente der 4. bis 6. Hauptgruppe
US7736400B2 (en) * 2006-02-14 2010-06-15 Gas Technology Institute Plasma assisted conversion of carbonaceous materials into a gas
US7758663B2 (en) * 2006-02-14 2010-07-20 Gas Technology Institute Plasma assisted conversion of carbonaceous materials into synthesis gas
DE102013004514B3 (de) * 2013-03-15 2014-07-10 Al-Ko Kober Ag Elektrodeneinrichtung für eine Plasmaentladung mit gleitendem Lichtbogen
CN104162360A (zh) * 2014-09-03 2014-11-26 深圳市普瑞美泰环保科技有限公司 一种等离子体催化空气净化装置
WO2015059702A1 (fr) * 2013-10-24 2015-04-30 Ionmed Ltd. Traitement par plasma froid
RU2579099C2 (ru) * 2014-07-31 2016-03-27 Открытое акционерное общество "Нефтяная компания "Роснефть" Способ некаталитического гидрообессеривания нефтепродуктов
RU2699124C1 (ru) * 2019-01-30 2019-09-03 Государственный научный центр Российской Федерации - федеральное государственное унитарное предприятие "Исследовательский Центр имени М.В. Келдыша" Плазмохимический способ получения синтез-газа и установка для его осуществления

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR102018002717A2 (pt) * 2018-02-08 2019-08-27 Carlos Pereira Filho Alberto queimador com combustão assistida a plasma

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1231683B (de) * 1961-05-09 1967-01-05 Produits Azotes Soc D Verfahren und Vorrichtung zur Erzeugung von Acetylen und AEthylen enthaltenden Gas-gemischen
US3607714A (en) * 1968-02-07 1971-09-21 Ugine Kuhlmann Device for cracking organic products in liquid phase by means of an electric arc
DE19735362A1 (de) * 1996-08-14 1998-02-19 Fujitsu Ltd Gasreaktor
FR2758317A1 (fr) * 1997-01-13 1998-07-17 Piotr Czernichowski Conversion d'hydrocarbures assistee par les arcs electriques glissants en presence de la vapeur d'eau et/ou de gaz carbonique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1231683B (de) * 1961-05-09 1967-01-05 Produits Azotes Soc D Verfahren und Vorrichtung zur Erzeugung von Acetylen und AEthylen enthaltenden Gas-gemischen
US3607714A (en) * 1968-02-07 1971-09-21 Ugine Kuhlmann Device for cracking organic products in liquid phase by means of an electric arc
DE19735362A1 (de) * 1996-08-14 1998-02-19 Fujitsu Ltd Gasreaktor
FR2758317A1 (fr) * 1997-01-13 1998-07-17 Piotr Czernichowski Conversion d'hydrocarbures assistee par les arcs electriques glissants en presence de la vapeur d'eau et/ou de gaz carbonique

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6356457B1 (en) 1999-06-07 2002-03-12 Sun Microsystems, Inc. Circuit card support mechanism and method
WO2003055795A1 (fr) * 2001-12-21 2003-07-10 Siemens Aktiengesellschaft Procede et dispositif de traitement ou de transformation de combustibles gazeux
US7736400B2 (en) * 2006-02-14 2010-06-15 Gas Technology Institute Plasma assisted conversion of carbonaceous materials into a gas
US7758663B2 (en) * 2006-02-14 2010-07-20 Gas Technology Institute Plasma assisted conversion of carbonaceous materials into synthesis gas
DE102006061188A1 (de) * 2006-12-22 2008-06-26 J. Eberspächer GmbH & Co. KG Verfahren zur Herstellung von Wasserstoff aus Wasserstoffverbindungen der Elemente der 4. bis 6. Hauptgruppe
DE102013004514B3 (de) * 2013-03-15 2014-07-10 Al-Ko Kober Ag Elektrodeneinrichtung für eine Plasmaentladung mit gleitendem Lichtbogen
WO2015059702A1 (fr) * 2013-10-24 2015-04-30 Ionmed Ltd. Traitement par plasma froid
RU2579099C2 (ru) * 2014-07-31 2016-03-27 Открытое акционерное общество "Нефтяная компания "Роснефть" Способ некаталитического гидрообессеривания нефтепродуктов
CN104162360A (zh) * 2014-09-03 2014-11-26 深圳市普瑞美泰环保科技有限公司 一种等离子体催化空气净化装置
WO2016033847A1 (fr) * 2014-09-03 2016-03-10 深圳市普瑞美泰环保科技有限公司 Dispositif plasma-catalytique de purification d'air
RU2699124C1 (ru) * 2019-01-30 2019-09-03 Государственный научный центр Российской Федерации - федеральное государственное унитарное предприятие "Исследовательский Центр имени М.В. Келдыша" Плазмохимический способ получения синтез-газа и установка для его осуществления

Also Published As

Publication number Publication date
WO2000013786A9 (fr) 2000-08-10
FR2786409B1 (fr) 2001-01-05
AU6384299A (en) 2000-03-27
FR2786409A1 (fr) 2000-06-02

Similar Documents

Publication Publication Date Title
US6007742A (en) Electrically assisted partial oxidation of light hydrocarbons by oxygen
AP1038A (en) Conversion of hydrocarbons assisted by gliding electric arcs in the presence of water vapor and/or carbon dioxide.
Zhang et al. Steam reforming of toluene and naphthalene as tar surrogate in a gliding arc discharge reactor
EP1012113B1 (fr) Oxydation partielle par de l'oxygene d'hydrocarbures legers, assistee electriquement
Czernichowski GlidArc assisted preparation of the synthesis gas from natural and waste hydrocarbons gases
Tatarova et al. Plasmas for environmental issues: From hydrogen production to 2D materials assembly
WO1998030524A9 (fr) Transformation d'hydrocarbures assistee par des arcs electriques glissants
KR101401423B1 (ko) 마이크로웨이브 플라즈마­촉매 하이브리드 공정을 이용한 이산화탄소로부터 가연성 합성가스 제조 장치 및 방법
Sun et al. Plasma catalytic steam reforming of a model tar compound by microwave-metal discharges
JPS60500625A (ja) 電気ア−ク変換法および装置
WO2000013786A1 (fr) Dispositif a plasma provenant de decharges electriques mobiles et ses applications pour transformer des matieres carbonees
Wnukowski et al. Sewage sludge-derived producer gas valorization with the use of atmospheric microwave plasma
US6326407B1 (en) Hydrocarbon synthesis
Bromberg et al. Plasma reforming of diesel fuel
CN1306151A (zh) 电和烃同时产生的方法
Czernichowski Gliding discharge reactor for H2S valorization or destruction
Slovetskii Plasma-chemical processes in petroleum chemistry
Khan et al. A comprehensive review of the methane decomposition using a gliding arc discharge reactor for hydrogen generation
Schmidt‐Szałowski et al. Catalytic effects of metals on the conversion of methane in gliding discharges
Aleknaviciute Plasma assisted decomposition of methane and propane and cracking of liquid hexadecane
Oliveira et al. A Review on Plasma Gasification of Solid Residues: Recent Advances and Developments. Energies 2022, 15, 1475
Saleem Treatment of biomass gasification tars with non-thermal plasmas
Rusu DEVELOPMENT TRENDS OF COLD PLASMA REACTORS IN THE GLOBAL CONTEXT OF CARBON EMISSION REDUCTION.
WO2024009192A2 (fr) Procédé de clivage homolytique et hétérolytique dans des molécules de gaz et de liquides
Schmidt-Szałowski et al. Plasma-catalytic processes in gliding discharges

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref country code: AU

Ref document number: 1999 63842

Kind code of ref document: A

Format of ref document f/p: F

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
AK Designated states

Kind code of ref document: C2

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: C2

Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

COP Corrected version of pamphlet

Free format text: PAGES 1/4-4/4, DRAWINGS, REPLACED BY NEW PAGES 1/4-4/4; DUE TO LATE TRANSMITTAL BY THE RECEIVING OFFICE

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase