EP1637575B1 - Wanderbettverfahren zur Produktion von Propylen mit Recycling von einer Fraktion des verwendeten Katalysators - Google Patents

Wanderbettverfahren zur Produktion von Propylen mit Recycling von einer Fraktion des verwendeten Katalysators Download PDF

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Publication number
EP1637575B1
EP1637575B1 EP05291650A EP05291650A EP1637575B1 EP 1637575 B1 EP1637575 B1 EP 1637575B1 EP 05291650 A EP05291650 A EP 05291650A EP 05291650 A EP05291650 A EP 05291650A EP 1637575 B1 EP1637575 B1 EP 1637575B1
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Prior art keywords
catalyst
moving bed
oligocracking
reactor
fraction
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French (fr)
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EP1637575A1 (de
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Sylvain Louret
Vincent Coupard
Patrice Font
Eric Sanchez
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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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1088—Olefins
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081—Recycling aspects
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • C10G2300/708—Coking aspect, coke content and composition of deposits
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins

Definitions

  • the invention relates to a process for converting at least part of propylene a hydrocarbon feed comprising olefins in the range of C2 to C12, for example a C4 and / or C5 steam cracking or FCC.
  • FCC acronym for "Fluid Catalytic Cracking" in the English terminology, means catalytic cracking in a fluidized bed and the term Cn denotes a hydrocarbon fraction having substantially n carbon atoms.
  • the feedstock of the process according to the invention is typically a light olefinic feed with a carbon number predominantly between 4 and 12, the conventional recycling of which is difficult.
  • the process for converting a light olefinic feed into a propylene cut described in the present invention employs catalytic reactions to directly convert these light olefins into propylene, ie without any independent preliminary step.
  • oligomerization of olefins This type of oligocracking process is described in one step, as opposed to the two-step process in which a first oligomerization step is followed by a step of cracking the effluents of the oligomerization carried out with a catalyst and operating conditions. distinct from those used in the first oligomerization step.
  • the catalysts used in this type of reaction are generally zeolitic catalysts of Si / Al ratio of between 50 and 1200, preferably between 60 and 800, and more preferably between 75 and 140, chosen from the two MFI and MEL groups. .
  • the Si / Al ratio considered is that of the zeolitic part alone of the catalyst.
  • the process according to the present invention is characterized by an implementation of the moving bed catalyst with a very precise control of the average activity of the catalyst within the reactor by means of recycling a portion of the spent catalyst taken out of the reactor.
  • the temperature is between 500 ° C and 600 ° C
  • the partial pressure of olefins is between 0.01 MPa and 0.2 MPa
  • (1 MPa 10 6 Pa)
  • the space velocity is between 5 h -1 and 30 h-1.
  • This process uses a moving bed, with intermittent catalyst removal that is regenerated and recycled.
  • the recycled and unregenerated catalyst fraction is introduced in admixture with the regenerated catalyst fraction.
  • the non-regenerated catalyst recycle flow control is performed automatically from the measured catalyst flow, regenerated catalyst and recycled catalyst measurements.
  • the used catalyst recycling described in the cited patent relates exclusively to a fluidized bed FCC unit, and not to a moving bed unit as in the case of the present invention, as will be explained hereinafter.
  • the invention makes it possible to reduce the overall average catalytic activity and to be able to adapt it to the value optimal.
  • This effect of reducing activity is moreover relatively more pronounced at the reactor head than at the bottom, because it is possible in particular to adjust the flow rate of the moving bed to adjust the activity of the spent catalyst.
  • the invention makes it possible to reduce the catalytic activity gradient between the head and the bottom of the reactor. This effect is beneficial because large disparities in catalytic activity inevitably result in yield losses due to poorly adapted reaction progress.
  • the invention can be defined as a catalytic oligocracking process of a light olefinic hydrocarbon feedstock comprising hydrocarbons having 2 to 12 carbon atoms, and preferably 4 to 12 carbon atoms, for the production of propylene this process using a supported catalyst comprising at least one zeolite having a shape selectivity, and Si / Al ratio of between 50 and 1200, preferably between 60 and 800, and more preferably between 75 and 140, said zeolite being within one of the following two groups: MEL, MFI, NES, EUO, FER, CHA, MFS, MWW, and the group: NU-85, NU-86 , NU-88 and IM-5, or can be a mixture of zeolites belonging to both groups, the process being characterized in that the cross-flow charge is circulated with respect to the catalyst in at least one radial reactor operating in a bed mobile, we shoot e continuously or discontinuously, in the lower part of the reactor a spent catalyst flow is recycled at the top of
  • the invention therefore relates to an improved process for moving-bed catalytic oligocracking, intended to produce propylene from olefinic hydrocarbon cuts with a carbon number predominantly between 4 and 12.
  • the feedstock of the catalytic oligocracking process in a moving bed typically contains from 20 to 100% by weight, often from 25 to 60% by weight of olefins, especially light olefins with 4 and / or 5 atoms. of carbon.
  • the catalyst may comprise at least one zeolite having a shape selectivity, this zeolite having a Si / Al ratio of between 50 and 1200, in particular between 60 and 800, and preferably between 75 and 140.
  • the supported catalyst comprises at least one zeolite having a shape selectivity, belonging to the group consisting of zeolites of one of the following structural types: MEL, MFI, NES, EUO, IRON, CHA, MFS, MWW, or belonging to the group consisting of the following zeolites: NU-85, NU-86, NU-88 and IM-5, or consist of a mixture of the two types of zeolites.
  • the zeolite (s) may be dispersed in a matrix based on silica, zirconia, alumina or silica-alumina, the proportion of zeolite often being between 15 and 80% by weight, preferably between 30% and 80% by weight.
  • Si / Al ratios within the preferred range of 75 to 140 can be obtained at the time of manufacture of the zeolite, or by dealumination and subsequent removal of alumina.
  • ZSM-5 commercial zeolites can be used: zeolites CBV 28014 (SilAI ratio: 140), and CBV 1502 (Si / Al ratio: 75) from Zeolyst International, Valley Forge PA., 19482 USA, or ZSM-5 Pentasil Si / Al 125 from Süd-Chemie (Munich, Germany).
  • the catalyst is used in a moving bed, preferably in the form of beads with a diameter of preferably between 1 mm and 3 mm.
  • the regeneration phase typically comprises a combustion phase of the carbonaceous deposits formed on the catalyst, for example using an air / nitrogen mixture, air or air depleted of oxygen (for example by recirculation of the fumes). and may optionally include other phases of catalyst processing and regeneration.
  • the catalytic oligocracking unit is usually carried out at a temperature of between 450 ° C. and 620 ° C., and preferably between 480 ° C. and 580 ° C., with a space velocity generally comprised between 0.5 and 6 hours. 1 and preferably between 1 and 4 h-1.
  • the operating pressure is generally between 0.1 MPa and 0.5 MPa.
  • the regeneration conditions of the oligocracking catalyst generally use a temperature of between 400 ° C. and 650 ° C., the pressure being most often close to the oligocracking pressure.
  • the yield per propylene pass based on the amount of olefins contained in the fresh feed of the process is between 25% and 50% by weight.
  • the mobile bed oligocracking process generally comprises a system for contacting and mixing the non-regenerated spent catalyst fraction and the regenerated catalyst complementary fraction located upstream of the reaction zone.
  • This contacting system may in some cases be a static mixer, or a fluidized bed which will be described more precisely in the detailed description.
  • the unregenerated spent catalyst flow recycled to the top of the oligocracking reactor may be subject to the on-line measurement of the butene content in the olefinic feedstock or the propylene content in the effluent.
  • Other line measurements of a physicochemical characteristic of the feedstock and / or the effluent are conceivable, and in no way limit the scope of the invention.
  • the process according to the invention makes it possible to obtain a high conversion, a selectivity and a high yield of propylene from an olefin feedstock of C2 to C12 and preferably of C4 to C12, thanks to an optimal control of the activity of the catalyst. in the reactor by recycling at the inlet of the moving bed reactor a fraction of spent catalyst withdrawn at the reactor outlet.
  • the typical feedstock of the process according to the invention is an olefinic feedstock generally derived from an FCC unit or a steam cracking unit.
  • the feedstock of the process according to the invention may also comprise C4 / C5 or larger fractions originating from a coking unit in a chamber or in a fluidized bed, or from a visbreaking unit or from a synthesis unit. Fischer-Tropsch synthesis.
  • the feed may also include fractions of a steam cracker gasoline or an FCC gasoline, or other olefinic gasoline.
  • Gasoline is defined as a hydrocarbon cut resulting for the most part from at least one conversion or synthesis unit such as FCC, visbreaking, coking, a Fischer-Tropsch synthesis unit, and the largest of which part consists of hydrocarbons having at least 5 carbon atoms and a final boiling point of 220 ° C.
  • the olefinic fraction constituting the charge of the process according to the invention generally comprises olefins having from 2 to 12 carbon atoms, and preferably from 4 to 12 carbon atoms. It is preferably chosen from the charges defined above, or it may consist of a mixture of the charges defined above.
  • It may also include ethylene, optionally small amounts of unfractionated propylene, hexenes, olefins having from 7 to 10 carbon atoms.
  • the feedstock also often includes highly unsaturated compounds such as dienes (diolefins) having 4.5 carbon atoms especially (especially butadiene), and small amounts of acetylenic compounds having 2 to 10 carbon atoms.
  • dienes diolefins
  • acetylenic compounds having 2 to 10 carbon atoms.
  • at least 80% by weight of the olefinic feed is derived directly from one or more hydrocarbon cracking units, for example units belonging to the group of the following units: FCC, steam cracking, visbreaking, coking.
  • the technology of a radial reactor operating in a moving bed with a catalyst regeneration loop is a well-known technology in the petroleum and petrochemical industry, and used in many processes, for example in continuous hydrocarbon catalytic reforming processes. .
  • the catalyst is in these processes in the form of approximately spherical particles of size between 1 and 3 mm.
  • One or more radial reactors operating in series with a catalyst regeneration loop common to all the radial reactors are typically used. Each radial reactor of the series is fed by the spent catalyst from the previous reactor.
  • radial reactor is meant a moving bed reactor in which the charge passes through the bed along an axis substantially perpendicular to the axis of flow of the catalyst, generally from the outside of the reactor to the interior. The effluents of the reaction are then collected in a well or central collector.
  • a lifting pot (lift pot” in the English terminology) is used to collect the catalyst and then transfer it by pneumatic transport, for example by means of a stream of nitrogen, to the next reactor, or the regeneration zone in which the catalyst is regenerated.
  • the regeneration phase typically comprises at least one combustion phase of the carbonaceous deposits formed on the catalyst, for example using an air / nitrogen or oxygen-depleted air mixture (for example by recirculation of fumes), or preferably dehydrated air, and may optionally include other phases of treatment and regeneration of said catalyst.
  • the regenerated catalyst is then transferred, by pneumatic transport to the upper part of the first reactor of the series, and optionally to supplement the other reactors of the series.
  • the regeneration zone can also be operated in a moving bed, at a pressure generally close to the average pressure of the process, and at a temperature generally of between 400 ° C. and 650 ° C.
  • the catalyst can, when using several reactors in series, flow in counter-current assembly, or co-current of assembly relative to the load.
  • flow in counter-current assembly or co-current of assembly relative to the load.
  • the invention relates to a process for the direct conversion by (oligo) catalytic cracking of a light olefinic hydrocarbon feedstock comprising mainly from 4 to 12 carbon atoms for the production of propylene, this process comprising the direct cracking of the charge on a supported catalyst.
  • the supported catalyst comprises at least one zeolite having a shape selectivity, belonging to the group consisting of zeolites of one of the following structural types: MEL, MFI, NES, EUO, IRON, CHA, MFS, MWW, or belonging to the group consisting of the following zeolites: NU-85, NU-86, NU-88 and IM-5.
  • the catalyst may in certain cases consist of a mixture of zeolites belonging to each of the 2 previously defined groups.
  • the filler circulates through the catalyst bed, preferably radially, at a temperature between 450 ° C and 580 ° C in at least one moving bed reactor using said catalyst.
  • a spent catalyst flow (that is to say containing a carbonaceous deposit generally called “coke”) is withdrawn, continuously or discontinuously, in the lower part of the reactor, a portion of which is directly recycled at the inlet of said reactor, and the other part of which is transferred to a regeneration zone where the spent catalyst is subjected to at least one controlled oxidation step.
  • the regenerated catalyst ie containing a reduced level of carbonaceous deposit relative to the spent catalyst
  • the regenerated catalyst is reintroduced, directly or indirectly, into the upper part of the first reactor of the series where it will mix with the part not containing undergone regeneration.
  • a system is used for mixing the unregenerated spent catalyst fraction and the regenerated catalyst complementary fraction.
  • This system can be a static mixer ("static mixer" in the English terminology) for mixing the regenerated catalyst with the part that has not been regenerated.
  • the mixer is placed in the pipe upstream of the reactor.
  • the type of mixer and its length will be chosen according to the percentage of recycled catalyst, therefore the ratio of regenerated catalyst flow rates and unregenerated catalyst.
  • the ratio of mixer length to diameter of the mixer may vary between 5 and 15, and preferably between 8 and 12.
  • the mixer may have, for example, fixed internal elements, with alternately inverted pitch, leading to vortices at the solid level. (for example, Kenics KM static mixer).
  • the mixer will be able to separate the solid flow into individual streams with subsequent contact (eg, Sulzer SMX static mixer).
  • the fluidization gas may be nitrogen injected uniformly at the base of the fluidized bed by means of a distributor.
  • the regenerated and unregenerated catalysts are brought into contact and mixed under the effect of the fluidization which leads to a large stirring of the fluidized solid.
  • the particles used in a moving bed have dimensions such that their fluidization ability is low, they are nevertheless fluidizable.
  • the mixture is generally correct and the solid is not entrained from the moment when the fluidization speed of the gas is between 2 and 10 times the minimum fluidization speed, and preferably between 3 and 8 times the minimum fluidization speed. .
  • the well-mixed solid is withdrawn at the base of the fluidized bed and then feeds the first reactor of the series.
  • the recycled (i.e., non-regenerated) used catalyst stream is determined in order to obtain an optimum average activity of the catalyst mixture in terms of yield and propylene selectivity in the reactor effluent.
  • the respective flow rates of regenerated catalyst and spent catalyst recycled to the inlet of the mixer situated upstream of the reactor are determined as a function of in-line measurements made on the feedstock, for example the butene content, or on-line measurements of the propylene yield. or online measurements of C4 conversion and selectivity to propylene, or any other measure of unit performance. It is also possible to use measurements of the percentage of butenes, of propylene, and of propane in the effluents simultaneously. In comparison with a kinetic model, the calculator deduces whether the average catalytic activity is correct or not, and modifies if necessary the flow of spent recycled catalyst and / or the average flow rate of the catalyst.
  • the respective flow rates of regenerated catalyst and spent catalyst directly recycled are controlled via the flow rates of transport gas injected into the jars.
  • the zeolite or zeolites used in the catalyst belong to the subgroup consisting of the structural type zeolites MEL, MFI and CHA, or the zeolite subgroup of structural type MFI.
  • ZSM-5 zeolite can be used.
  • the catalyst used can also be a mixture of these different zeolites.
  • the process according to the invention may use one or more reactors, or several reaction zones situated inside the same reaction chamber.
  • the space velocity PPH defined as the ratio of the mass flow rate of the hydrocarbon feedstock to the catalyst mass contained in each reaction zone can be, for example, between 0.5 h -1 and 6 h -1, and preferably between 1 h -1 and 4 h-1.
  • the feed before being introduced into the moving bed oligocracker unit can undergo selective hydrogenation, in a preliminary step, to remove diolefins and other acetylenic impurities often present in the feedstock.
  • the effluent of the moving-bed catalytic oligocracker unit is typically subjected to a fractionation step most often comprising a compression of the gases and one or more distillations to separate the effluents and produce a C3 cut rich in propylene, or substantially pure propylene. Distillations can be performed using distillation columns having an inner wall, allowing a gain on the operating and construction costs.
  • the mobile bed catalytic oligocracker unit according to the invention is located on the same site as a steam cracking unit, or an FCC unit, the effluents of said moving bed catalytic oligocracking unit can be combined with those of steam cracking or FCC, to be fractionated in common.
  • a charge (50) is introduced in vapor form into a moving bed reactor (105).
  • the charge flows radially through the catalyst bed and reacts by producing the effluent (51).
  • the effluent (51) is collected at the center of the reactor and then sent to the subsequent treatments.
  • An additional fresh catalyst (1) is introduced into the lower hopper (100) of the regenerator where it is mixed with the used catalyst (10) from the upper hopper (109) of the regenerator.
  • the catalyst mixture (2) is conducted semi-continuously in a first zone of the mobile bed radial regenerator (101) by gravity flow where it undergoes combustion in the presence of an air-enriched gas (21) (20). ).
  • the combustion gases (22) are extracted and sent to the exchanger (120).
  • the catalyst is then calcined in a second zone in the presence of a gas (21) enriched with air (22).
  • the combustion gases (23) are also sent to the exchanger (120) for cooling to a temperature suitable for dehydration in the dryer (121).
  • the dried gases (25) are then introduced into a compressor (122).
  • the compressed flue gases (26) are heated in the oven (123) before being mixed with air (20) and reintroduced into the regenerator.
  • the regenerated catalyst (3) passes into a hopper (102) and into a lift pot (103) to be conveyed into the upper hopper of the reactor (104) by pneumatic transport with transport nitrogen (27).
  • the regenerated catalyst (5) is mixed with the spent catalyst (11) from the secondary lift of the reactor (108).
  • a scan (40) allows to evacuate the fines created during transport to a particulate filter (41).
  • the mixture (6) of a regenerated catalyst portion (5) and a spent catalyst portion (11) is introduced into the moving bed radial reactor (105) where it is contacted with the charge (50) .
  • the catalyst flows gravitarily into the reactor and is collected in the bottom in a hopper (106).
  • Part of the catalyst (9) is sent to the regeneration by pneumatic transport using the primary lift (107) of the reactor, while a fraction of the used catalyst (11) is returned directly to the reactor head at the reactor. using the secondary elevation pot (108) of the reactor.
  • the lift (108) is fed with spent catalyst also from the hopper (106) by a line not shown. Both risers of the reactor are supplied with gas (nitrogen) by the line (27).
  • the figure 2 proposes means for controlling the respective flow rates of spent and regenerated catalyst.
  • Measuring means (1000) and (1002) are respectively arranged on the load (50) and the effluent (51). These means make it possible, for example, to measure the content of butenes and / or propylene and / or propane of the feedstock and the effluent.
  • a calculator (1001) makes it possible to calculate the conversions and selectivities in propylene.
  • the information from the calculator which includes a kinetic model, is sent to the conveyor gas flow control valves (1003), (1004) and (1005) for adjusting respectively the recycled used catalyst flow (11) from the lifting pot (108), the spent catalyst flow (9) from the lifting pot (107) towards the regeneration zone, and the regenerated catalyst flow (5) from the lifting pot (103).
  • Examples 1 (prior art) and 2 (according to the invention) are obtained from an MFI zeolite of Si / Al ratio of 75, and Examples 3 (prior art) and 4 (according to the invention) are obtained on an MFI zeolite with a Si / Al ratio of 140.
  • the charge to be treated consists of 100% isobutene.
  • the charge is injected into a reactor operating in a moving bed.
  • the catalyst used is a CBV1502 containing 80% MFI type zeolite having a Si / Al ratio of 75.
  • the catalyst is regenerated in a regeneration zone operating at a temperature of 823 K and a pressure of 0.10 MPa.
  • the catalyst cycle time is 48 hours.
  • the reaction is carried out at a temperature of 853 K and a total pressure of 0.12 MPa.
  • the liquid space velocity is 4.5 h-1.
  • compositions obtained at the outlet of the reactors are indicated in Table 1.
  • Table 1 - Composition at the outlet of a moving bed without catalyst recycling The performance of the unit in terms of selectivity and yield are: Compound Composition (% mass) Methane 1.92 Ethylene 15.30 Ethane 1.00 propylene 24.95 Propane 5.22 isobutane 4.02 isobutene 5.21 1-Butene 2.60 Butane 2.50 Trans-2-Butene 3.19 Cis-2-butene 2.40 3-methylbutene-1 0.14 isopentane 0.69 Pentene-1 0.23 2-methylbutene-1 0.71 pentane 0.24 Pentene-2 Trans 0.58 Pentene-2 Cis 0.32 2-methylbutene-2 1.29 1-Trans-3-Pentadiene 0.03 1-Cis-3-Pentadiene 0.05 cyclopentene 0.14 cyclopentane 0.48 others (C6 +) 26.78 Total 100.00 Ethylene selectivity 19.10% Propylene selectivity 31.15% Ethylene
  • the charge to be treated and the catalyst are the same as those of Example 1 according to the prior art. 49% mass of the used catalyst flow is directly recycled to the top of the moving bed reactor, mixed with the additional 51% of regenerated catalyst. The catalyst is regenerated under the same conditions as those of Example 1 according to the prior art.
  • compositions obtained at the outlet of the reactors are indicated in Table 2.
  • Table 2 Output composition of a moving bed with spent catalyst recycling
  • the performance of the unit in terms of selectivity and efficiency are: Compound Composition (% mass) Methane 0.73 Ethylene 9.61 Ethane 0.36 propylene 28.97 Propane 2.08 isobutane 2.15 isobutene 12.98 1-Butene 6.38 Butane 1.80 Trans-2-Butene 7.90 Cis-2-butene 5.99 3-methylbutene-1 0.29 isopentane 0.34 Pentene-1 0.48 2-methylbutene-1 1.44 pentane 0.16 Pentene-2 Trans 1.19 Pentene-2 Cis 0.67 2-methylbutene-2 2.59 1-Trans-3-Pentadiene 0.06 1-Cis-3-Pentadiene 0.06 cyclopentene 0.22 cyclopentane 0.40 others (C6 +) 13.16 Total 100 Ethylene selectivity 15.30% Propylene selectivity 46.13% Ethylene yield 9.6
  • the charge to be treated consists of 100% isobutene.
  • the charge is injected into a reactor operating in a moving bed.
  • the catalyst used is a CBV28014 containing 30% MFI type zeolite having an Si / Al ratio of 140.
  • the catalyst is regenerated at a temperature of 823 K and a pressure of 0.10 MPa.
  • the catalyst cycle time is 48 hours.
  • the reaction is carried out at a temperature of 783 K and a total pressure of 0.12 MPa.
  • the liquid space velocity is 1.7 h-1.
  • compositions obtained at the outlet of the reactors are indicated in Table 3.
  • Table 3 Composition at the outlet of a moving bed without catalyst recycling
  • the performance of the unit in terms of selectivity and yield are: Compound Composition (% mass) Methane 0.10 Ethylene 3.63 Ethane 0.08 propylene 23.61 Propane 1.46 isobutane 2.19 isobutene 14.08 1-Butene 6.71 Butane 1.51 Trans-2-Butene 9.97 Cis-2-butene 7.30 3-methylbutene-1 0.47 isopentane 0.67 Pentene-1 0.70 2-methylbutene-1 2.72 pentane 0.29 Pentene-2 Trans 2.06 Pentene-2 Cis 1.10 2-methylbutene-2 5.62 1-Trans-3-Pentadiene 0.03 1-Cis-3-Pentadiene 0.02 cyclopentene 0.22 cyclopentane 0.33 others (C6 +) 15.12 Total 100.00 Ethylene selectivity 6.24% Propylene selectivity 40.55% Ethylene yield
  • Example 3 the charge to be treated and the catalyst are the same as those of Example 3 according to the prior art.
  • the catalyst is regenerated under the same conditions as those of Example 3.
  • 25% mass of the used catalyst flow is directly recycled to the top of the moving bed reactor mixed with 75% regenerated catalyst.
  • compositions obtained at the outlet of the reactors are indicated in Table 4.
  • Table 4 Output composition of a moving bed with spent catalyst recycling
  • the performance of the unit in terms of selectivity and yield are: Compound Composition (% mass) Methane 0.09 Ethylene 3.25 Ethane 0.07 propylene 23.29 Propane 1.24 isobutane 1.95 isobutene 14.86 1-Butene 7.21 Butane 1.37 Trans-2-Butene 10.72 Cis-2-butene 7.85 3-methylbutene-1 0.49 isopentane 0.59 Pentene-1 0.72 2-methylbutene-1 2.80 pentane 0.26 Pentene-2 Trans 2.12 Pentene-2 Cis 1.13 2-methylbutene-2 5.77 1-Trans-3-Pentadiene 0.03 1-Cis-3-Pentadiene 0.02 cyclopentene 0.21 cyclopentane 0.31 others (C6 +) 13.67 Total 100 Ethylene selectivity 5.80% Propylene selectivity 41.56% Ethylene yield 3.25%

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Claims (12)

  1. Verfahren zum katalytischen oligomeren Cracken, das heißt, zur direkten katalytischen Umwandlung in Propylen in einem einzigen Schritt, einer leichten olefinischen Kohlenwasserstoffbeschickung, die Kohlenwasserstoffe umfasst, die 2 bis 12 Kohlenstoffatome und bevorzugt 4 bis 12 Kohlenstoffatome hat, wobei dieses Verfahren einen geträgerten Katalysator verwendet, der mindestens einen Zeolithen umfasst, der eine Formselektivität aufweist und ein Si/AI-Verhältnis im Bereich zwischen 50 und 1.200, wobei der Zeolith aus einer der zwei folgenden Gruppen ausgewählt ist: einerseits der Gruppe MEL, MFI, NES, EUO, FER, CHA, MFS, MWW und andererseits der Gruppe: NU-85, NU-86, NU-88 und IM-5, oder der eine Mischung aus Zeolithen der 2 Gruppen sein kann, wobei das Verfahren dadurch gekennzeichnet ist, dass die Beschickung, bezogen auf den Katalysator, im Kreuzstrom in mindestens einem Radialreaktor, der mit Wanderbett arbeitet, zirkuliert wird, im unteren Teil des Reaktors ein Strom aus verbrauchtem Katalysator kontinuierlich oder diskontinuierlich entnommen wird, eine erste Fraktion dieses verbrauchten Katalysators zum Reaktorkopf recycelt wird, die zusätzliche Fraktion aus verbrauchtem Katalysator in eine Regenerationszone transportiert wird, wo sie mindestens einem Schritt der kontrollierten Oxidation unterzogen wird, die Fraktion aus regeneriertem Katalysator, gemischt mit der ersten Fraktion aus verbrauchtem Katalysator wieder in den oberen Teil des Reaktors eingeführt wird.
  2. Verfahren zum oligomeren Cracken im Wanderbett nach Anspruch 1, wobei die Regenerationsphase mindestens eine Phase der Verbrennung der kohlenstoffhaltigen Ablagerungen, die sich auf dem Katalysator gebildet haben, mittels einer Luft/Stickstoff-Mischung, Luft oder an Sauerstoff verarmter Luft bei einer Temperatur im Bereich zwischen 400°C und 650 °C umfasst.
  3. Verfahren zum oligomeren Cracken im Wanderbett nach Anspruch 1, wobei die Reaktionstemperatur im Bereich zwischen 450°C und 620 °C liegt.
  4. Verfahren zum oligomeren Cracken im Wanderbett nach einem der Ansprüche 1 bis 3, wobei die Raumgeschwindigkeit, definiert als das Verhältnis zwischen dem Massenstrom der Beschickung und der Masse des Katalysators im Bereich zwischen 0,5 h-1 und 6 h-1 liegt.
  5. Verfahren zum oligomeren Cracken im Wanderbett nach einem der Ansprüche 1 bis 4, wobei der Betriebsdruck im Bereich zwischen 0,1 MPa und 0,5 MPa liegt.
  6. Verfahren zum oligomeren Cracken im Wanderbett nach einem der Ansprüche 1 bis 5, wobei die Propylenausbeute des Verfahrens pro Durchgang, bezogen auf die Menge an Olefinen, die in der frischen Beschickung enthalten sind, im Bereich zwischen 25 Gew.-% und 50 Gew.-% liegt.
  7. Verfahren zum oligomeren Cracken im Wanderbett nach einem der Ansprüche 1 bis 6, wobei die Fraktion aus nicht regeneriertem verbrauchtem Katalysator und die zusätzliche Fraktion aus regeneriertem Katalysator mittels eines statischen Mischers in Kontakt gebracht werden, der stromaufwärts der Reaktionszone liegt.
  8. Verfahren zum oligomeren Cracken im Wanderbett nach einem der Ansprüche 1 bis 6, wobei die Fraktion aus nicht regeneriertem verbrauchtem Katalysator und die zusätzliche Fraktion aus regeneriertem Katalysator mittels eines Fließbetts in Kontakt gebracht werden, das stromaufwärts der Reaktionszone liegt.
  9. Verfahren zum oligomeren Cracken im Wanderbett nach einem der Ansprüche 1 bis 8, wobei der Strom aus nicht regeneriertem verbrauchtem Katalysator, der zum Kopf des Reaktors zum oligomeren Cracken recycelt wird, der In-line-Messung des Gehalts an Butenen in der olefinischen Beschickung unterworfen wird.
  10. Verfahren zum oligomeren Cracken im Wanderbett nach einem der Ansprüche 1 bis 8, wobei der Strom aus nicht regeneriertem verbrauchtem Katalysator, der zum Kopf des Reaktors zum oligomeren Cracken recycelt wird, der In-line-Messung des Gehalts an Propylen im Abfluss unterworfen wird.
  11. Verfahren zum oligomeren Cracken im Wanderbett nach Anspruch 7, wobei der statische Mischer, der am Reaktorkopf verwendet wird, ein Verhältnis Länge zu Durchmesser im Bereich zwischen 5 und 15 hat.
  12. Verfahren zum oligomeren Cracken im Wanderbett nach Anspruch 8, wobei das Fließbett, das am Reaktorkopf verwendet wird, mit einer Fluidisierungsgeschwindigkeit im Bereich zwischen 2 und 10 Mal der Mindestfluidisierungsgeschwindigkeit betrieben wird.
EP05291650A 2004-09-15 2005-08-01 Wanderbettverfahren zur Produktion von Propylen mit Recycling von einer Fraktion des verwendeten Katalysators Expired - Fee Related EP1637575B1 (de)

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FR2905122B1 (fr) 2006-08-24 2009-07-24 Inst Francais Du Petrole Procede de production de propylene en presence d'un catalyseur macroporeux se presentant sous forme de billes spheriques
FR2932495B1 (fr) * 2008-06-17 2011-03-25 Inst Francais Du Petrole Dispositif de controle des conditions operatoires dans une unite de craquage catalytique a deux risers.
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WO2011019037A1 (ja) * 2009-08-11 2011-02-17 三菱化学株式会社 触媒の製造方法
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JP5030408B2 (ja) 2012-09-19
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US7566811B2 (en) 2009-07-28
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