EP0291408B1 - Dampfspaltungsverfahren in einer Wirbelschicht-Reaktionszone - Google Patents

Dampfspaltungsverfahren in einer Wirbelschicht-Reaktionszone Download PDF

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Publication number
EP0291408B1
EP0291408B1 EP88401145A EP88401145A EP0291408B1 EP 0291408 B1 EP0291408 B1 EP 0291408B1 EP 88401145 A EP88401145 A EP 88401145A EP 88401145 A EP88401145 A EP 88401145A EP 0291408 B1 EP0291408 B1 EP 0291408B1
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EP
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Prior art keywords
particles
enclosure
solid particles
effluent
cooling
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EP88401145A
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English (en)
French (fr)
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EP0291408A1 (de
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Gérard Martin
Alain Feugier
Germain Martino
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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
    • C10G9/002—Cooling of cracked gases
    • 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
    • C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
    • C10G51/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only
    • C10G51/023—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only only thermal cracking steps
    • 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
    • C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
    • C10G51/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only
    • C10G51/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only including only thermal and catalytic cracking steps
    • 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
    • C10G9/28—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material
    • C10G9/32—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material according to the "fluidised-bed" technique

Definitions

  • the invention relates to an improved process for steam cracking of hydrocarbons in a reaction zone in a fluid bed intended to produce light olefins, and more particularly ethylene and propylene. It also relates to a device for implementing the method.
  • coke is due to side reactions such as the formation of condensed polycyclic aromatic hydrocarbons, as well as to the polymerization of the olefins formed.
  • the evolution of the technology has mainly focused on the pyrolysis (b) and quenching (c) phases, in an attempt to satisfy the requirements mentioned above and the diversity of the charges to be treated, which extend to current time from ethane to vacuum diesel.
  • the ovens must be heated from very good quality fuels containing little sulfur, for example natural gas or fuel-gas produced by steam cracking itself, which contributes to increasing the cost price of the process.
  • the technology is oriented towards temperature exchangers arranged on the transfer lines of the effluents from the pyrolysis reaction (exchangers called TLX, "transfer line exchanger” described for example in U.S. Patent 4,097,544).
  • exchangers The purpose of these exchangers is to carry out the abrupt reduction of the effluent gases from the pyrolysis reactors as quickly as possible to temperatures at which side reactions of the olefin polymerization type do not occur.
  • the temperature to which the effluent is brought to the outlet of the quench exchanger varies as a function of the steam-cracked charge.
  • the step of bringing the hot particles into contact with the charge, the primary separation step and the cyclone separation step are carried out in different enclosures, which is costly in engineering and which substantially lengthens the total residence time of the effluent before being cooled, not counting that relating to passages in the transfer lines from one enclosure to another.
  • the object of the present invention is to provide a process which overcomes these various drawbacks and allows the steam cracking of a hydrocarbon - or a mixture of hydrocarbons -, comprising at least two carbon atoms, leading to improved yields. ethylene and propylene compared to existing processes.
  • the invention relates to a process for steam cracking in a reaction zone in a fluid bed of a hydrocarbon charge with at least two carbon atoms per molecule, comprising a stage of heating of said charge in a first part of said reaction zone by brought into contact with first particles of hot solids, this heating stage delivering a first gaseous effluent.
  • the method further comprises a stage for cooling said effluent by contacting second particles of cooling solids (or cold particles) in a second part of said reaction zone.
  • said first part of the reaction zone comprises at least one enclosure having a central axis and an internal periphery, in that a mixture of said charge is circulated at least partly in vaporized form with the water vapor at the internal periphery of said enclosure in which contact is established between said mixture and said first particles of solids, heated to a temperature T1 of between 500 and 1800 ° C., said mixture and said particles of hot solid circulating generally co-current from top to bottom or bottom to top, in that, after stirring between at least the particles of hot solids and said mixture, said particles are separated in said enclosure of at least part of said first gaseous effluent resulting from said mixing, said effluent is sent, at least in part, into the second part of said reaction zone opening into said enclosure substantially along its central axis, contact is established between said effluent and said second particles of cooling solids which are circulated in said second part of the reaction zone and which are at a temperature T2 at most equal to 800 ° C., said temperature T2 being
  • the process according to the invention has the advantage of bringing the mixture to the optimum steam cracking temperature in a minimum of time, of maintaining this temperature as constant as possible in the enclosure for a very short time and of carrying out rapid quenching and effective steam cracking effluents.
  • the heat flux density is very high insofar as there is a direct gas-particle contact, and this, over a very large surface, which is the total surface of all the particles.
  • the first particles of hot solids intended for heating the mixture and the second particles of solids, cold, intended for the cooling of the steaming effluent can circulate co-current from top to bottom or from bottom to top; in this first case (see Figure 1 below) the cooling zone is adapted to a downward circulation of cold particles and the gaseous effluent and in the second case, the cooling zone is adapted to an upward circulation, the zone cooling zone and the zone of contact of the hot solid particles with the mixture being generally at vertically opposite poles of the enclosure.
  • the first particles of hot solids and the second cold particles can circulate against the current.
  • the particles of hot solids and the mixture circulate first, then the gaseous effluents and the cold particles follow an ascending path in the cooling zone; or the particles of hot solids and the mixture can rise in the enclosure while the gaseous effluents and the cold catalytic particles follow a downward path in the cooling zone.
  • the cooling zone and the zone for bringing the mixture into contact with the particles of hot solids are generally situated substantially at the same end of the enclosure.
  • These hot or cold particles are advantageously the same, which has the advantage of not posing any problem of contamination of a population of a loop by that of another loop.
  • Solid particles intended for heating or cooling generally have a specific surface of less than 100 m 2 / g (so-called BET method using nitrogen absorption), preferably less than 50 m 2 / g and even more preferred, less than 30 m 2 / g. They have a weak catalytic activity (lower than for example around 10%, the value 100% corresponding arbitrarily to the usual average activity of a cracking catalyst). They are of low cost and it is therefore recommended to reject some of them from time to time, and to replace them with the same fresher quantity, if it turns out that they are polluted in the long run.
  • the particles of solids, hot or cold are generally chosen from the group formed by calcite, dolomite, limestone, bauxite, baryte, chromite, magnesia, perlite, alumina and silica of small surface specific.
  • the cold particles may contain an amount of a catalyst representing from 2 to 95%, preferably from 10 to 50% and more particularly from 12 to 45% by weight of the total fraction of cold particles, which makes it possible to control and increase the selectivity in a desired product, in propylene for example.
  • the catalyst optionally added to the particles intended for cooling the feed could be chosen from catalysts making it possible to carry out the metathesis of an internal olefin with ethylene.
  • These catalysts are generally based on compounds of molybdenum, tungsten, vanadium, niobium, tantalum or rhenium deposited on a matrix of silica, alumina, silica-alumina, zirconium oxide, thorium oxide, etc. This catalyst is suitable for final distribution of steam cracking effluents.
  • These catalytic particles can have a particle size between approximately 20 and 2000 micrometers and advantageously between 50 and 500 micrometers. They usually have a specific surface greater than 100 m 2 / g (BET method) and among these, those which have good thermal stability in the presence of water vapor will be advantageously used.
  • the temperature of the first particles of heating solids is usually between about 500 and 1800 ° C and advantageously between about 800 ° C and 1300 ° C while the temperature of the second cooling particles is usually between about 200 and 800 ° C and advantageously between 300 and 600 ° C.
  • the bringing of said mixture into contact with said first particles can be carried out in a zone of said enclosure situated substantially upstream of the inlet of the second part of said reaction zone, that is to say - say the cooling zone of the steam cracking effluent.
  • the method according to the invention comprises the following steps:
  • Said first hot particles are introduced into a stream of water vapor adapted to generate a particle speed of 10 to 80 m / s, advantageously from 15 to 30 m / s and so as to produce a helical flow of said first solid particles in said enclosure.
  • At least part of said charge is injected into said enclosure by spraying or atomizing it, if the charge is still liquid after preheating, or by introducing it, for example, through nozzles if the charge is gaseous, so that the charge exit speed is between approximately 10 and 150 m / s, advantageously between approximately 50 and 100 m / s, the quantity of water vapor entrained in said first particles being such that the mass ratio of vapor flow rate d water relative to the charge rate is between about 0.1 and 2, preferably between about 0.3 and 0.8.
  • the mixture thus obtained is left in contact in said enclosure during a residence time of between approximately 0.1 and 2 s at a temperature T3 of between approximately 500 and 1500 ° C., preferably between 700 and 1100 ° C.
  • Said first particles are separated from said gaseous effluent, said gaseous effluent is sent to the second part of said reaction zone in which said second cooling particles are circulated in a stream of carrier gas (water vapor for example) adapted to generate a particle speed of about 0.5 to 10 m / s and advantageously from 2 to 5 m / s.
  • carrier gas water vapor for example
  • the said gaseous effluent is left in contact in said second part of the reaction zone during a residence time of between approximately 0.1 and 100 s at a temperature T4 of between 300 and 600 ° C.
  • the said second effluent is separated from said second particles. steam cracking, and we collect it.
  • separation of the first particles of the gaseous effluent in the enclosure is meant conventional separation and separation by stripping.
  • the flow rate of hydrocarbons entrained by these particles during this overall separation step towards the regenerator can represent from 0.01 to 0.5% of the flow rate of the total charge, which is particularly advantageous.
  • the invention it is possible to carry out at least one regeneration in a fluidized bed of the first particles of solids, which has the double effect of at least partially removing the coke deposited on these particles during the steam cracking reaction. and warm these particles. If necessary, it is possible to carry out an additional heating of said particles by combustion of an auxiliary fuel introduced substantially at the base of a first regeneration zone so as to stagger its combustion all along the zone. This regeneration of the first particles takes place at a temperature of between 500 and 1800 ° C.
  • the major part of the combustion gases are then separated from the regenerated particles, at least partially recycles said particles of solids regenerated in said enclosure and at least periodically the particles of hot solids from the regeneration step are removed without returning them to said enclosure.
  • said regeneration and said reheating of said first particles can be carried out, in at least two stages, the first in a substantially vertical and elongated tubular zone whose UD ratio (where L is the length of the tube and D its diameter) is between 20 and 400, at a temperature T5 between 500 and 1500 ° C using an oxygen-based carrier gas or a gas comprising molecular oxygen, followed by a second regeneration of heating particles and possibly of the end of the combustion of the auxiliary fuel, in a second zone by means of an oxygen-based carrier gas to a gas comprising molecular oxygen at a temperature T6 between around 700 and 1800 ° C, T6 being higher than T5.
  • said second cold particles which have been heated by contact with the gaseous effluent are generally cooled to a temperature of between 200 and 800 ° C. in at least one cooling zone. fluidized bed located downstream of said enclosure, for example in the tubular cooling zone and / or in the separation zone for the steam cracking effluents from the particles.
  • fuels having for example initial boiling points of the order of 400 ° C. in particular heavy fuels, atmospheric residues, residues vacuum or asphalt, that is to say fuels which may contain heteroatoms such as sulfur, nitrogen and heavy metals and having a very low price, which is a particularly advantageous advantage compared to the conventional heating of steam cracking processes with good quality fuels suitable for minimizing corrosion of tubular chemical heating reactors.
  • fuels having for example initial boiling points of the order of 400 ° C. in particular heavy fuels, atmospheric residues, residues vacuum or asphalt, that is to say fuels which may contain heteroatoms such as sulfur, nitrogen and heavy metals and having a very low price, which is a particularly advantageous advantage compared to the conventional heating of steam cracking processes with good quality fuels suitable for minimizing corrosion of tubular chemical heating reactors.
  • petroleum cokes, coals or related products: lignite, peat etc ... as well as their mixtures.
  • an adsorbent can be introduced at the same time as the fuel so as to carry out the desulfurization in situ combustion effluents. It can be a compound comprising calcium such as limestone, dolomite, calcite, alone or associated with other inert particles.
  • the hydrocarbon feedstocks usable in the context of the invention generally comprise 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 an end 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. It is also possible to use a charge comprising crude oil.
  • the load can be preheated before being brought into contact with the particles, for example at 250 ° C.
  • the cooling zone for example the ascending zone (or riser) comprises an upper part of diameter R containing said cooling means and a lower part of diameter r opening into the enclosure substantially along its central axis. , such that the ratio R / r is between approximately 1 and 10.
  • This configuration has the advantage of limiting the consumption of steam necessary for entraining the particles until entering the cooling reactor, allowing implantation of exchange surfaces in the reactor, which allows homogeneous cooling of the steam cracking effluent and of the second particles in the same zone and finally of limiting the entrainment of the second particles out of the cooling reactor, which avoids to have to do a significant recycling.
  • the first particles of solid, hot and substantially inert particles which come from the reheating zone are introduced into the ejector 1, where they are suspended and accelerated by a current of water vapor, injected by line 2.
  • the load preheated to around 250 ° C. for example, is conveyed by line 3 and introduced into the suspension by a device 4.
  • This device 4 can simply consist of a ring provided with introduction or spraying and surrounding the tube 5 where the vapor-hot particles suspension flows.
  • the heating of the charge very quickly by the hot particles to the steam cracking temperature is generally carried out in line 6 and the steam cracking reaction develops essentially in the upper part 7a of the enclosure 7 which is a Uniflow cyclone, of substantially circular section, with direct passage, with helical flow without reversal of the effluent gas spiral.
  • the reaction temperature is kept substantially constant at this level.
  • the particles are gradually separated from the gaseous effluents by centrifugal effect and fall by gravity into the lower part 7b of the cyclone uniflow.
  • a line 23 brings the water vapor which ensures the desorption of the hydrocarbons fixed on the particles in the lower part 7b.
  • the gaseous effluents substantially free of hot particles pass through inlet means 9 comprising at least one orifice in the upper part of a descending cooling column (or dropper) 8 opening into the enclosure 7 substantially along the axis of said enclosure.
  • a fluidized bed 11 located at the bottom of the enclosure 10.
  • This fluidized bed is equipped with exchanger tubes 12 known per se which lower the temperature of the particles. It is fluidized by steam supplied by line 13 under conditions which ensure effective stripping of the hydrocarbons adsorbed on the grains or which could be entrained by the current of cold particles.
  • a cyclone 14 in connection with the enclosure 10 ensures efficient gas-solid separation before sending the steam cracking effluents to a further treatment by line 15.
  • the cooled particles are then raised by the lift 16, supplied with driving water vapor by the line 17 in a storage silo 18, which can optionally operate in a fluidized bed and be equipped it too, if necessary, exchange surfaces for further cooling of the particles. These particles pass through a cyclone 19 which separates the particle-entrainment vapor.
  • the storage silo 18 feeds the dropper 8 via the line 20.
  • the control of the flow of cooling solids is ensured by the valve 22, which in particular makes it possible to modify the intensity of the heat exchange.
  • the first particles of solid, hot, freed from steam cracking hydrocarbons are directed through a valve 32b, by the line 25 connected to the enclosure 7 towards the lower part of a regeneration and possible reheating assembly which includes a lift 26 and a fluidized storage bed 27.
  • This lift is a substantially vertical tubular column with a UD ratio advantageously between 30 and 200. It allows the combustion in part of the coke deposited or of the hydrocarbons of the feed which have not been steam cracked, ensures thus the regeneration of hot particles and at the same time, the heating of these particles.
  • the lift 26 opens into the enclosure 27 where the combustion of the coke deposited on the grains and the combustion of the auxiliary fuel are terminated, in a fluidized bed, by a supply of air through the line 30.
  • This enclosure 27 also performs a function of storing the particles before they are introduced into the steam cracking zone. This return to the steam cracking zone is ensured by line 31.
  • the flow of heating solids is controlled by valve 32.
  • the heating and regeneration effluents are separated from the hot particles and discharged by line 33 after passing through the cyclone 34 which is connected to the storage and regeneration enclosure.
  • FIG. 2 illustrates the apparatus according to the inventive method where the cooling column is ascending.
  • FIG. 2 The references in FIG. 2 are the same as those in FIG. 1 and correspond to the same means.
  • the gaseous effluent after having been cracked in the upper part 7a of the enclosure 7, is separated from the hot particles in the lower part 7b where the stripping of the particles is also carried out by means of water vapor brought by the line 23. It enters the cooling column 8 by the inlet means 9.
  • the second particles of cooling solids arrive via line 46 of the storage enclosure 10 in the lower part 8a of the column 8 which opens into the lower part of the enclosure 7 along the axis of said enclosure.
  • Water vapor or a recycling of light hydrocarbons supplied by line 41 ensures the fluidization of the particles in the cooling loop.
  • the gaseous effluent is largely cooled in column 8 and enters the separation and storage enclosure 10 where it is separated from the particles and at the same time desorbed from the particles thanks to the supply of water vapor brought by line 13 which also maintains fluidization.
  • a cyclone 14 connected to the storage enclosure refines the separation of the steam cracking effluents which are collected by line 15.
  • a heat exchanger 12 in and / or around the storage enclosure 10 makes it possible to remove the thermal energy accumulated by the cooling particles during the cooling of the effluent.
  • the particles are then recycled through line 46 and valve 22, the latter making it possible to control their flow in the column.
  • a variant of the device according to the invention (fig. 3) consists in providing an ascending cooling pipe 8 where its upper part (defined from the outlet of the column of the enclosure (7) of diameter R contains means for cooling 42 (for example parietal exchange surfaces described for example in patent FR 2575546)
  • This diameter R is such that it is in a ratio R / r (r being the diameter of said column in the enclosure (7) preferably between 2 and 4.
  • the column 8 ensures the cooling of the steam cracking effluent as well as that of the cooling particles, thereby resulting in a simplification of the apparatus because it avoids having to handle high solid particle flow rates in the recycling part.
  • a cyclone 43 collects the particles of solids entrained by the stream of hydrocarbons which are brought into the storage silo 45.
  • the steam cracking effluent is collected by line 44 connected to cyclone 43.
  • An additional steam stripping step using a line 47 in the silo 45 makes it possible to desorb the particles and recover these desorbed effluents by another line (not shown in the figure).
  • the particles are then recycled via line 46 to the cooling column 8 and their flow rate is controlled by valve 22.
  • the pressures in the various chambers are adjusted so that the pressure of the chamber 7 is greater than the pressure of the cooling zone 8, which limits the passage of cooling, inert and / or catalytic particles in enclosure 7.
  • FIG. 4 shows a more detailed view of the cyclone 7 at the level of the upper zone 7a where the steam cracking takes place by contact with the particles of hot solids and at the level of the zone of entry of the gaseous effluent into the column upward cooling.
  • the possibly preheated charge can arrive via line 3b, is divided and injected by means of at least one level of atomizers 50 for atomization or spraying in the case of liquid charges or conventional introduction into the case of gaseous charges, which are known to those skilled in the art and which are arranged on the external wall of the cooling zone 8, for example cylindrical.
  • These injectors can be arranged in a circle perpendicular to the axis of the pipe or in a helix.
  • injectors are generally placed so as to distribute the charge to be vaporized as uniformly as possible over the hot solids entering the cyclone and which circulate at high speed along its periphery.
  • the size of the droplets when the load is liquid is generally between 10 and 300 micrometers (10 and 300 x 10- 6 m).
  • the speed of entry into the cyclone and the speed of ejection of the charge are usually adjusted so that the droplets are substantially vaporized before they strike the hot solids lining the wall. As shown in FIG.
  • the injectors can be arranged in the upper part 7a of the cyclone 7, so as to advantageously send the charge in the direction of flow of the spiral at an angle of about 0 to 80 ° by relative to the radius of the tube passing through the injector and preferably at an angle of about 30 to 60 ° , at a speed generally varying from 10 to 150 m / s, preferably 30 to 80 m / s towards the solid particles hot, which open tangentially into cyclone 7 at a speed generally of 10 to 80 m / s, preferably 20 to 40 m / s.
  • the entry of gaseous effluents into the cooling zone can be arranged on at least one level 9a and advantageously on at least two levels 9a and 9b of the cooling reactor 8 so that these effluents are better distributed over the cooling particles.
  • the conduit 8a and the reactor 8 are preferably constructed so that their external diameter is substantially the same. According to a preferred but nonlimiting embodiment and if we consider the direction of flow of the cooling particles upwards, the internal diameter of the pipe downstream of level 9a is greater than that located upstream of this same level 9a and less than the diameter located downstream from level 9b. This arrangement facilitates the high-speed circulation of the cooling particles and limits their escape into the cyclone. It also ensures better contact of the hydrocarbons with the particles.
  • the openings 9a, 9b are cut in a bevel so that the effluents retain at the entrance the circular movement and the high speed which they acquire in the cyclone (FIG. 6) and they are advantageously directed downwards to favor the contact of the two phases.
  • FIG. 7 shows another mode of admission of the cooling particles into the enclosure 7, which can be applied to the steam cracking loop illustrated in FIG. 1, that is to say in cyclones with or without turning the spiral with a descending cooling reactor 8
  • the inlet pipe 8 for the cooling particles passing through the upper part of the cyclone 7 substantially along its central axis is arranged in its interior to channel the particles towards the middle zone 7b of the cyclone where it is put in contact with gaseous effluents.
  • the cold particles fall into a bed 51 fluidized by steam or light hydrocarbons (C1 to C3) introduced by distributors (sparged-tubes) 52. It then enters by overflow into troughs 53 distributed uniformly over the section from the fluidized bed, which direct the cooling particles to the inlet means 9 of the reactor 8, the upper end of which is contained in the cyclone 7 substantially at the level of the zone 7b.
  • the inlet 9a of the reactor 8 and the outlet of the pipe 8a for the cooling particles preferably have a beveled shape allowing high-speed entry of hydrocarbon vapors substantially tangential to the flow of the particles. This arrangement largely avoids the dispersion of cold particles outside the cooling zone. In addition, the particles flowing by gravity from the spouts are accelerated by the vapors of the effluents which enter the reaction zone at high speed, which promotes rapid and homogeneous contact of the vapors with the cooling particles.
  • Example 1 With inert cooling particles.
  • Example 2 With inert cooling particles and with catalytic particles.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
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  • Engineering & Computer Science (AREA)
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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (18)

1. Verfahren zum Dampfkracken einer kohlenwasserstoffhaltigen Charge mit wenigstens zwei Kohlenstoffatomen pro Molekül in einer wirbelbettreaktionszone, mit einer Heizstufe für diese Charge in einem ersten Teil dieser Reaktionszone durch Kontaktieren mit heißen Feststoffprimärpartikeln, wobei diese Heizstufe einen ersten gasförmigen Abstrom liefert und im übrigen eine Kühlstufe für diesen Abstrom durch Kontaktieren mit sekundären Kühlpartikeln in einem zweiten Teil dieser Reaktionszone umfaßt, dadurch gekennzeichnet, daß dieser primäre Teil der Reaktionszone wenigstens eine Kammer mit einer mittigen Achse und einem Innenumfang umfaßt, daß man ein Gemisch dieser Charge zum Teil wenigstens in verdampfter Form, mit Wasserdampf am Innenumfang dieser Kammer zirkulieren läßt, in welcher ein Kontakt zwischen diesem Gemisch und diesen Feststoffprimärmaterialien hergestellt ist, die auf eine Temperatur T1 zwischen 500 und 1800°C erwärmt sind, wobei dieses Gemisch und diese Feststoffpartikel allgemein im Gleichstrom von oben nach unten oder von unten nach oben zirkulieren, daß bei Ende eines Durchrührungsvorgangs zwischen wenigstens den Feststoffpartikeln und diesem Gemisch man in dieser Kammer diese Partikel von wenigstens einem Teil dieses gasförmigen primären Abstroms, der aus diesem Rührvorgang resultiert, trennt, wenigstens zum Teil diesen Abstrom in den zweiten Teil dieser Reaktionszone leitet, die in diese Kammer im wesentlichen längs deren zentraler Achse mündet, man einen Kontakt zwischen diesem Abstrom und diesen Feststoffsekundärkühlpartikeln herstellt, die man in diesem zweiten Teil der Reaktionszone zirkulieren läßt und die sich auf einer Temperatur T2 höchstens gleich 800°C befinden, wobei diese Temperatur T2 niedriger als die Temperatur T1 ist, man diese zweiten Partikel von einem zweiten Dampfkrackabstrom trennt, der aus dem Kontaktieren eines ersten Abstroms und dieser festen Sekundärpartikel resultiert und man diesen Dampfkrackungsabstrom sammelt.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß diese Feststoffprimärpartikel im wesentlichen inerte Partikel sind und diese zweiten Partikel entweder im wesentlichen inert sein können oder eine Menge an katalytischen Partikeln enthalten können, wobei diese Primär- und Sekundärpartikel eine Granulometrie zwischen etwa 20 und 2000 Mikrometer sowie eine Dichte zwischen etwa 500 und 6000 kg/m3 haben.
3. Verfahren nach einem der Ansprüche 1 bis 2, dadurch gekennzeichnet, daß das Kontaktieren dieses Gemisches mit diesen Primärpartikeln in einer Zone dieser Kammer stattfindet, die im wesentlichen vor dem Eintritt in die zweite Zone dieser Reaktionskammer angeordnet ist.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß man diese heißen Primärpartikel in einen Wasserdampfstrom einführt, der von der Art ist, daß eine Geschwindigkeit der Partikel von 10 bis 80 m/sek. erzeugt wird und derart, daß eine schrauben- bzw. spiralförmige Strömung dieser festen Primärpartikel in dieser Kammer hervorgerufen wird, man entweder vor dieser Kammer oder in diese Kammer wenigstens einen Teil dieser Charge derart injiziert, daß die Austrittsgeschwindigkeit der Charge zwischen 10 und 150 m/sek. liegt, wobei die von diesen Primärpartikel mitgerissene Wasserdampfmenge derart ist, daß das Massenverhältnis Wasserdampf bezogen auf den Chargendurchsatz zwischen etwa 0,1 und 2 beträgt, man in dieser Kammer dieses so erhaltene Gemisch während einer Verweilzeit zwischen etwa 0,1 und 2,0 sek. bei einer Temperatur T3 beläßt, die zwischen etwa 500 und 1500°C beträgt, man diese Primärpartikel von diesem gasförmigen Abstrom trennt, man diesen gasförmigen Abstrom in den zweiten Teil dieser Reaktionszone leitet, in der man diese sekundären Kühlpartikel in einem Trägergasstrom zirkulieren läßt, der so ausgebildet ist, daß eine Partikelgeschwindigkeit von 0,5 bis 10 m/sek. erzeugt wird, man in diesem zweiten Teil der Reaktionszone diesen gasförmigen Abstrom während einer Verweilzeit zwischen etwa 01 bis 100 sek. bei einer Temperatur von T4 zwischen 300 und 600°C im Kontakt beläßt, man von diesen Sekundärpartikeln diesen sekundären Dampfkrackabstrom trennt und man diesen zweiten Dampfkrackabstrom sammelt.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man wenigstens eine Regenerierung der Feststoffprimärpartikel und gegebenenfalls wenigstens ein Wiedererhitzen dieser Partikel durch Verbrennen eines Hilfsbrennstoffes im Wirbelbett bei einer Temperatur zwischen 500 und 1800°C in Anwesenheit von Sauerstoff oder einem molekularen Sauerstoff enthaltenden Gases vornimmt, man den größeren Teil der Verbrennungsgase von den regenerierten Partikeln trennt, man wenigstens zum Teil diese regenerierten Feststoffpartikel in diese Kammer recyclisiert und wenigstens periodisch diese aus der Regenerierungsstufe stammenden Feststoffprimärpartikel abzieht, ohne sie in diese Kammer zu leiten.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß man diese Regenerierung und dieses wiedererhitzen in wenigstens zwei Stufen durchführt, die erste in einer röhrenförmigen im wesentlichen vertikalen und länglichen Zone, deren Verhältnis L/D zwischen 20 und 400 (L gleich die Länge des Rohres und D sein Durchmesser) bei einer Temperatur T5 zwischen 500 und 1500°C vornimmt und zwar vermittels eines Trägergases auf der Basis von Sauerstoff oder eines molekularen Sauerstoff umfassenden Gases, gefolgt von einer zweiten Regenerierung und gegebenenfalls dem Ende der Verbrennung des Hilfsbrennstoffs in einer zweiten Zone vermittels eines Trägergases auf der Basis von Sauerstoff oder eines molekularen Sauerstoff umfassenden Gases bei einer Temperatur T6 zwischen etwa 700 und 1800°C, wobei T6 größer als T5 ist.
7. Verfahren nach einem der Ansprüche 5 bis 6, dadurch gekennzeichnet, daß man diesen Brennstoff im wesentlichen an der Basis der röhrenförmigen Zone einführt.
8. Verfahren nach einem der Ansprüche 5 bis 7, dadurch gekennzeichnet, daß dieser Brennstoff gewählt ist aus der Gruppe, die gebildet ist durch die schweren Heizöle, die atmosphärischen Rückstände und/oder Vakuumrückstände, die Asphalte, die Petrolkokse, die Kohlen, die Torfe, die Lignite und deren Gemische.
9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die Feststoffpartikel gewählt sind aus der Gruppe gebildet durch Kalzit, Dolomit, Kalkstein, Bauxit, Baryt, Chromit, Magnesiumoxid, Perlit, Alumminiumoxid und Siliziumoxid mit geringer spezifischer Oberfläche.
10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß man diese Sekundärpartikel in wenigstens einer Kühlzone im Wirbelbett kühlt, die hinter dieser Kühlkammer angeordnet ist und zwar bei einer Temperatur zwischen etwa 200 und 800°C und man diese gekühlten Partikel wenigstens zum Teil in diese Kammer recyclisiert.
11. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß die Temperatur der heißen Feststoffprimärpartikel zwischen etwa 500 und 1800°C beträgt und die der zweiten kalten Feststoffpartikel zwischen etwa 200 und 800°C beträgt.
12. Verfahren nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß diese Feststoffprimärpartikel und dieses Gemisch im allgemeinen zusammen entweder im Gleichstrom oder im Gegenstrom zu diesen Sekundärpartikeln zirkulieren.
13. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß diese kalten Sekundärpartikel im übrigen einen Katalysator mit einer Matrix umfassen, die gewählt ist aus Siliziumoxid, Aluminiumoxid, Siliziumoxid-Aluminiumoxid, Zirkonoxid, Thoriumoxid und Verbindungen des Molybdäns, Wolframs, Vanadiums, Niobs, Tantals oder Rheniums enthält, wobei dieser Katalysator 2 bis 95 Gew.-% der kalten Sekundärpartikel darstellt.
14. Vorrichtung zur Durchführung des Verfahrens nach Anspruch 1, dadurch gekennzeichnet, daß sie umfaßt (Fig. 1):
-wenigstens eine Kammer (7) vom Zyklontyp mit einer mittigen Achse und einem Innenumfang,
- Mittel (4), zum Einführen (3b, 50, Fig. 4) einer kohlenwasserstoffhaltigen (3) flüssigen oder gasförmigen Charge, die entweder anströmseitig angeordnet und mit dieser Kammer verbunden oder in dieser Kammer angeordnet sind,
- Mittel zum Einführen (2) von Wasserdampf vor diesen Einführungsmitteln der Charge derartiger Ausbildung, daß sie diese heißen Primärpartikel in diese Kammer (7) mitreißen,
- Mittel zum Einführen (6) dieser heißen festen Primärpartikel, welche diesen Partikeln eine schraubenförmige oder spiralförmige Bewegung am Innenumfang dieser Kammer (7) in der Richtung der Strömung, die aus der Charge und dem Wasserdampf resultiert, erteilen,
- Mittel zum Trennen (7b, 23) der Feststoffpartikel von einem gasförmigen Abstrom in dieser Kammer (7),
- Mittel zum Transport (25) der Feststoffprimärpartikel, die mit diesen Trennmitteln verbunden sind, gegen wenigstens ein Regenerationsmittel (26) und gegebenenfalls zum Wiedererhitzen (29) dieser Feststoffpartikel,
- Mittel zum Speichern (27) und Recyclisieren (31, 32) dieser Feststoffpartikel, die mit diesen Regenerationsmitteln (26) und gegebenenfalls mit diesen Wiedererhitzungsmitteln (29) verbunden sind gegen diese Kammer (7),
- Mittel zum Einführen der festen Sekundärkühl- oder Kaltpartikel (8a) in diese Kammer (7),
- wenigstens ein Mittel (g) zum Einführen dieses gasförmigen Abstroms sowie der kalten Feststoffpartikel in einen Kühlreaktor, der eine Kolonne (8) länglicher röhrenförmiger und im wesentlich vertikaler Gestalt ist, der im Inneren dieser Kammer im wesentlichen längs ihrer mittigen Achse mündet, unter Gleichstromzirkulation des gasförmigen Abstroms und der kalten Feststoffsekundärpartikel entweder von oben nach unten (dropper) oder von unten nach oben (riser),
- Trennmittel zum Strippen (stripping) (10, 11) eines zweiten Dampfkrackabstroms und den kalten Feststoffpartikel am Ende der Kolonne, das dem Ende gegenüberliegt, über den dieser gasförmige Abstrom und die kalten Feststoffpartikel eingeführt wurden,
- Mittel zum Kühlen (12) der kalten Sekundärpartikel in dieser Kolonne und/oder in diesen Trennmitteln (10,11),
- Mittel zum Austritt (15) dieses zweiten Dampfkrackungsabstroms, die mit diesen Trennmitteln (10, 11) verbunden sind,
- Mittel zum Transport (16) der kalten Feststoffsekundärpartikel, welche mit diesen Trennmitteln verbunden sind gegen ein Speichermittel (18), und
- Mittel zum Recyclisieren (20, 22), dieser Sekundärpartikel wenigstens zum Teil zu diesem Kühlreaktor.
15. Vorrichtung nach Anspruch 14, dadurch gekennzeichnet, daß das Regenerierungsmittel (26) eine längliche röhrenförmige Kolonne umfaßt, die an ihrer Basis Injektionsmittel (29) für einen Hilfsbrennstoff enthält.
16. Vorrichtung nach einem der Ansprüche 14 bis 15, dadurch gekennzeichnet, daß die Eintrittsmittel für die primären Feststoffpartikel sich im oberen Teil (7a) der Kammer (7) befinden und daß die Kolonne (8) zur aufsteigenden Zirkulation des gasförmigen Abstroms und der Kalten Feststoffsekundärpartikel ausgebildet ist.
17. Vorrichtung nach einem der Ansprüche 14 bis 15, dadurch gekennzeichnet, daß die Mittel für den Eintritt der Feststoffprimärpartikel sich im oberen Teil (7a) der Kammer befinden und daß die Kolonne (8) für die absteigende Zirkulation des gasförmigen Abstroms sowie der kalten Sekundärfeststoffpartikel ausgebildet ist.
18. Vorrichtung nach einem der Ansprüche 14 bis 16, dadurch gekennzeichnet, daß die Kolonne (8) (Fig. 3) einen oberen Teil von einem Durchmesser R umfaßt, welcher diese Kühlmittel (12) enthält und einen unteren Teil vom Durchmesser r umfaßt, der in diese Kammer (7) derart mündet, daß das Verhältnis R/r zwischen etwa 1 und 10 und vorzugsweise zwischen 2 und 4 beträgt.
EP88401145A 1987-05-11 1988-05-10 Dampfspaltungsverfahren in einer Wirbelschicht-Reaktionszone Expired - Lifetime EP0291408B1 (de)

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JPS63304091A (ja) 1988-12-12
EP0291408A1 (de) 1988-11-17
ES2018353B3 (es) 1991-04-01

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