EP1637575A1 - 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

Info

Publication number
EP1637575A1
EP1637575A1 EP05291650A EP05291650A EP1637575A1 EP 1637575 A1 EP1637575 A1 EP 1637575A1 EP 05291650 A EP05291650 A EP 05291650A EP 05291650 A EP05291650 A EP 05291650A EP 1637575 A1 EP1637575 A1 EP 1637575A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
reactor
oligocracking
fraction
moving bed
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP05291650A
Other languages
English (en)
French (fr)
Other versions
EP1637575B1 (de
Inventor
Sylvain Louret
Vincent Coupard
Patrice Font
Eric Sanchez
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
IFP Energies Nouvelles IFPEN
Original Assignee
IFP Energies Nouvelles IFPEN
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by IFP Energies Nouvelles IFPEN filed Critical IFP Energies Nouvelles IFPEN
Publication of EP1637575A1 publication Critical patent/EP1637575A1/de
Application granted granted Critical
Publication of EP1637575B1 publication Critical patent/EP1637575B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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 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 (Si / Al 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).
  • Figure 2 provides a 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% of MFI type zeolite having an Si / Al ratio of 75.
  • the catalyst is regenerated in a regeneration zone operating at a temperature of 823 K and at 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.
  • 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.
  • 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.
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP05291650A 2004-09-15 2005-08-01 Wanderbettverfahren zur Produktion von Propylen mit Recycling von einer Fraktion des verwendeten Katalysators Not-in-force EP1637575B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR0409795A FR2875234B1 (fr) 2004-09-15 2004-09-15 Procede de production de propylene fonctionnant en lit mobile avec recyclage d'une fraction de catalyseur use

Publications (2)

Publication Number Publication Date
EP1637575A1 true EP1637575A1 (de) 2006-03-22
EP1637575B1 EP1637575B1 (de) 2009-04-15

Family

ID=34948357

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05291650A Not-in-force EP1637575B1 (de) 2004-09-15 2005-08-01 Wanderbettverfahren zur Produktion von Propylen mit Recycling von einer Fraktion des verwendeten Katalysators

Country Status (5)

Country Link
US (1) US7566811B2 (de)
EP (1) EP1637575B1 (de)
JP (1) JP5030408B2 (de)
DE (1) DE602005013870D1 (de)
FR (1) FR2875234B1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1892229A1 (de) * 2006-08-24 2008-02-27 Ifp Verfahren zur Herstellung von Propylen in Gegenwart eines makroporösen Katalysators in Form von sphärischen Kügelchen
CN102285856A (zh) * 2010-06-18 2011-12-21 中国石油化工股份有限公司 增产丙烯和乙烯的方法

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2892126B1 (fr) * 2005-10-19 2010-04-30 Inst Francais Du Petrole Procede de conversion directe d'une charge comprenant des olefines a quatre, et/ou cinq atomes de carbone, pour la production de propylene avec une co-production d'essence desulfuree
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.
US8007728B2 (en) * 2008-12-11 2011-08-30 Uop Llc System, apparatus, and process for cracking a hydrocarbon feed
DE102009019436A1 (de) * 2009-04-29 2010-11-04 Bayer Materialscience Ag Verfahren zur Herstellung von aromatischen Aminen
DE102009031911B4 (de) * 2009-07-01 2013-02-21 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren und Reaktoranlage zur Reinigung eines Brenngases
WO2011019037A1 (ja) * 2009-08-11 2011-02-17 三菱化学株式会社 触媒の製造方法
US20120296138A1 (en) * 2011-05-22 2012-11-22 Fina Technology, Inc. Method for alkylation of toluene to form styrene and ethylbenzene utilizing a moving bed reactor
US8993824B2 (en) 2011-09-28 2015-03-31 Uop Llc Fluid catalytic cracking process
EP3620499A1 (de) * 2018-09-06 2020-03-11 INDIAN OIL CORPORATION Ltd. Verfahren zur selektiven herstellung von leichten olefinen und aromaten aus gecracktem leichtem naphtha
CN115364890B (zh) * 2022-08-29 2024-03-19 中国石油大学(北京) 一种负载型甲烷热催化裂解催化剂及其制备方法与应用

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3838039A (en) 1971-12-14 1974-09-24 Universal Oil Prod Co Continuous conversion and regeneration process
US5336829A (en) 1992-03-26 1994-08-09 Institut Francais Du Petrole Continuous process for the dehydrogenation of paraffinic to olefinic hydrocarbons
US5849976A (en) 1994-07-27 1998-12-15 Uop Llc Moving bed solid catalyst hydrocarbon alkylation process
EP0921179A1 (de) * 1997-12-05 1999-06-09 Fina Research S.A. Herstellung von Olefinen
US6284939B1 (en) 1998-07-31 2001-09-04 Institut Francais Du Petrole Process for liquid-phase conversion with a moving-bed catalyst using a stripper-lift
EP1195424A1 (de) 2000-10-05 2002-04-10 ATOFINA Research Verfahren zur Krackung von olefinreichen Kohlenwasserstoffeinsätzen
WO2003000399A2 (en) * 2001-06-22 2003-01-03 Uop Llc Reaction and regeneration system
EP1365004A1 (de) * 2002-05-23 2003-11-26 ATOFINA Research Verfahren zur Herstellung von Olefinen
US20030223918A1 (en) 2001-03-23 2003-12-04 Cammy Neal E. FCC process and apparatus with automatic catalyst recycle control

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61289049A (ja) * 1985-05-27 1986-12-19 Agency Of Ind Science & Technol プロピレンの製造方法
GB9026775D0 (en) * 1990-12-10 1991-01-30 Shell Int Research Process for the preparation of an olefins-containing mixture of hydrocarbons
EP0921181A1 (de) * 1997-12-05 1999-06-09 Fina Research S.A. Herstellung von Propen
GB2345294B (en) * 1998-08-25 2002-10-23 Asahi Chemical Ind Method for producing ethylene and propylene
IT1318527B1 (it) * 2000-05-19 2003-08-27 Enichem Spa Procedimento per la produzione di propilene da correnti olefiniche.
US7371911B2 (en) 2005-02-25 2008-05-13 Fina Technology, Inc. Critical phase alkylation and transalkylation process in the presence of a beta zeolite

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3838039A (en) 1971-12-14 1974-09-24 Universal Oil Prod Co Continuous conversion and regeneration process
US5336829A (en) 1992-03-26 1994-08-09 Institut Francais Du Petrole Continuous process for the dehydrogenation of paraffinic to olefinic hydrocarbons
US5849976A (en) 1994-07-27 1998-12-15 Uop Llc Moving bed solid catalyst hydrocarbon alkylation process
EP0921179A1 (de) * 1997-12-05 1999-06-09 Fina Research S.A. Herstellung von Olefinen
US6284939B1 (en) 1998-07-31 2001-09-04 Institut Francais Du Petrole Process for liquid-phase conversion with a moving-bed catalyst using a stripper-lift
EP1195424A1 (de) 2000-10-05 2002-04-10 ATOFINA Research Verfahren zur Krackung von olefinreichen Kohlenwasserstoffeinsätzen
US20030223918A1 (en) 2001-03-23 2003-12-04 Cammy Neal E. FCC process and apparatus with automatic catalyst recycle control
WO2003000399A2 (en) * 2001-06-22 2003-01-03 Uop Llc Reaction and regeneration system
EP1365004A1 (de) * 2002-05-23 2003-11-26 ATOFINA Research Verfahren zur Herstellung von Olefinen

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1892229A1 (de) * 2006-08-24 2008-02-27 Ifp Verfahren zur Herstellung von Propylen in Gegenwart eines makroporösen Katalysators in Form von sphärischen Kügelchen
FR2905122A1 (fr) * 2006-08-24 2008-02-29 Inst Francais Du Petrole Procede de production de propylene en presence d'un catalyseur macroporeux se presentant sous forme de billes spheriques
US7880048B2 (en) 2006-08-24 2011-02-01 Ifp Process for producing propylene in the presence of a macroporous catalyst in the form of spherical beads
CN102285856A (zh) * 2010-06-18 2011-12-21 中国石油化工股份有限公司 增产丙烯和乙烯的方法

Also Published As

Publication number Publication date
US7566811B2 (en) 2009-07-28
US20060063957A1 (en) 2006-03-23
EP1637575B1 (de) 2009-04-15
DE602005013870D1 (de) 2009-05-28
JP5030408B2 (ja) 2012-09-19
FR2875234A1 (fr) 2006-03-17
JP2006083173A (ja) 2006-03-30
FR2875234B1 (fr) 2006-11-03

Similar Documents

Publication Publication Date Title
EP1637575B1 (de) Wanderbettverfahren zur Produktion von Propylen mit Recycling von einer Fraktion des verwendeten Katalysators
JP5436209B2 (ja) 転換増強方法及び生成物流を生産する生産方法
EP1661617B1 (de) Festbett- oder Wanderbettreaktor mit mehreren Zonen und integriertem Wärmetauscher
EP1814654B1 (de) Reaktionsgerät mit einigen wirbelbettzonen mit versorgung in jeder regenerierten oder neuen katalysatorzone
EP1487768B1 (de) Mehrstufenverfahren zur umsetzung einer beschickung, die olefine mit drei, vier oder mehr kohlenstoffatomen enthält, zur herstellung von propylen
EP1800742B1 (de) Reaktor mit zwei fluidisierbaren Reaktionsstufen und einem integrierten Gas/Feststofftrennsystem
RU2580829C2 (ru) Способ и устройство каталитического крекинга для получения пропилена
WO2006067305A1 (fr) Procede de conversion directe d’une charge comprenant des olefines a quatre et/ou cinq atomes de carbone, pour la production de propylene avec une co-production d’essence
EP1668094B1 (de) Verfahren zur direktumwandlung eines olefine mit mindestens vier oder fünf kohlenstoffatomen enthaltenden einsatzstoffs zur herstellung von propylen
EP0489726B1 (de) Verfahren und einrichtung zum dampfkracken von kohlenwasserstoffen in der wirbelschichtphase
JPH03197591A (ja) 炭化水素の接触分解方法
FR2659346A1 (fr) Procede de craquage avec oligomerisation ou trimerisation des olefines presentes dans les effluents.
KR20210006415A (ko) 다단계 촉매 반응 및 재생성을 이용한 최대 올레핀 생산
CN1912059A (zh) 一种多产丙烯的催化转化方法
FR3053355B1 (fr) Procede d'oligomerisation utilisant un catalyseur zeolithique et un catalyseur comprenant une silice alumine
JP2002241764A (ja) 重質油の流動接触分解法
RU2823585C2 (ru) Преобразование сырой нефти в псевдоожиженном слое, содержащем зоны с разным временем контакта
FR2770225A1 (fr) Procede et dispositif de vaporisation selective des charges d'hydrocarbures en craquage catalytique
RU2799345C2 (ru) Максимальное производство олефинов с применением многоступенчатой реакции в присутствии катализатора и его регенерации
EP0323784B1 (de) Anwendung eines einen Zeoliten aus der Erionitfamilie enthaltenden Katalysators in einem Krackverfahren, das zumindest eine Regenerationszone enthält
US20240150663A1 (en) Processes for producing petrochemical products from crude oil
RU2262527C1 (ru) Способ каталитического крекинга тяжелых нефтяных фракций
FR2868788A1 (fr) Procede de conversion d'une alimentation d'hydrocarbures
FR2621322A1 (fr) Procede de vaporisation d'une charge liquide dans un procede de craquage catalytique en lit fluide
FR3090683A1 (fr) Conversion d’un brut pétrolier en lit fluidisé compartimenté

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

17P Request for examination filed

Effective date: 20060922

AKX Designation fees paid

Designated state(s): BE DE GB NL

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE GB NL

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REF Corresponds to:

Ref document number: 602005013870

Country of ref document: DE

Date of ref document: 20090528

Kind code of ref document: P

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20100118

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602005013870

Country of ref document: DE

Owner name: IFP ENERGIES NOUVELLES, FR

Free format text: FORMER OWNER: INSTITUT FRANCAIS DU PETROLE, RUEIL-MALMAISON, HAUTS-DE-SEINE, FR

Effective date: 20110331

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20200827

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20200825

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20200825

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20201029

Year of fee payment: 16

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602005013870

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20210901

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20210831

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20210801

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210901

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210801

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220301

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210831