EP0542597A1 - Verfahren zur thermischen Pyrolyse von Kohlenwasserstoffen mit Elektroofen - Google Patents

Verfahren zur thermischen Pyrolyse von Kohlenwasserstoffen mit Elektroofen Download PDF

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Publication number
EP0542597A1
EP0542597A1 EP92402951A EP92402951A EP0542597A1 EP 0542597 A1 EP0542597 A1 EP 0542597A1 EP 92402951 A EP92402951 A EP 92402951A EP 92402951 A EP92402951 A EP 92402951A EP 0542597 A1 EP0542597 A1 EP 0542597A1
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EP
European Patent Office
Prior art keywords
sheaths
gas
heating
zone
reactor
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EP92402951A
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English (en)
French (fr)
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EP0542597B1 (de
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Jacques Alagy
Paul Broutin
Christian Busson
Jérôme Weill
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/24—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by heating with electrical means
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/919—Apparatus considerations
    • Y10S585/921—Apparatus considerations using recited apparatus structure
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/919—Apparatus considerations
    • Y10S585/921—Apparatus considerations using recited apparatus structure
    • Y10S585/924—Reactor shape or disposition
    • Y10S585/926—Plurality or verticality

Definitions

  • the invention relates to a process for thermal pyrolysis of hydrocarbons using an electric furnace. This process is in particular intended to produce light olefins, and more particularly ethylene and propylene.
  • thermal pyrolysis and notably steam cracking furnaces has essentially been geared towards obtaining shorter residence times and a reduction in pressure drop, which has led manufacturers to reduce the length of tubular reactors, therefore to increase the density of heat flux.
  • the increase in this last factor can be essentially obtained by increasing the skin temperature of the tubular reactors and / or by reducing the diameter of the tubes (which makes it possible to increase the s / v ratio, s being the exchange surface and v the reaction volume).
  • the technique has also evolved towards the use of smaller diameter tubes, placed in parallel in order to maintain a satisfactory capacity, and to remain in a suitable pressure drop range.
  • thermal pyrolysis reactors and in particular steam cracking has thus evolved, from the use of horizontal tubes of approximately 100 meters (m) in length and internal diameters of the order of 90 to 140 millimeters (mm), up to to the classic technique of vertically hanging tubes of approximately 40 m in length and diameter of around 60 mm operating with residence times of around 0.3 to 0.4 seconds (s), and finally the so-called millisecond technique proposed by PULLMAN-KELLOG (patent US-A-3671198) which uses tubes of approximately 10 m in length, vertical and straight, with an internal diameter of 25 to 35 mm, these tubes being brought to temperatures of 1100 ° C (temperature most often very close to that of the limit of use of the metal).
  • the residence time of the charges is, in this type of oven, of the order of 0.07 s; the pressure drop observed is of the order of 0.9 to 1.8 bar (1 bar is equal to 0.1 megapascal), and the calculation of the ratio of the exchange surface s to the reaction volume v leads to values of the order of 120 m ⁇ 1.
  • the present invention proposes a method and a device for its implementation bringing notable improvements compared to the embodiments according to the prior art such as for example an easier, more flexible and better controlled implementation and a lower cost, also both at the investment level and at the utility level.
  • the flexibility of use is linked to the use of electricity which makes it possible to regulate the heat flow and therefore the temperature profile of the process gas as desired.
  • the invention relates to a process for thermal pyrolysis of hydrocarbons in a reaction zone, of elongated shape in a direction (an axis), comprising a heating zone and a cooling zone, following said heating zone, in which a gaseous mixture containing at least one hydrocarbon containing at least two carbon atoms is circulated in the heating zone, in a flow direction substantially parallel to the direction (at l axis) of the reaction zone, said heating zone comprising a plurality of electric heating means arranged in sheets, substantially parallel to one another, forming in transverse projection a beam with triangular, square or rectangular pitch, said heating means being grouped together by successive transverse sections substantially perpendicular to the direction (to the axis) of the reaction zone, independent of each other and supplied with electrical energy so as to determine at least two parts in the heating zone, the first part making it possible to carry the charging up to a temperature at most equal to about 1300 ° C.
  • the electrical heating means are isolated from direct contact with the gas mixture containing at least one hydrocarbon by sheaths into which a gas G, called sheath gas or gas, is introduced sealing, said sheaths having an appropriate permeability and the gas being introduced inside said sheaths at a pressure such that there is diffusion, at least in certain points, of at least part of this gas G from the inside said sheaths towards the outside of said sheaths, this gas G can then be diluted in said gaseous mixture.
  • a gas G called sheath gas or gas
  • the gas mixture circulating in the reaction space can also contain up to 20% by volume of methane. This mixture will preferably contain less than 10% by volume of methane.
  • the thermal pyrolysis process of the present invention applies in particular to the thermal pyrolysis of ethane or of a mixture of hydrocarbons containing ethane, in the presence of hydrogen.
  • the gaseous mixture, circulating in the reaction space can also contain water vapor.
  • the thermal pyrolysis process is usually described under the term steam cracking. The following description of the process of the present invention is made in connection with this case.
  • the heating zone is heated by supplying electrical energy through heating means such as electrical resistors, the heat released by the Joule effect in these resistors is transmitted mainly by radiation to the sheaths arranged around the resistors in a non-contiguous manner.
  • These sheaths are usually made of ceramic material or any refractory material supporting the required temperatures and the reducing and / or oxidizing atmospheres of the medium, such as for example certain new metal alloys from the firm KANTHAL SA such as KANTHAL AF, or KANTHAL APM.
  • the gas mixture containing at least one hydrocarbon, which circulates in the heating zone in a manner substantially perpendicular to the axis of the ducts, is heated essentially by convection and by radiation.
  • Heat exchanges are one of the key elements for this type of very endothermic reaction where it is necessary to transfer very large amounts of energy from the resistors to the gas mixture containing at least one hydrocarbon containing at least two carbon atoms called below gas process.
  • the heat exchange from the resistance to the sheath is an exchange essentially radiative, but on the other hand there is little radiative exchange between the sheath and the process gas. In fact, this usually consists essentially of a hydrocarbon-water mixture, a mixture which absorbs little of the radiation emitted by the sheaths.
  • the thermal transfer, between the process gas and the sheaths, is therefore in the case envisaged in the present invention mainly a convection transfer.
  • the quality of the heat exchanges will be directly linked to the available exchange surface and to the surface / volume ratio.
  • the walls participate in an important way in the heat exchange, since they are able to absorb the radiation emitted by the sheaths and consequently the temperatures of the sheaths and the walls tend to equilibrate. So he is possible to significantly increase the exchange surface and practically to double it by modifying the design of the device as follows: whereas, in the initial design, the sheaths protecting the resistors and permitting the transfer of heat to the process gas were preferably staggered, according to a preferred embodiment of the present invention, they will be aligned, which makes it possible to constitute n rows or layers of m resistors in the longitudinal direction (for a total number of resistors equal to nxm), this will form at least one longitudinal zone and most often at least two longitudinal zones each comprising at least one and often several layers of heating elements, each zone being separated from the next by a wall of refractory material.
  • the term heating element designates the assembly consisting of a protective sheath and at least one resistance inside said sheath.
  • each zone will comprise a single layer of heating elements.
  • the convective exchanges between the process gas and the walls are greatly increased and they can be further improved by imposing significant speeds on the process gas and by creating zones of turbulence.
  • the increase in the speed of the process gas can for example be obtained by using walls whose shape favors this increase in speed and the appearance of zones of turbulence. Particularly shaped walls are shown without limitation in Figure 1C.
  • the walls are usually made of refractory material. Any refractory material can be used to make the walls and we can cite as examples not limiting zirconia, silicon carbide, mullite and various refractory concretes.
  • the sheaths can have a width of the order of 150 mm, for a wall thickness having a value of the order of 50 mm, which only causes an increase in overall width of the oven. around 30%.
  • An additional advantage of this embodiment comprising walls is to allow a simpler embodiment of the oven, the vertical walls allowing, in addition to improving the heat transfer by convection, to support the roof of the oven.
  • each wall has at least one means for balancing the pressures in the longitudinal zones located on either side of the wall.
  • a simple but effective means for balancing the pressures mention may be made of the creation of zones comprising one or more perforations or of porous zones.
  • the electrical resistances which supply heat to the heating zone are supplied independently with electrical energy, either individually or in transverse rows, or even in small groups, so as to define heating sections along the heating zone and thus be able to modulate the quantity of energy supplied while in the ding of this zone.
  • the heating zone is usually composed of 2 to 20 heating sections, preferably 5 to 12 sections.
  • the mixture gaseous containing at least one hydrocarbon previously heated to about 600 ° C, is usually brought to a temperature at most equal to about 1300 ° C, and advantageously between 800 and 1100 ° C (the start of the heating zone is located at the where the charge is introduced).
  • the modulation of these heating sections is carried out in a conventional manner; the heating elements corresponding to the aforementioned sections are generally supplied by thyristor modulator assemblies. Transformers can be used to adapt the voltages a priori, while the modulators allow fine and continuous adjustment of the injected power.
  • each heating section can be provided with a thermocouple pyrometric rod adapted to the temperature level; these rods are arranged in the spaces where the load circulates, the information is transmitted to the regulator which controls the thyristor modulator.
  • the length of the first part of the heating zone usually represents from 5 to 50% of the total length of the heating zone, advantageously from 10 to 20%.
  • the electrical energy supplied to this first part of the heating zone is such that it generates a strong temperature gradient which makes it possible to have a relatively high average temperature of the load, over the entire heating zone, which is favorable to the selectivity in light olefins.
  • the electrical energy supplied to the different heating sections of this zone is modulated so that the temperature variation throughout this zone is small, usually less than about 50 ° C. (+ or - 25 ° C around the setpoint value) and advantageously less than about 20 ° C (+ or - 10 ° C around the setpoint value).
  • the length of the heating zone is usually about 50 to about 90% of the total length of the reaction zone.
  • the heating zone is followed by a cooling (or quenching) zone so as to very quickly lower the temperature of the effluents from the heating zone to around 300 ° C. for example.
  • Areas heating and quenching may or may not be incorporated in the same enclosure, hereinafter referred to as a reactor.
  • a direct quenching is carried out; the reaction effluents leave the heating zone and are very quickly cooled by direct contact with a cooling fluid which is injected into the effluents by means of at least one injector, usually made of ceramic material, disposed at the periphery of the reactor. Hydrocarbon oils or water can be used as the coolant.
  • the total effluents resulting from the mixture are then collected and separated.
  • reaction effluents from the heating zone are cooled by indirect contact with a cooling fluid, for example by circulating said fluid in sealed conduits inside the cooling zone .
  • the hydrocarbon feedstocks usable within the general framework of the present invention include saturated aliphatic hydrocarbons, such as ethane, mixtures of alkanes, or petroleum fractions such as naphthas, atmospheric gas oils and vacuum gas oils, the latter can have a final point of distillation of the order of 570 ° C.
  • the petroleum fractions can have, if necessary, undergone a pretreatment such as, for example, a hydrotreatment.
  • These feedstocks can also contain hydrogen in an amount which can range, for example, up to 90% by volume.
  • These charges generally include at least one hydrocarbon having two carbon atoms in its molecule. Fillers are very often used comprising mainly (more than 50% by volume) of hydrocarbons having at least two carbon atoms in their molecule.
  • the thermal cracking of these cuts is preferably done using hydrogen as diluent.
  • the sealing gas G which is introduced into the sheaths surrounding the resistors will preferably be substantially pure hydrogen; given the use of such a sealing gas, the sheaths will be made of a preferably non-porous material, the leakage of gas G to the process gas will result from the sealing on each sheath which will be carried out voluntarily imperfectly.
  • the weight ratio of the dilution water vapor to the hydrocarbon charge varies according to the charges to be treated. It can be from approximately 0.2: 1 to approximately 1.5: 1, generally, the ratio used is of the order of 1: 1 when using diesel under vacuum and of the order of 0, 5: 1 for steam cracking naphtha.
  • Part of the dilution water vapor can be introduced with gas G. This fraction introduced with gas G can then represent up to 100% of the amount of water required for steam cracking. Preferably, this fraction represents from 0 to 50% of this amount.
  • the charges to be treated have a residence time in the reaction zone, usually from about 2 milliseconds to about 1 second and preferably from about 30 to about 400 milliseconds.
  • the gas G which is introduced into the sheaths surrounding the resistors is usually a gas free from any hydrocarbon capable of a thermal conversion reaction leading to the formation of coke. This gas is also chosen so that it does not damage the resistors used and does not cause accelerated aging of these resistors.
  • This gas can be steam alone, hydrogen alone, a mixture of gases containing steam and hydrogen.
  • This gas G can also be an inert gas such as nitrogen or a rare gas such as helium or argon.
  • This gas G can also be a mixture of gases containing, in addition to water vapor and / or hydrogen, an inert gas or a rare gas such as for example those mentioned above.
  • a gas G containing water vapor and / or hydrogen it is usually preferred to use a gas G containing water vapor and / or hydrogen and most often a gas containing a proportion of water vapor and / or hydrogen by volume greater than about 50%. In most cases, it is recommended to use a G gas containing water vapor.
  • the permeability of the sheaths must be sufficient to allow, at least at certain points, the diffusion of at least part of the gas G introduced into the space of the resistors towards the process space. It would not go beyond the scope of the invention if the sheath permeability is such that it allows the diffusion of all of the gaseous compounds, contained in the gas G introduced into the space of the resistors, towards the process area.
  • This permeability can result from a tightness on each sheath produced voluntarily imperfectly and / or from the use of a material constituting the sheaths having an open porosity allowing the passage of at least part of the gas G, it is in other words, a permeable material. Most often, it is recommended to use a permeable material.
  • the sheaths, insulating the electrical heating means from direct contact with the gas mixture containing at least one hydrocarbon are made of a porous material whose porosity is sufficient to allow the diffusion of 'at least part of the gas G through said sheaths.
  • These sheaths are thus preferably made of a porous material having an open porosity of at least about 1% and at most about 40% by volume relative to the volume of the wall, and usually from about 5% to about 30 %.
  • gas G containing water vapor and / or hydrogen, which diffuses at least in part towards the process space, provides several advantages. It does not complicate the separations downstream of the pyrolysis oven since the water vapor is a compound present in the process space and the hydrogen can be a compound present in the process space as a product of the cracking reaction. and possibly also as a component of the load.
  • the cost of producing the furnace is reduced while also decreasing thermo-mechanical constraints at the sheath connections, which increases the reliability of the entire device.
  • ceramic sheaths in particular of silicon carbide, of medium quality, having an open porosity of at least about 1% by volume (for example about 20% by volume), is thus not only possible but even desirable, which lowers the cost of making the oven. Furthermore, the very existence of this open porosity creates on the surface of the ceramic sheath on the process space side a partial pressure of the gas G introduced into the space of the resistors insulating in a way the surface of the ceramic from the process gas which, without wishing to be bound by any theory, explains the notable reduction in the formation of coke since this usually usually forms on the surface of the sheaths and, on the contrary, the products formed will be in a less favorable local atmosphere to the formation of coke.
  • the description of the present invention designates the porosity consisting of microcavities included in the solid ceramic pieces considered, the open adjective signifying that there is free passage on the one hand between most of said microcavities, and on the other hand between said microcavities and the internal and external surfaces of the parts considered; the concept of free passage must also be considered according to the nature of the environment and the physical conditions in which the ceramic is found. For example, for small molecules such as hydrogen or helium, free passage will be easy, all the more so if there is a pressure difference between the two surfaces of the part ceramic. In this case, the part is said to be permeable, for example with hydrogen, or not waterproof.
  • closed porosity designates the porosity consisting of microcavities which do not communicate with the surface of the part. In this case, this closed porosity only causes an overall decrease in the density of the part.
  • the method according to the invention can be implemented in a device comprising a reactor (1) of elongated shape along an axis, preferably of square or rectangular section, comprising at a first end supply means (5) in mixture gaseous, containing at least one hydrocarbon, at the opposite end of the means for discharging (10) the effluents produced and between these two ends of the means for supplying cooling fluid, said reactor comprising in a first part (side of the first end ) a plurality of electric heating means (3) surrounded by sheaths (4), said means substantially parallel to each other being arranged in substantially parallel sheets, perpendicular to the axis of the reactor so as to define between the sheaths and / or the sheets formed by these sheaths spaces or passages for the circulation of gas mixtures and / or effluents, said heating means and said sheaths being adapted to heat said successive cross-sectional passages, independent and substantially perpendicular to the axis of the reactor, said reactor further comprising control and modulation heating
  • the means for introducing gas G at an appropriate pressure are those known to those skilled in the art. They may also comprise means for regulating and controlling the pressures prevailing inside and outside said sheaths.
  • Said cooling means are means suitable for cooling by direct contact or by indirect contact the effluents leaving the heating zone.
  • the sheaths surrounding the resistors can be arranged in a superimposed or staggered fashion and can form in transverse projection a beam with triangular, square or rectangular pitch.
  • the total number of layers comprising heating means and the number of heating means in each sheath and per layer are not decisive in the process; they are obviously a function of the size, the heating means, the sheaths which surround them and, where they exist, the walls separating the sheets.
  • the heating elements can be identical to each other or different, both in size and in heating power.
  • a heating element may include inside the sheath from 1 to 5 resistors and most often from 1 to 3 resistors.
  • the number of heating elements determines the maximum electrical power available for a given reaction volume and also influences the residence time of the load; it will be chosen according to the admissible charge flow, taking into account these parameters.
  • the electric heating means which can be used in the context of the present invention are preferably heating resistors capable of being used up to temperatures of the order of 1500 ° C .; it is preferred to use resistors made of molybdenum bisilicide, for example hairpin resistors.
  • the sheaths which surround the resistors, so as to avoid direct contact between the gas mixtures of the load and the resistors, are preferably of tubular shape.
  • These refractory sheaths are usually either ceramic or sintered metal. Ceramics such as mullite, cordierite, silicon nitride, silicon carbide, silica or alumina can be used; silicon carbide is the preferred material because it has good thermal conductivity. In the case where the sheets are separated by walls, the material chosen to make these walls may be the same as that used for the sheaths, but it is often different, in particular for reasons of cost of manufacturing the oven.
  • ducts are usually used tubular or cylindrical with diameter D usually from about 1.2 xd to about 8 xd, and most often about 1 , 5 xd to about 4 x d.
  • the heating elements are arranged in parallel layers substantially perpendicular to the direction of flow of the charge (process gas), preferably substantially aligned, so that the distance between two neighboring ducts is as small as possible, while taking into account allowable pressure drop requirements; the distance between the sheaths of two neighboring plies or that between the sheaths of a ply and the nearest wall in the case where the plies are separated by walls is usually the same as that between two consecutive sheaths in a given ply.
  • This distance will usually be such that the passages formed between the sheaths or between the sheaths and the nearest wall, passages in which the gas mixture containing hydrocarbons circulates will have a dimension of approximately 1 to approximately 100 mm, and most often d '' about 5 to about 40 mm.
  • the free spaces or passages defined above, intended for the circulation of the process gas are at least partially occupied by linings, usually made of ceramic, preferentially heat conductors. It is thus possible, for a given type of reactor, to reduce the residence time of the charge in this reactor while homogenizing the flow of the gaseous mixture and better distributing the dissipated heat.
  • linings can have various shapes and be presented for example in the form of rings (Raschig, Lessing or Pall rings), saddles (Berl saddles), bars, closed cylindrical tubes.
  • a vertical reactor (1) of elongated shape and of rectangular section comprising a distributor (2) making it possible to supply the reactor with an inlet orifice (5) in reaction gas mixture.
  • the latter which contains a mixture of steam and at least one hydrocarbon, has been preheated in a conventional preheating zone, not shown in the figure, preferably by convection.
  • the reactor comprises a plurality of electrical heating means (3) surrounded by sheaths (4) arranged in parallel sheets and forming in a plane (plane of the figure) a bundle with square pitch. These layers define transverse heating sections substantially perpendicular to the axis of the reactor defined in the direction of flow of the charge.
  • thermocouple pyrometric probes 7 in FIGS. 1D and 1E are housed in the spaces where the charge circulates between the sheaths (4) and allow regulation automatically the temperature of each heating section, by a conventional regulator and modulator device not shown in the figure.
  • the ducts are heated so that the temperature of the charge rapidly rises from 600 ° C (preheating temperature) to approximately 900 ° C; this heating zone generally represents approximately 15% of the total length of the heating zone; the gas mixture then circulates in the second part of the heating zone where the temperature is generally maintained at a constant value substantially equal to that reached at the end of the first heating zone, that is to say approximately 900 ° C.
  • the electrical power supplied to several heating sections which constitute the second part of the heating zone is modulated; this results in a temperature variation not exceeding around 10 ° C around the setpoint value.
  • the length of this second heating zone represents approximately 85% of the total length of the heating zone.
  • reaction effluents On leaving the heating zone, the reaction effluents are cooled in a cooling zone (8). They are brought into contact with a quenching agent such as water introduced via injectors (9), quenching, arranged at the periphery of the reactor (1) and connected to an external source of water not represented. All of the effluent gases are cooled to a temperature of approximately 500 ° C. and collected by an outlet orifice (10) at the end of the reaction zone (1).
  • a quenching agent such as water introduced via injectors (9), quenching
  • the effluents can be cooled by circulating through sealed conduits arranged in the zone (8) through which the quenching agent flows, these conduits being connected to the external source of the quenching.
  • the reactor identical to that shown diagrammatically in FIG. 1A, comprises in the space where the charge circulates a lining (20), advantageously made of ceramic material, which is retained by a grid ( 21) at the end of the heating zone.
  • the sheaths (4) are arranged in parallel layers and form in a plane (plane of the figure) a beam with triangular pitch (staggered arrangement).
  • FIG. 1C there is shown, according to one embodiment, a horizontal reactor (1) of elongated shape and of rectangular section, which differs from the reactor shown in FIG. 1A only in that it is substantially horizontal, that it comprises sheaths arranged in parallel plies and forming in a plane (plane of the figure) a bundle with square pitch, and in that these plies are separated from each other by walls (22) advantageously made of ceramic material.
  • These walls have a shape, adapted to create turbulence, comprising cells at each sheath (4).
  • FIG. 1F differs from that shown diagrammatically in FIG. 1C only in that several layers of heating elements are situated between two walls (22).
  • FIG. 1D represents, for a horizontal reactor, the same elements as those described in connection with FIG. 1A; there is shown, moreover, a protective housing (11) comprising an orifice (12) through which gas G containing for example steam is introduced and an orifice (13) provided with a valve (24) making it possible to regulate the flow of this gas G.
  • This box (11) is fixed to the metal frame of the reactor (1) and surrounds all the electrical resistances and sheaths containing them, with the exception of the ends of the electrical resistances where the electrical energy is supplied.
  • the resistors (3), in a pin, are positioned in the sheaths (4) using washers (18), for example made of ceramic fiber, having passages (23) allowing gas G, for example steam d water, to enter the space between the resistors and the sheaths.
  • washers (18) for example made of ceramic fiber, having passages (23) allowing gas G, for example steam d water, to enter the space between the resistors and the sheaths.
  • Figure 1E shows the same elements as those described in connection with Figure 1A; there is shown, moreover, the protective boxes (11) provided with orifice (12) and (13) allowing the circulation in the boxes of the gas G containing for example water vapor which penetrates into the space of the resistances through the holes (23) of the washers (18) ensuring the positioning of the resistances.
  • the orifices (13) are provided with valves (24) allowing easier regulation of the flow of the gas G containing for example water vapor.
  • These boxes (11) are fixed to the metal frame of the reactor and surround all the electrical resistances and sheaths containing them, with the exception of the end of the electrical resistances through which the electrical energy is supplied.
  • the circulation of the gas G is carried out in slight overpressure compared to the pressure of the process gas within the reactor, thus ensuring a perfectly controlled atmosphere and a better diffusion of this gas G towards the process space.
  • the absolute pressure difference between the space of the resistors and the process space, or overpressure will preferably be such that the pressure in the space of the resistors is at least 0.1% higher and most often at least minus 1% at the pressure in the process space. It is not necessary to have a very high overpressure and most often the pressure in the space of the resistors remains less than 2 times the pressure in the process space.
  • FIG. 2 shows a detail of an embodiment of the heating zone according to the invention.
  • Resistors (3) of cylindrical shape are used as the means of electric heating. These resistors comprise at each of their ends cold zones and a part of the central zone which is the hot zone representing for example approximately 68% of the total length.
  • a reactor of rectangular section is produced, the walls of which are made of insulating refractory concrete (14) and by a metal frame (15).
  • a circular hole is drilled in two opposite side walls, through which a sheath (4), for example made of ceramic, is passed, with a diameter twice that of the electrical resistance (3).
  • the sheath (4) is positioned by means of a cable gland system (16) acting in a groove at the level of the metal frame on a braid of refractory material (17), for example a braid of ceramic material.
  • the positioning of the resistance (3) in the sheath (4) is carried out by means of washers (18), for example made of ceramic fiber, comprising orifices (23) allowing the passage of the gas G, containing for example steam of water, introduced into the housing (11) through the conduit (12) into the space of the resistors (24).
  • washers (18) for example made of ceramic fiber, comprising orifices (23) allowing the passage of the gas G, containing for example steam of water, introduced into the housing (11) through the conduit (12) into the space of the resistors (24).
  • the hot zone of the resistor (3) is positioned so that it does not enter the opening through the wall of insulating concrete. It is not essential to use a braid (17) at the level of the cable gland since the latter has, within the framework of the invention, the role of positioning means and that it does not have the main purpose to ensure as perfect a seal as possible between the inside and the outside of the reactor.
  • This gland can also advantageously be replaced by a simpler means of positioning the sheaths such as for example simple washers made of refractory material.
  • heating resistors sheathed in walls for example of ceramic material, in successive horizontal rows, these rows preferably being aligned so that, on the side walls of the oven, they form a bundle square or rectangular pitch.
  • a housing (11), of which only protrude the ends of the resistors and / or their electrical supply (6), is traversed by a stream of gas G containing for example water vapor.
  • a horizontal indirect quenching reactor is used, the length of the pyrolysis zone of which is 2.21 meters and of rectangular section of 1.4 ⁇ 3.72 m.
  • the heating means of this reactor consist of electrical resistors made of hairpin, made of molybdenum bisilicide (MoSi2); these resistors are surrounded by ceramic sheaths, arranged concentrically with respect to the center of the circle encompassing the resistors.
  • sheaths are made of silicon carbide and have an open porosity of 15% by volume. Each sheath, closed at one end, surrounds 2 pin resistors (Figure 1C and 1D). These sheaths are arranged perpendicular to the direction of flow of the load (vertically), in parallel sheets, and form in perpendicular projection a beam with square pitch.
  • the length of each branch of the pin of the electrical resistance is 1.4 m and the diameter of the resistance is 9 mm.
  • the ceramic sheaths have a length of 1.4 m, an outside diameter of 150 mm and an inside diameter of 130 mm; the distance Eg ( Figure 1C) separating two neighboring sheaths is 20 mm.
  • the sheath layers are separated by a refractory concrete wall based on electrofused alumina.
  • the distance Ee ( Figure 1C) between the ducts and the walls or dimension of the passages is 10 mm.
  • the walls have in their thinnest part a thickness Ep ( Figure 1C) of 15 mm.
  • the first part of the heating zone 34 cm long, includes 20 resistance layers, each layer comprising 2 sheaths; in this zone, the load, preheated to 600 ° C, is brought to 900 ° C.
  • This zone is thermally regulated by means of thermocouples arranged in the spaces where the charge circulates.
  • the second part of the heating zone adjacent to said first part, is 1.87 m long; it consists of 20 layers of 11 sheaths, arranged in the same way as in the first part of the heating zone.
  • This zone is made up of 5 heating sections, independently regulated, ensuring that the temperature in this zone is maintained at 900 ° C plus or minus 10 ° C.
  • the effluent gases are firstly cooled to 500 ° C by indirect exchange with the gases in the feed; other temperature exchangers then make it possible to lower their temperature to approximately 350 ° C.
  • Naphtha with a density d 20/4 0.715 and whose boiling range is between 38 and 185 ° C. diluted with water in a water vapor / charge weight ratio of 0.5 is used as the charge. : 1.
  • This mixture is preheated to 600 ° C and cracked at 900 ° C in the reactor described above.
  • the absolute pressure of the gas mixture in the reactor is kept substantially constant and equal to 0.170 MPa. Resistors of substantially pure water are introduced into the space so as to obtain and maintain in this space a substantially constant absolute pressure equal to 0.175 MPa.
  • Example 1 of US Pat. No. 4,780,196 comprising a multichannel pyrolysis zone, made of silicon carbide, each channel having a square section of 10 mm side and having a length of 3 m.
  • the operating conditions are such that the feed is introduced into this reactor at the temperature of 600 ° C. and the effluents at the end of the pyrolysis are at 900 ° C. In this installation, heating is provided by a heat transfer fluid.
  • the process according to the invention therefore makes it possible to obtain the ethylene-propylene assembly with an improved yield of approximately 14% and to reduce the initial maximum coking speed by approximately 33%.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
EP92402951A 1991-11-08 1992-10-30 Verfahren zur thermischen Pyrolyse von Kohlenwasserstoffen mit Elektroofen Expired - Lifetime EP0542597B1 (de)

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FR9113976A FR2683543B1 (fr) 1991-11-08 1991-11-08 Procede de pyrolyse thermique d'hydrocarbures utilisant un four electrique.
FR9113976 1991-11-08

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EP0733609A1 (de) * 1995-03-23 1996-09-25 Institut Francais Du Petrole Verfahren zur thermischen Umsetzung von aliphatischen gesättigten oder ungesättigten Kohlenwasserstoffen in acetylenischen Kohlenwasserstoffen
EP0781828A1 (de) 1995-12-27 1997-07-02 Institut Francais Du Petrole Kontinuerliches Pyrolyse- und Entkohlungsverfahren, insbesondere zur Anwendung in der Herstellung
FR2748273A1 (fr) * 1996-05-06 1997-11-07 Inst Francais Du Petrole Procede et dispositif de conversion thermique d'hydrocarbures en hydrocarbures aliphatiques plus insatures que les produits de depart, combinant une etape de vapocraquage et une etape de pyrolyse
WO2020047091A1 (en) * 2018-08-31 2020-03-05 Dow Global Technologies Llc Systems and processes for improving hydrocarbon upgrading
WO2020046638A1 (en) * 2018-08-31 2020-03-05 Dow Global Technologies Llc Systems and processes for improving hydrocarbon upgrading
EP3725865A1 (de) * 2019-04-17 2020-10-21 SABIC Global Technologies B.V. Verwendung von erneuerbarer energie in der olefinsynthese
EP3730592A1 (de) * 2019-04-24 2020-10-28 SABIC Global Technologies B.V. Verwendung von erneuerbarer energie bei der olefinsynthese
WO2023016968A1 (en) * 2021-08-12 2023-02-16 Sabic Global Technologies B.V. Furnace including electrically powered heating elements arranged for uniform heating and related methods

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FR2750140B1 (fr) * 1996-06-25 1998-08-07 Inst Francais Du Petrole Installation de vapocraquage avec moyens de protection contre l'erosion
AU734708B2 (en) * 1997-10-08 2001-06-21 Shell Internationale Research Maatschappij B.V. Flameless combustor process heater
DE19746040A1 (de) * 1997-10-17 1999-04-22 Basf Ag Verfahren zur Herstellung von Propen
FR2791665B1 (fr) * 1999-03-31 2001-05-18 Inst Francais Du Petrole Procede de production de methylacetylene et de propadiene
FR2830205B1 (fr) 2001-09-28 2003-12-12 Inst Francais Du Petrole Enceinte reactionnelle comprenant une enveloppe contenant au moins un module relie par des moyens souples a l'enveloppe et contenant des moyens d'echange de chaleur
BRPI0608336B1 (pt) * 2005-03-10 2018-09-11 Shell Int Research sistema de processamento, sistema de aquecimento direto de quatro tubos para queima de um combustível e aquecimento direto de um fluido de processamento e método
AU2006223449A1 (en) * 2005-03-10 2006-09-21 Shell Internationale Research Maatschappij B.V. Method of starting up a direct heating system for the flameless combustion of fuel and direct heating of a process fluid
JP2008532747A (ja) * 2005-03-10 2008-08-21 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ 燃料の燃焼とプロセス流体の加熱のための伝熱システム及びその使用方法
CN101443759B (zh) * 2006-05-12 2010-08-11 北京乐图在线科技有限公司 多语言信息检索的方法和系统
WO2009014979A2 (en) * 2007-07-20 2009-01-29 Shell Oil Company A flameless combustion heater
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US9862606B1 (en) 2017-03-27 2018-01-09 Lyten, Inc. Carbon allotropes
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US11299678B2 (en) 2017-09-06 2022-04-12 Bioforce Tech Corporation Efficient procedure and system to process solid organic waste
US10465128B2 (en) 2017-09-20 2019-11-05 Lyten, Inc. Cracking of a process gas
US11345859B2 (en) 2018-06-24 2022-05-31 Bioforce Tech Corporation Hybrid pyrolysis system and method
EP4313389A2 (de) * 2021-03-25 2024-02-07 Nova Chemicals (International) S.A. Intern beheizter reaktor zur umwandlung von kohlenwasserstoffen
KR20230126666A (ko) * 2022-02-23 2023-08-30 주식회사 엘지화학 유체 가열 장치

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EP0323287A1 (de) * 1987-12-31 1989-07-05 Institut Français du Pétrole Verfahren zur thermischen Umsetzung von Methan in Kohlenwasserstoffe mit höherem Molekulargewicht, sowie dabei zu verwendender Reaktor
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FR1305287A (fr) * 1961-11-20 1962-09-28 Union Rheinische Braunkohlen Procédé pour la fabrication de mélanges gazeux à forte teneur en oléfines, notamment en éthylène, à partir d'hydrocarbures gazeux ou vaporisés
EP0323287A1 (de) * 1987-12-31 1989-07-05 Institut Français du Pétrole Verfahren zur thermischen Umsetzung von Methan in Kohlenwasserstoffe mit höherem Molekulargewicht, sowie dabei zu verwendender Reaktor
EP0457643A1 (de) * 1990-05-17 1991-11-21 Institut Français du Pétrole Verfahren zur thermischen Umsetzung von Methan und Vorrichtung zur Durchführung des Verfahrens

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FR2732014A1 (fr) * 1995-03-23 1996-09-27 Inst Francais Du Petrole Procede de conversion thermique d'hydrocarbures aliphatiques satures ou insatures en hydrocarbures acetyleniques
EP0733609A1 (de) * 1995-03-23 1996-09-25 Institut Francais Du Petrole Verfahren zur thermischen Umsetzung von aliphatischen gesättigten oder ungesättigten Kohlenwasserstoffen in acetylenischen Kohlenwasserstoffen
US6027635A (en) * 1995-12-27 2000-02-22 Institute Francais Du Petrole Continuous pyrolysis and decoking process for use in the production of acetylene
EP0781828A1 (de) 1995-12-27 1997-07-02 Institut Francais Du Petrole Kontinuerliches Pyrolyse- und Entkohlungsverfahren, insbesondere zur Anwendung in der Herstellung
FR2743007A1 (fr) * 1995-12-27 1997-07-04 Inst Francais Du Petrole Procede de pyrolyse et de decokage en continu applicable notamment a la production d'acetylene
US6322760B1 (en) 1996-05-06 2001-11-27 Institut Francais Du Petrole Process and apparatus for thermal conversion of hydrocarbons to aliphatic hydrocarbons which are more unsaturated than the starting products, combining a steam cracking step and a pyrolysis step
US5976352A (en) * 1996-05-06 1999-11-02 Institut Francais Du Petrole Process for thermal conversion of hydrocarbons to aliphatic hydrocarbons which are more unsaturated than the starting products, combining a steam cracking step and a pyrolysis step
EP0806467A1 (de) * 1996-05-06 1997-11-12 Institut Français du Pétrole Verfahren und Einrichtung zur thermischen Umsetzung von Kohlenwasserstoffen zu ungesättigten aliphatischen Kohlenwasserstoffen durch Kombination einer Dampfkrackung und einer Pyrolysestufe
FR2748273A1 (fr) * 1996-05-06 1997-11-07 Inst Francais Du Petrole Procede et dispositif de conversion thermique d'hydrocarbures en hydrocarbures aliphatiques plus insatures que les produits de depart, combinant une etape de vapocraquage et une etape de pyrolyse
WO2020047091A1 (en) * 2018-08-31 2020-03-05 Dow Global Technologies Llc Systems and processes for improving hydrocarbon upgrading
WO2020046638A1 (en) * 2018-08-31 2020-03-05 Dow Global Technologies Llc Systems and processes for improving hydrocarbon upgrading
US11505751B2 (en) 2018-08-31 2022-11-22 Dow Global Technologies Llc Systems and processes for improving hydrocarbon upgrading
US11679367B2 (en) 2018-08-31 2023-06-20 Dow Global Technologies Llc Systems and processes for improving hydrocarbon upgrading
EP3725865A1 (de) * 2019-04-17 2020-10-21 SABIC Global Technologies B.V. Verwendung von erneuerbarer energie in der olefinsynthese
EP3730592A1 (de) * 2019-04-24 2020-10-28 SABIC Global Technologies B.V. Verwendung von erneuerbarer energie bei der olefinsynthese
WO2023016968A1 (en) * 2021-08-12 2023-02-16 Sabic Global Technologies B.V. Furnace including electrically powered heating elements arranged for uniform heating and related methods

Also Published As

Publication number Publication date
US5321191A (en) 1994-06-14
CA2082290A1 (fr) 1993-05-09
JPH05222379A (ja) 1993-08-31
DE69208595T2 (de) 1996-08-22
DE69208595D1 (de) 1996-04-04
JP3151641B2 (ja) 2001-04-03
EP0542597B1 (de) 1996-02-28
FR2683543B1 (fr) 1994-02-11
FR2683543A1 (fr) 1993-05-14

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