EP3548426A1 - Réacteur à plasma et procédé pour faire fonctionner un réacteur à plasma - Google Patents

Réacteur à plasma et procédé pour faire fonctionner un réacteur à plasma

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Publication number
EP3548426A1
EP3548426A1 EP17818441.2A EP17818441A EP3548426A1 EP 3548426 A1 EP3548426 A1 EP 3548426A1 EP 17818441 A EP17818441 A EP 17818441A EP 3548426 A1 EP3548426 A1 EP 3548426A1
Authority
EP
European Patent Office
Prior art keywords
hydrocarbon
plasma
hydrocarbon fluid
reactor
pressure
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.)
Pending
Application number
EP17818441.2A
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German (de)
English (en)
Inventor
Olaf Kühl
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.)
CAPHENIA GMBH
Original Assignee
Ccp Technology GmbH
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 Ccp Technology GmbH filed Critical Ccp Technology GmbH
Publication of EP3548426A1 publication Critical patent/EP3548426A1/fr
Pending legal-status Critical Current

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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J19/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/087Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J19/088Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J12/00Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
    • B01J12/002Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor carried out in the plasma state
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J19/002Avoiding undesirable reactions or side-effects, e.g. avoiding explosions, or improving the yield by suppressing side-reactions
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • CCHEMISTRY; METALLURGY
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/20Graphite
    • C01B32/205Preparation
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00051Controlling the temperature
    • B01J2219/00054Controlling or regulating the heat exchange system
    • B01J2219/00056Controlling or regulating the heat exchange system involving measured parameters
    • B01J2219/00058Temperature measurement
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00051Controlling the temperature
    • B01J2219/00054Controlling or regulating the heat exchange system
    • B01J2219/00056Controlling or regulating the heat exchange system involving measured parameters
    • B01J2219/00065Pressure measurement
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    • B01J2219/00049Controlling or regulating processes
    • B01J2219/00162Controlling or regulating processes controlling the pressure
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J2219/00164Controlling or regulating processes controlling the flow
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    • B01J2219/0822The electrode being consumed
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    • B01J2219/0824Details relating to the shape of the electrodes
    • B01J2219/0826Details relating to the shape of the electrodes essentially linear
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    • B01J2219/0807Processes 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
    • B01J2219/0824Details relating to the shape of the electrodes
    • B01J2219/0826Details relating to the shape of the electrodes essentially linear
    • B01J2219/083Details relating to the shape of the electrodes essentially linear cylindrical
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J2219/0807Processes 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
    • B01J2219/0837Details relating to the material of the electrodes
    • B01J2219/0839Carbon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/0807Processes 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
    • B01J2219/0837Details relating to the material of the electrodes
    • B01J2219/0841Metal
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J2219/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0869Feeding or evacuating the reactor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/0894Processes carried out in the presence of a plasma
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J2219/08Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
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    • B01J2219/0898Hot plasma
    • CCHEMISTRY; METALLURGY
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0266Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0272Processes for making hydrogen or synthesis gas containing a decomposition step containing a non-catalytic decomposition step
    • CCHEMISTRY; METALLURGY
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    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0805Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0861Methods of heating the process for making hydrogen or synthesis gas by plasma
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205Composition of the feed
    • C01B2203/1211Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235Hydrocarbons

Definitions

  • the present invention relates to a plasma reactor and method of operating a plasma reactor to decompose a hydrocarbon fluid.
  • US Pat. No. 5,997,837 A1 describes a known plasma reactor which was used in the 1990s as an experimental reactor for the production of carbon particles or C particles.
  • the known plasma reactor has a reactor chamber which is enclosed by a reactor wall.
  • a plasma torch is fixed, which has annular electrodes.
  • the plasma torch has a burner part which projects into the reactor chamber.
  • In the center of the annular electrodes is a central hydrocarbon inlet which is suitable for introducing a hydrocarbon fluid in the axial direction.
  • the reactor chamber is substantially cylindrical, and on its outer wall a plurality of further radially oriented hydrocarbon inlets are provided.
  • the plasma reactor has an outlet through which the materials resulting from the decomposition of the introduced hydrocarbon fluid can escape.
  • an annular plasma is formed on the burner part along the annular electrodes in the time average.
  • a hydrocarbon fluid is introduced into the central region of the annular plasma via the central hydrocarbon inlet.
  • the hydrocarbon fluid is split into hydrogen and carbon particles at operating temperatures of up to 2000 ° C.
  • the additional radially directed hydrocarbon inlets introduce additional hydrocarbon fluid which is split into additional hydrogen and additional carbon.
  • the extra carbon attaches to the already existing C particles and produces larger C particles.
  • the C particles and the hydrogen exit from the outlet of the plasma reactor as H 2 / C aerosol.
  • a similar system is described in WO93 / 20152.
  • a major problem in the decomposition of hydrocarbons into C particles and hydrogen is the uncontrolled deposition of C particles (so-called fouling) on the walls of the reactor chamber and on other parts of the device. While fouling leads to solid carbon deposits or crusts that only can be difficult to solve, is an accumulation of loose carbon particles (so-called sediments) less problematic, since these loose sediments either dissolve by themselves during operation or can be easily solved mechanically, for example by scratching or brushing. Prediction of the occurrence of fouling has heretofore been difficult, and the phenomenon has been poorly understood in the art. Partly stored in the known plasma reactors within a few minutes so much carbon on the walls of the reactor chamber from that the reactor chamber was "overgrown" and the operation had to be stopped. On the other hand, plasma reactors with electrodes made of graphite eroded the electrodes, which also led to the termination of the operation.
  • a plasma reactor for splitting a hydrocarbon fluid which has a reactor chamber, which is surrounded by a reactor wall and has at least one hydrocarbon inlet and one outlet.
  • a plasma torch having at least two electrodes having a base portion at a first end is attached to the reactor wall.
  • the electrodes have at a second end a burner part which projects into the reactor chamber, and a plasma zone is defined at the end of the burner parts of adjacent electrodes.
  • an electrical voltage is applied between the electrodes, whereby a plasma is generated at the end of the burner parts.
  • the hydrocarbon inlet opens into the reactor chamber, and the hydrocarbon inlet is aligned with the plasma zone so that outflowing hydrocarbon fluid is directed towards the plasma zone.
  • carbon particles carbon black, activated carbon
  • the plasma reactor disclosed here mainly produces small C particles which prevent the fouling or growth of the reactor chamber. Furthermore, some large and heavy C particles, which can form statistically, penetrate through the plasma cloud and can specifically attach to the electrodes. This compensates for material loss of the electrodes by erosion. Consequently, the plasma reactor described here can achieve significantly longer periods of use without interruption compared to the prior art.
  • At least the supply of electrical energy to the graphite electrodes and the inlet pressure and rate of introduction of the hydrocarbon fluid are controlled so that the temperature at the top is hotter than 2800 ° C but colder than 3900 ° C.
  • the temperature at the tip of the plasma torch was not precisely controlled.
  • gaseous carbon is generated, which evaporates from a graphite electrode.
  • the gaseous carbon is continuously drained by this flow toward the outlet.
  • the electrode erodes at its hottest zones (especially the tip).
  • the introduction of the hydrocarbon fluid directly to the plasma zone results in the advantageous effect that the partial pressure of gaseous carbon in the vicinity of the electrode is increased. Consequently, the partial pressure is no longer maintained by evaporation of the electrode, and the erosion of the electrode is stopped.
  • the vapor pressure of the carbon at the electrode becomes too high, the carbon re-sublimes on the electrode because the temperature of the electrode is below the sublimation temperature of the graphite.
  • the hydrocarbon inlet of the plasma reactor is formed by a conduit fixed to the reactor wall at a first end and having a hydrocarbon fluid discharge port at an opposite second end, and the conduit is shaped to provide the hydrocarbon fluid discharge port Plasma zone is aligned.
  • the introduction of hydrocarbon fluid can be carried out in the reactor chamber in a simple manner and the line can be additionally cooled, if the cooling is not sufficient by the introduced hydrocarbon fluid.
  • the hydrocarbon inlet of the plasma reactor is formed by a bundle of hydrocarbon conduits, the bundle of Hydrocarbon lines attached at a first end to the reactor wall, and wherein each hydrocarbon line at an opposite second end having a discharge port for hydrocarbon fluid.
  • the bundle of hydrocarbon lines in this case is shaped so that each of the hydrocarbon fluid discharge ports is aligned with the plasma zone. Further, the output of hydrocarbon fluid from the individual hydrocarbon lines of the bundle is separately controllable.
  • the output of hydrocarbon fluid ie, the introduction into the plasma reactor
  • the pressure of the hydrocarbon fluid prior to discharge pre-pressure
  • the flow rate at the discharge port can be varied over a wide range, eg, in terms of mass per time, the pressure of the hydrocarbon fluid prior to discharge (pre-pressure), the flow rate at the discharge port.
  • the individual hydrocarbon lines each have discharge openings with differently sized flow cross-sections. With a constant mass flow, this allows the flow velocity of the hydrocarbon fluid to be changed. Alternatively, the mass flow can be changed at a constant flow rate. These possibilities for change again influence the size of the C particles and their motion impulse.
  • the pressure and the flow rate are controlled so that the cloud of hydrocarbon fluid comes close to the electrode tips.
  • the pressure and the flow rate are controlled in such a way that the edges of the cloud of the hydrocarbon fluid are directed to the tip of the electrode (fine adjustment).
  • the flow cross-sections of the hydrocarbon conduit discharge ports are different, wherein an output of hydrocarbon fluid from a first hydrocarbon conduit having a first delivery port can be varied via valves via a first hydrocarbon fluid delivery region, and wherein an output of hydrocarbon fluid is from at least one second hydrocarbon Hydrocarbon conduit having a corresponding second discharge opening can be varied by means of valves via at least one second output range for hydrocarbon fluid, wherein the at least one second discharge area is at least partially offset from the first discharge area for Hydrocarbon fluid is different.
  • the first discharge portion and the at least one second discharge portion cooperatively constitute a whole hydrocarbon feed output portion of the hydrocarbon inlet.
  • the output parameters can be varied over a wide range without interrupting the operation of the plasma reactor.
  • the plasma reactor can be adjusted for different hydrocarbons and varying operating conditions.
  • the plasma reactor has an apparatus for measuring a particle size.
  • a control device of the plasma reactor can regulate the operating parameters depending on the particle size. If the particle size is continuously measured, and at the same time individual operating parameters are changed, a map can further be created that represents the relationship between the particle size and the various operating parameters.
  • the plasma reactor may include a pressure sensor configured to sense the pressure in the reactor chamber (corresponding to the back pressure for (pre-) pressure before the discharge opening).
  • a pressure sensor configured to sense the pressure in the reactor chamber (corresponding to the back pressure for (pre-) pressure before the discharge opening).
  • the object of the invention is further achieved by a method for operating a plasma reactor, wherein the plasma reactor is designed for splitting a hydrocarbon fluid and has a reactor chamber, which is enclosed by a reactor wall and has at least one hydrocarbon inlet and one outlet.
  • a plasma torch having at least two electrodes is disposed in the reactor chamber, and a plasma zone is defined between adjacent elongate electrodes.
  • the method comprises the steps of: introducing hydrocarbon fluid toward the plasma zone into a region of the reactor chamber between the plasma zone and the outlet, and decomposing the hydrocarbon fluid into carbon particles and hydrogen; Varying at least one parameter of introduction of hydrocarbon fluid; Determining a correlation between a particle size of the carbon particles and the at least one parameter of the introduction of hydrocarbon fluid during the varying.
  • a map can further be created which represents the relationship between the particle size and the various operating parameters. From the correlation between particle size and the at least one parameter of the introduction of hydrocarbon fluid, parameters can be selected in which mainly small C particles are generated, which prevent the fouling or growth of the reactor chamber. Likewise targeted large and heavy C particles can be generated, which penetrate through the plasma cloud and attach specifically to the electrodes to compensate for a loss of material of the electrodes by erosion. Furthermore, an adjustment of the operating parameters is considered, in which some large and heavy C particles are generated statistically, and compensate for the loss of material of the electrodes. Consequently, the method described here achieves significantly longer periods of use without interruption compared to the prior art.
  • the adjusted operating parameter of the introduction of hydrocarbon fluid is advantageously at least one of the following:
  • a flow rate of the hydrocarbon fluid at the hydrocarbon inlet (the flow rate may be influenced by changing the flow cross-section of the hydrocarbon inlet or by changing the mass flow).
  • the method includes the step of determining the at least one parameter of hydrocarbon fluid introduction based on the determined correlation to control so that the particle size of the carbon particles is minimal.
  • the size of the C particles depends on the length of the time interval in which the growing C particle encounters thermally decomposable hydrocarbon molecules.
  • thermally decomposable hydrocarbon molecules it depends on the spatial availability of agglomeratable C atoms, that is, the availability of C atoms in close proximity, which can combine to form a C particle. This spatial availability can be increased by turbulent flow.
  • a pressure difference between (i) a pressure of the hydrocarbon fluid at a location in front of the hydrocarbon inlet and (ii) a pressure in the reactor chamber or a pressure at a point after the outlet is continuously sensed and a sudden change in the sensed Detected pressure difference.
  • the pressure in the reactor chamber and the temperature outside the plasma zone are kept slightly below the sublimation conditions of graphite (about 3900 ° C. at 20 bar), in particular the pressure in the reactor chamber kept at 20 bar and the temperature outside the plasma zone below 3900 ° C held.
  • Particle formation then occurs immediately and is essentially completed before the formed C particle arrives near the reactor wall.
  • the C-particle formed does not tend to deposit (ie, condense) on the reactor wall.
  • the hydrocarbon inlet is formed by a bundle of hydrocarbon conduits, the bundle of hydrocarbon conduits being attached to the reactor wall at a first end, and each hydrocarbon conduit having an output port for hydrocarbon fluid at an opposite second end.
  • the discharge openings for hydrocarbon fluid are aligned with the plasma zone and have discharge openings with different flow cross-sections.
  • the method includes the step of separately controlling the output of hydrocarbon fluid from the hydrocarbon lines.
  • the output of hydrocarbon fluid can be varied over a wide range, eg, in terms of mass per time, pressure, flow rate.
  • the output of hydrocarbon fluid may be varied over a still wider range when a process is used wherein the hydrocarbon inlet has a bundle of at least N hydrocarbon conduits, and the following steps are performed, wherein the mass flow of the hydrocarbon effluent in steps a) and b) is equal to:
  • the erosion of the electrodes can be reduced or prevented if, in the method, a distribution of the size of the carbon particles based on the correlation is influenced so that a small part of the carbon particles is sufficiently large to travel through the plasma zone. Part of these carbon particles are then deposited on the ends of the electrodes. Further, the time of introducing hydrocarbon fluid and the thickness of deposition of the carbon particles on the electrode ends are measured during this time. The course of the deposition of carbon on the electrode can, inter alia, by continuous Measuring the electrical resistance at the electrode to be monitored. The flow rate at which the hydrocarbon fluid is introduced is then modified so that the deposition of the carbon on the electrode ends is as fast as the erosion of the electrode ends due to sublimation of the carbon at high temperatures. In particular, there are advantages when the distribution of the size of the carbon particles is influenced by the following parameters of the output of hydrocarbon fluid:
  • a change in these parameters of the output of hydrocarbon fluid affects the size of the C particles and their momentum so that targeted C particles can be generated which have sufficient magnitude and momentum or momentum to traverse the plasma zone and the electrodes to reach.
  • the size of the C particles can be adjusted and it is possible to counteract the erosion of the electrodes.
  • This arrangement is an improvement over the prior art where the introduction of hydrocarbon fluid into the reactor chamber has heretofore been variable only with respect to the pressure in a small range and erosion of the electrodes has occurred. Due to the orientation of the hydrocarbon inlet (ie, the discharge opening (s)), large C particles with high kinetic energy can penetrate into the plasma zone and migrate through the plasma zone.
  • FIG. 1 shows a plasma reactor for splitting a hydrocarbon fluid according to an embodiment of the present disclosure
  • FIG. 2 shows a plasma reactor for splitting a hydrocarbon fluid according to another embodiment of the present disclosure
  • FIG. Fig. 3 shows a sectional detail Z of a hydrocarbon inlet for a
  • FIG. 4a shows a sectioned detail Z of an alternative hydrocarbon inlet for a plasma reactor according to one embodiment
  • FIG. 4b shows a plan view of the detail Z from FIG. 4a
  • FIG. 5 shows the plasma reactor according to one of the exemplary embodiments described in operation.
  • the hydrocarbon fluid described herein is preferably natural gas, methane, liquefied petroleum gas, biogas, heavy oil, synthetic hydrocarbons or a mixture thereof (more preferably preferably from a stream of conventional or non-conventional natural gas and liquefied gases, also called "wet gases").
  • the hydrocarbons are preferably in
  • Hydrocarbons which are liquid or highly viscous under normal ambient conditions may be gaseous, diluted, or may also be introduced in a finely atomized form prior to introduction into the reactor. All of these forms are referred to herein as hydrocarbon fluid.
  • the plasma reactor 1 has a reactor chamber 2 enclosed by a reactor wall 3 having a base 3a and a lid 3b.
  • the reactor chamber 2 may also be divided at a different location than shown in the figures.
  • the reactor chamber 2 is substantially cylindrical and has a central axis 4.
  • the plasma reactor 1 continues at least one hydrocarbon inlet 5 connected to a supply (not shown) of a pressurized hydrocarbon fluid (for example with a tank and / or a pump).
  • a plasma torch 7 Attached to the lid 3b of the reactor wall 3 is a plasma torch 7 which has elongated electrodes (not shown in more detail).
  • the plasma torch 7 has a base part 9, which is attached to the reactor wall 3 (here on the lid 3b).
  • the plasma burner 7 has at its other end opposite to the base part 9 a burner part 1 1 at a free end of the electrodes, which projects into the reactor chamber 2.
  • the electrodes which are not shown in greater detail in the figures, are preferably tubular electrodes or tube electrodes arranged in one another (for example known from US Pat. No. 5,481,080 A). But it is also conceivable that rod electrodes are used, for example, two juxtaposed rod electrodes.
  • the electrodes may be made of metal or graphite.
  • hydrogen and carbon are generated from hydrocarbons (C n H m ) by means of the energy of a plasma.
  • a plasma zone 13 is generated by means of an arc between the electrodes, preferably with H 2 as plasma gas, since this is obtained anyway in the decomposition of the hydrocarbons.
  • plasma gas any other suitable gas can be selected, for example, inert gases such as argon or nitrogen, which do not influence or participate in the reaction or splitting in the plasma arc.
  • a plasma is formed in operation, which can be influenced by a plasma control device 14, for example by magnetic force.
  • the plasma reactor 1 has an outlet 15 through which the substances which result from the splitting up of the introduced hydrocarbon fluid can escape.
  • the outlet 15 is arranged at an axial end of the reactor chamber 2.
  • FIG. 2 shows a plasma reactor 1 with a plurality of outlets 15.
  • a first outlet 15-1 is provided for discharging an H 2 / C aerosol, as in FIG. 1.
  • a second outlet 15 - 2 may also be used to discharge a portion of the H 2 / C aerosol, for example in another Reactor or process can be used that should.
  • hydrogen H 2 is discharged via the second outlet 15-2, the second outlet 15-2 being designed so that the gaseous hydrogen H 2 separates from the solid C particles.
  • the second outlet 15-2 can be used in all embodiments described here.
  • the hydrocarbon inlet 5 is formed by a conduit 7 which is fixed at a first end to the reactor wall 3 (for example, here at the lower part 3b), and which has at least one outlet opening 21 for hydrocarbon fluid at an opposite end.
  • the hydrocarbon inlet 5 opens into the reactor chamber 2.
  • the discharge opening 21 is aligned with the plasma zone 3 in such a way that hydrocarbon fluid flowing out of it is conducted to the plasma zone 13.
  • the hydrocarbon fluid discharge port 21 is thus aligned with the plasma zone.
  • the conduit 7 has a hydrocarbon conduit 18 and a protective gas conduit 19.
  • the hydrocarbon line 18 and the protective gas line 19 can run next to each other or can lie inside one another, the hydrocarbon line 18 preferably being arranged in the protective gas line 19.
  • the hydrocarbon line 18 and the inert gas line 19 can also partially extend next to one another and lie close to the dispensing opening 21.
  • the hydrocarbon inlet 5 is formed by a bundle of hydrocarbon lines 18-1, 18-n.
  • the hydrocarbon lines 18-1,... 18-n are in this case surrounded by a common protective gas line 19.
  • the bundle of hydrocarbon lines 18-1, 18-n is again attached to the reactor wall 3 at a first end, and each hydrocarbon line 18-118-n has at an opposite second end a hydrocarbon fluid discharge port 21-1, 21-n , Also in this case, each of the discharge openings 21 -1, 21 -n for hydrocarbon fluid to the plasma zone 13 aligned tet.
  • the output of hydrocarbon fluid from the individual hydrocarbon lines 18-1 18-n is separately controllable.
  • each of the hydrocarbon lines 18-1, 18-n may be surrounded by its own protective gas line 19 (not shown in the figures), so that the output of protective gas can also be controlled separately.
  • the hydrocarbon lines 18-1, 18-n are optionally cooled by a coolant in one or more coolant lines 20. Cooling by the coolant lines 20 prevents the hydrocarbon fluid from decomposing in an uncontrolled manner. Although the coolant lines 20 are shown only in Fig. 4a for ease of illustration, they may be provided in all embodiments.
  • the individual hydrocarbon lines 18-1, 18-n have discharge openings 21 -1, 21 -n with different flow cross-sections.
  • an output of hydrocarbon fluid from a first hydrocarbon conduit 18-1 having a first delivery port 21-1 may be varied by means of valves (not shown) through a first output range of hydrocarbon fluid, and an output of hydrocarbon fluid from a second hydrocarbon conduit 18-2 a corresponding second dispensing opening 21 -2 can be varied via a second output range for hydrocarbon fluid.
  • the first output port 21-1 is used for a different range of output speeds than the second output port 21-2.
  • the first output port 21-1 is used for a different range of the mass flow than the second output port 21-2.
  • the output areas are different and may be adjacent or overlapping. The first and second discharge areas together form a total output area for hydrocarbon fluid.
  • the location and shape of the cloud of hydrocarbon fluid can be varied as the hydrocarbon fluid is dispensed through multiple dispensing ports simultaneously.
  • a large-flow discharge port is located in the center of the group of discharge ports (corresponding to 18-7 in FIG. 4b)
  • the position of the cloud of the hydrocarbon fluid relative to the tips of the electrodes of the torch member 1 may be affected.
  • the pressure of the hydrocarbon fluid increases upon introduction, the cloud of hydrocarbon fluid shifts closer to the tips of the electrodes.
  • the pressure of the hydrocarbon fluid is reduced at introduction, the cloud of hydrocarbon fluid moves away from the tips of the electrodes.
  • the shape of the cloud of the hydrocarbon fluid can also be influenced, for example approximately round, oval or conical.
  • the cloud of the hydrocarbon fluid may flow toward the reactor wall 3 or be moved away from it.
  • the hydrocarbon line (s) 18 or 18-1, 18-n and the inert gas line 19 are arranged so that in operation an outflowing hydrocarbon fluid is surrounded by a protective gas.
  • the output velocity of the shielding gas is significantly less than the output rate of the hydrocarbon fluid, in particular at least five times lower.
  • an optional purge gas line 22 is arranged in the vicinity of the base part 9 of the plasma burner 7.
  • the purge gas line 22 By means of the purge gas line 22, a curtain of purge gas between the reactor wall 3 and the plasma torch 7 can be initiated.
  • the purge gas may be the same gas that is also used as the plasma gas.
  • the mass flow of the purge gas is less than the mass flow of the hydrocarbon fluid, preferably at least 10 times lower.
  • the plasma reactor 1 has, in the lower region of the reactor chamber 2 or at the outlet 15, a device 24 for measuring a size of the C particles of the H 2 / C aerosol.
  • Devices for measuring a particle size are known and are described, for example, in: Leschonski, Kurt “Fundamentals and Modern Methods of Particle Measurement", Institute of Mechanical Process Engineering and Environmental Engineering, Clausthal University of Technology, 1988.
  • Various measuring methods can be used, and the device 24 can, for example - se is one of the following: a differential mobility analyzer (DEMC), a differential mobility analyzer (DE-MAS) or a laser diffraction analyzer (Laser Diffraction Analyzer) is not on these are restricted.
  • DEMC differential mobility analyzer
  • DE-MAS differential mobility analyzer
  • Laser Diffraction Analyzer Laser Diffraction Analyzer
  • the plasma reactor 1 has a pressure sensor 26, which is arranged in connection with the reactor chamber 2 and can sense the pressure in the reactor chamber 2, ie the backpressure.
  • the pressure sensor 26 is arranged, for example, in the lower region of the reactor chamber 2 in order to protect it from the direct influence of the plasma.
  • the pressure sensor 26 may, for example, be arranged along the center axis 4 at approximately the same distance from the plasma torch 7, in which the lines 17, 18, 19 for hydrocarbon and inert gas are attached to the reactor wall 3.
  • the plasma reactor 1 further includes a second pressure sensor (not shown) which can sense the pressure of the hydrocarbon fluid in front of the discharge port 21 or 21-1, 21-n, that is, the admission pressure.
  • Hydrocarbon fluid is introduced through the hydrocarbon line 18 in the direction of the plasma zone 13. Individual hydrocarbon molecules can not penetrate the high-viscosity plasma, as has been shown by experiments and calculations. Due to the high temperature of the plasma, the hydrocarbon fluid on the way to the plasma zone 3 is first decomposed into product gas (C atoms and H atoms). At the same time, C particles (carbon black particles - a kind of graphite) form from the C atoms. This process takes about 8-12 ms.
  • one or more hydrocarbon fluid introduction parameters are varied, in particular (a) a flow area of the hydrocarbon inlet (with constant mass flow, the flow rate of the hydrocarbon fluid can thereby be changed and, alternatively, the mass flow can be changed at a constant flow rate); (b) a pressure difference between a pressure in the reactor chamber and a pressure of the hydrocarbon fluid at a position in front of the hydrocarbon inlet (thereby, the mass flow and the flow velocity can be changed, in particular finely adjusted); or (c) a flow rate of the hydrocarbon fluid at the hydrocarbon inlet (the flow rate may be influenced by changing the flow area of the hydrocarbon inlet or by changing the mass flow).
  • These operating parameters influence the size of the C particles and their motion impulse.
  • a correlation between a particle size of the C particles and the at least one parameter of the introduction of hydrocarbon fluid can be determined.
  • the operation of the plasma Reactor 1 is controlled by a controller (not shown), and the correlation between the particle size and the operating parameters is stored in a map in a memory of the controller.
  • the parameters for the introduction of hydrocarbon fluid are controlled so that the particle size of the C particles is minimal to avoid hard or solid deposits.
  • small C particles can be processed better. Small C particles are particularly advantageous when the C particles are to be converted to CO, for example, when the plasma reactor 1 is used in a device for producing CO or synthesis gas as a hydrocarbon converter.
  • a plasma reactor 1 with a plurality of outlets 15-1 and 15-2 ( Figure 2) is advantageous for a device for generating CO or synthesis gas, since a portion of the hydrogen can be discharged via the second outlet 15-2 and the ratio of CO can be changed to H 2 .
  • a pressure difference between (i) a pressure of the hydrocarbon fluid at a point in front of the hydrocarbon inlet and (ii) a pressure in the reactor chamber or a pressure at a point after the outlet is continuously sensed and a sudden change in the sensed pressure difference is detected ,
  • the pressure at a position downstream of the outlet 15 is related to the pressure in the reactor chamber 2.
  • a significant change in the pressure or pressure rise in the reactor chamber is an indication that the product gas described above is generated from C atoms and H atoms and the desired flow of product gas to the wall of the reactor chamber occurs.
  • the size of the C particles generated from the C atoms of the product gas is somewhat randomized. That is, very large C particles (or very small C particles) can not be completely avoided.
  • the flow of most of the product gas to the wall of the reactor chamber ensures that predominantly small C particles are produced from this part of the product gas.
  • the measurement of the pressure difference and the measurement of the particle size can be carried out independently.
  • the measurement of the pressure difference is used as a support to improve the accuracy and speed of the control.
  • the pressure in the reactor chamber 2 and the temperature outside the plasma zone 13 are kept slightly below the sublimation conditions of graphite.
  • the pressure in the reactor chamber 2 is maintained at about 20 bar (+/- 10%), and the temperature outside the plasma zone 13 is kept below 3900 ° C., so that the C particles do not sublime and condense on the reactor wall 3 ,
  • the output of hydrocarbon fluid from the hydrocarbon lines 18-1, 18-n is separately transferred controlled different output ranges.
  • the output of hydrocarbon fluid can be varied over a wide range, e.g. in terms of mass per time, pressure, flow rate.
  • the output velocity and the difference between the primary pressure and the back pressure of the first dispensing opening 21 -1 are varied to introduce hydrocarbon in a first portion of the mass flow in the reactor chamber 2.
  • the size of the second dispensing opening 21-2 is suitable for a different range of mass flow, and accordingly the dispensing speed and the difference between the pre-pressure and the back pressure are varied in a mating other area.
  • the size of the third output port 21-3 is again suitable for another range of mass flow, and so on.
  • the parameters for introducing hydrocarbon fluid may be varied for the output areas of the dispensing openings 21 -1, 21-n, as shown in the following Table 1:
  • the output ranges differ and are contiguous, ie, the velocity range v 2 i -2 , min to v 2 i- 2 , max of the next adjoin the velocity range v 2 i- 1 im in to V2i-i, max of the output aperture 21 -1 Output port 21 -2, and so on until 21-7.
  • the range of the pressure difference Ap 2 is adjacent. min to Ap 21- i. max between the pre-pressure and the back pressure of the discharge port 21-1 to the range of the pressure difference ⁇ p 2 i-2, min to ⁇ p 2 -i-2.ma of the next discharge port 21-2, and so on until 21-7.
  • the range m 2 ii, min to m 2 ii, ma of the mass flow from the discharge opening 21 -1 adjoins the range m 2 i-2, min to m2i- 2 , max of the mass flow from the discharge port 21 -2, and continue until 21 -7.
  • the adjacent discharge areas of the discharge openings 21 -1, 21-7 together form an entire discharge area in which the output with respect to flow rate, mass flow and pressure difference can be varied without interrupting the operation.
  • the output areas of the dispensing openings 21 -1, 21 -n may also be partially over-lapping so that a smooth transition between the dispensing openings 21 -1, 21-n is possible.
  • hydrocarbon lines 18 - 1, 18 - n can be used simultaneously, the hydrocarbon starting from an initial number of hydrocarbon lines 18 - 1, 18 - n - Hydrogen fluid is additionally or less introduced into the reactor chamber 2 by one or more hydrocarbon lines 18-1, 18-n.
  • the hydrocarbon fluid is first discharged from the discharge ports 21-1, 21-n of four hydrocarbon lines 18-1, 18-n with a first pressure difference.
  • the hydrocarbon fluid is first discharged from the discharge ports 21-1, 21-n of five hydrocarbon lines 18-1, 18-n with a second pressure difference, the mass flow remaining the same regardless of how many hydrocarbon lines 18-1, 18- n the hydrocarbon fluid to the plasma zone 13 flows.
  • a longer uninterrupted operation of the plasma reactor 1 can be achieved independently of whether the hydrocarbon inlet 5 is a single hydrocarbon line 18 or several 17 hydrocarbon lines 18-18. 1, 18-n.
  • hydrocarbon fluid is introduced toward the plasma zone 13.
  • the heat decomposes the hydrocarbon fluid to form C particles and hydrogen.
  • the C particles continue to flow to the plasma zone 13 because of the orientation of the hydrocarbon inlet 5 and its pulse.
  • decomposition of the hydrocarbon fluid and C particle formation takes about 8-12 ms (9 ms on average).
  • the decomposition of the hydrocarbon fluid and growth of the finished C particles in this case takes about 9 ms, according to the inventors' calculations in this case. Therefore, although C particles reach the plasma zone 13, the plasma represents a barrier for the C particles. In order to penetrate into the plasma zone 13, a minimum energy (momentum) is necessary.
  • the operating temperature in the plasma reactor 1 is 2500-3500 ° C between the arc at the burner part 1 1 and the reactor wall 3, wherein the temperature decreases in the direction of the reactor wall 3.
  • the sublimation temperature of graphite (C particles) is about 3800 ° C. Since the temperature in the plasma zone 13 is about 5000-15000 ° C, submerge the C-particles after entering the plasma zone 13 continuously with reformation to atomic carbon (carbon atom). The parameters for the introduction of the hydrocarbon fluid are therefore controlled so that large C particles are generated.
  • the parameters for the initiation are set, for example, based on the characteristic map in the memory of the control device of the plasma reactor 1.
  • a size distribution of the carbon particles is influenced, for example, by means of the following parameters of the output of hydrocarbon fluid: flow cross-section of the hydrocarbon inlet; Pressure difference between (i) a pressure of the hydrocarbon fluid at a location in front of the hydrocarbon inlet and (ii) a pressure in the reactor chamber or a pressure after the outlet; Flow rate of the hydrocarbon fluid at the hydrocarbon inlet.
  • the size of the C particles can be measured by means of the particle size measuring device 24.
  • Controlling the flow rate of the hydrocarbon fluid from the hydrocarbon inlet 5 is particularly advantageous.
  • the mass of a C atom is a constant, and the momentum of a C particle is additively composed of the momenta of the C atoms of which it consists.
  • Pulse of a C-particle with n carbon atoms: Pc- pa rticie nm C - a tom v.
  • the momentum of a C particle depends only on the number of carbon atoms (ie the particle size) and the flow velocity v.
  • the parameters for introducing the hydrocarbon fluid are controlled based on the map so that at least a portion of the C particles is sufficiently large to penetrate the plasma zone 13 and to migrate to the electrodes of the plasma torch 7.
  • the number and size of the C particles (and the total number of carbon atoms contained therein) is subject to a statistical distribution function, with all C particles having a velocity dependent on the flow velocity from the output port (s) 21 or 21 -1, 21 -n to have.
  • the parameters for the introduction of the hydrocarbon fluid in particular the flow velocity v
  • the statistical distribution function of the size of the C particles can be influenced so that a small part of the C particles is sufficiently large and has sufficient kinetic energy (momentum) to and to pass through the plasma zone 13. Although these sufficiently large C particles are subject to sublimation in the plasma zone 13, some of these C particles deposit on the electrode and compensate for erosion.
  • the particle size is not the sole decisive parameter, but also the momentum of the particles. Therefore, a definite particle size can not be specified.
  • a small particle has a diameter of less than 20 nm
  • a medium particle has a diameter of 20 nm to 60 nm
  • a large particle has a diameter of more than> 60 nm.
  • Small C particles can not enter the plasma zone 13. Although medium-sized C particles can penetrate into the plasma zone 13, they are greatly attenuated. slows.
  • the small and medium-sized C particles sublime to C atoms and flow laterally to the reactor wall 3, the C atoms newly forming on cooling to small C particles. Since the entire H 2 / C aerosol consistently cools, no "cold methane" grows on existing C particles (as in WO93 / 20152).
  • the large C particles with high kinetic energy can penetrate into the plasma zone 13 and penetrate them, while at the same time small and large After sublimation on or in the plasma zone 3, transform medium-sized C particles into very small C particles.
  • the size of the C particles, which flow laterally to the reactor wall 3 and down to the outlet 15, is thus smaller than in the case of known plasma reactors, namely in the range of less than 50 nm diameter, preferably less than 30 nm diameter. Further, the thickness of the deposition of the carbon on the electrode ends and the time of introducing hydrocarbon fluid are measured.
  • the flow velocity v at which the hydrocarbon fluid is introduced is adjusted so that the deposition of the carbon on the electrode ends is as fast as the erosion of the electrode due to the sublimation of the carbon.
  • the resistance that the plasma gas brings to the C particles depends on the composition of the plasma gas, its flow velocity, its viscosity (temperature, degree of ionization) and its extent (reactor design, mass flow per unit time). It should be noted that for a given plasma reactor 1 there is not a fixed flow rate of the hydrocarbon in which the deposition of carbon on the electrode is always equal to erosion by sublimation. This balance depends on many secondary parameters that can be varied independently.
  • the power of the electrode (the injected amount of current in MW and thus the energy introduced by the electrode into the plasma reactor 1) can be increased significantly if the carbon deposition on the electrode is correspondingly increased.
  • the increased by the electrical power increase rate of sublimation of the electrode material is compensated by a higher carbon deposition and the electrode remains virtually erosion-free.
  • targeted deposition of C particles on the electrode it is thus possible not only to increase the service life of the electrode but at the same time also to increase the capacity of the plasma reactor 1. It should be understood that the methods described herein may be practiced regardless of whether the hydrocarbon inlet 5 has a single hydrocarbon line 18 or multiple hydrocarbon lines 18-1, 18-n.

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Abstract

L'invention concerne un réacteur à plasma prévu pour décomposer des hydrocarbures et conçu pour fonctionner de manière stable sur une durée prolongée. Cet objectif est atteint au moyen d'un réacteur à plasma (1) destiné au craquage d'un fluide hydrocarbure et présentant une chambre (2) délimitée par une paroi (3, 3a, 3b) et présentant au moins une admission (5) et une évacuation (15) d'hydrocarbure. Une torche à plasma (7), munie d'au moins deux électrodes présentant sur une première extrémité une embase (9), est fixée sur la paroi du réacteur. Sur une seconde extrémité, les électrodes présentent une partie formant torche (11) dépassant dans la chambre de réacteur, et une zone de plasma (13) est définie entre les parties formant torche d'électrodes adjacentes. L'admission d'hydrocarbure débouche dans une zone située entre la zone de plasma et l'évacuation dans la chambre de réacteur, et l'admission d'hydrocarbure est orientée vers la zone de plasma, de telle sorte que l'hydrocarbure fluide qui s'en écoule soit canalisé vers la zone de plasma. Avec le réacteur à plasma décrit ici, on note pratiquement aucun dégagement de particules de carbone, ce qui empêche l'encrassement ou les dépôts dans la chambre de réacteur. En outre, quelques particules de carbone grosses et lourdes, statistiquement susceptibles de se former, pénètrent dans le nuage de plasma et peuvent se déposer de manière ciblée sur les électrodes.
EP17818441.2A 2016-12-02 2017-11-30 Réacteur à plasma et procédé pour faire fonctionner un réacteur à plasma Pending EP3548426A1 (fr)

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FR3112767B1 (fr) * 2020-07-27 2023-05-12 Plenesys Production optimisée d’hydrogène à partir d’un hydrocarbure.
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NO174180C (no) 1991-12-12 1994-03-23 Kvaerner Eng Innföringsrör for brenner for kjemiske prosesser
NO175718C (no) 1991-12-12 1994-11-23 Kvaerner Eng Fremgangsmåte ved spalting av hydrokarboner samt apparat for bruk ved fremgangsmåten
NO176522C (no) 1992-04-07 1995-04-19 Kvaerner Eng Fremgangsmåte ved fremstilling av karbon med definerte fysikalske egenskaper samt apparat for gjennomföring av fremgangsmåten
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