WO2006067305A1 - 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 - Google Patents
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 Download PDFInfo
- Publication number
- WO2006067305A1 WO2006067305A1 PCT/FR2005/003141 FR2005003141W WO2006067305A1 WO 2006067305 A1 WO2006067305 A1 WO 2006067305A1 FR 2005003141 W FR2005003141 W FR 2005003141W WO 2006067305 A1 WO2006067305 A1 WO 2006067305A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- unit
- oligocracking
- cut
- catalyst
- effluent
- Prior art date
Links
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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
- C10G69/126—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step polymerisation, e.g. oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/10—Catalytic processes with metal oxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- 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
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
-
- 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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
-
- 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
- C10G2400/02—Gasoline
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the invention relates to a process for converting at least a part of propylene a hydrocarbon feed comprising olefins whose carbon number is mainly equal to 4 or 5, this cut - which will be called in the following text cut C4 / C5- most often from an FCC unit or a steam cracking unit.
- FCC refers to the process of fluidized catalytic cracking of petroleum fractions having a boiling point greater than about 350 ° C, for example a vacuum distillate, optionally deasphalted oil or an atmospheric residue.
- the feedstock of the process according to the invention may also comprise C4 / C5 or larger fractions from a chamber or fluidized bed coking unit, a visbreaking unit or a Fischer-Synthesis unit. Tropsch.
- the feed may also include fractions of a steam cracking gasoline.
- the feedstock of the process according to the present invention is therefore an olefinic C4 / C5 cut, that is to say typically a light olefinic feed, containing predominantly (that is to say for more than 50%) of preferably at least 60%) of the C4 and / or C5 olefins, whose end point of distillation is generally less than 320 ° C., most often less than 250 ° C.
- the olefinic feedstock of the present invention also comprises highly unsaturated compounds, such as dienes (diolefins), especially with 4 or 5 carbon atoms (in particular butadiene) and small amounts of acetylenic compounds having 2 to 10 carbon atoms.
- French patent FR-B-2 608 595 describes the metathesis process which converts into propylene an ethylene + n-butene mixture.
- the method according to the invention does not use metathesis, which avoids the use of other olefins than those of C4 and C5 (such as ethylene) in large quantities, such olefins can obviously be found as impurities. It does not require massive consumption of ethylene, a product of high cost.
- the process according to the invention makes it possible not only not to use ethylene as a filler, but also to co-produce ethylene with propylene. Since the co-production of ethylene is typically lower than that of propylene, this increases the propylene to ethylene ratio of the steam cracker, which is in line with market trends.
- the process described in the international application WO-A-01/04237 is another process for the production of propylene in one step from light olefins which can be considered as a variant of the FCC process using a catalyst comprising a zeolite ZSM- 5.
- a disadvantage of this process is that fluidized bed technology is expensive from an investment point of view and requires a relatively tricky process operation. In addition, it leads to significant losses of catalyst attrition.
- the process according to the invention has turned to another type of process and does not use the FCC.
- the catalyst used comprises an MFI-type zeolite whose Si / Al ratio (Silicon / Aluminum atomic ratio) is greater than or equal to 180, preferably a ZSM-5 zeolite with an Si / Al ratio of between 300 and 1000.
- US-A-6,049,017 which can be considered as the closest prior art, describes a process for producing ethylene and propylene from an olefinic cut comprising the following succession of steps: a) a separation of ethylene, propylene and diolefins (for example by selective hydrogenation); b) a separation of the n-olefins and iso-olefins by conversion of the iso-olefins using an oxidizing agent and an acid catalyst to form oxygenated compounds (for example by etherification); (c) a separation of oxygenates and d) a cracking of n-olefins using a small pore catalyst (for example zeolitic or preferably non-zeolitic containing SAPO) to obtain ethylene and propylene.
- a small pore catalyst for example zeolitic or preferably non-zeolitic containing SAPO
- the present invention also uses a unit for separating n-olefins and iso-olefins, but on a unit which does not use any oxidizing agent.
- the disadvantage of such an agent methanol, ethanol is that it requires a separation unit (distillation, washing with water, etc.) and poses problems of pollution or even toxicity with regard to methanol. .
- the process according to the present invention leads to the formation of propylene, but also additional quantity of gasoline of excellent quality.
- the present invention relates to a process for converting an olefinic C4 / C5 cut to propylene and gasoline, comprising the following sequence of steps:
- step (2) selective oligomerization of iso-olefins of at least a portion of the effluent from step (1), followed by distillation, so as to obtain a gasoline fraction and at least one remaining cut containing less than 10 % weight of isobutenes, and
- step 3 oligocracking the n-olefins, operating in one step, on at least part of the remaining cut of step (2), on a catalyst comprising at least one zeolite having a shape selectivity and an Si / Al atomic ratio from 50 to 500, followed by separation to obtain a gasoline fraction, propylene and a residual C4 / C5 cut.
- the C4 and C5 olefinic feedstock is generally derived from a steam cracking or catalytic cracking unit (FCC).
- FCC catalytic cracking unit
- the aromatic-rich gasoline fraction resulting from the oligocracking step may advantageously be at least partially mixed with the gasoline cut from selective oligomerization to form a gasoline having an RON octane number of at least 94.
- the process according to the invention ultimately makes it possible to obtain a propylene yield of at least 19%, preferably greater than 22%.
- the invention also relates to an installation which comprises: a selective hydrogenation unit containing at least one catalyst comprising at least one metal selected from the group formed by Ni, Pd and Pt, deposited on a non-acid refractory oxide support, the unit being provided with conduits for the entry of the C4 / C5 olefinic cut to be treated and hydrogen and for the outlet of the effluent; a selective oligomerization unit of the iso-olefins, comprising successively a drying unit, a desulfurization unit and a reaction unit containing at least one selective oligomerization acid catalyst, the unit being provided with conduits for the passage of effluents between said successive units, for the entry of at least a portion of the effluent from the hydrogenation unit and for the outlet of the effluent;
- a distillation column separating a gasoline fraction and at least one remaining cut
- the hydrogenation unit comprises a fixed-bed reactor with a downward flow of the feedstock, a pipe bringing the effluent obtained into a second fixed-bed reactor at the upward co-current of said effluent and hydrogen.
- the plant further comprises an aromatics extraction unit provided with a pipe for the entry of the oligocracking effluent and an outlet pipe for the deflavored gasoline.
- FIG 1 shows the diagram of the method and the installation according to the invention which will allow an easier understanding of the detailed description which follows.
- the feed to be treated (1) is introduced into a selective hydrogenation unit (a) and produces an effluent (2).
- a charge of another origin (2 1 ) may be added to this effluent (2) provided that the unsaturated content of said feedstock (2 1 ) is between 10 ppm and 1000 ppm, preferably between 50 ppm and 300 ppm. .
- (2 ') may be an FCC gasoline that does not need to be hydrotreated.
- a lighter hydrocarbon cut (4) mostly consisting of C4 and C5 fractions and
- an oligomer (3) mainly consisting of C8 olefins and may contain a certain proportion of compounds up to C16.
- the C4 / C5 cut corresponding to the flow (4) is sent in admixture with the recycle stream (5), after purging, to the oligocracking unit (c).
- the oligocracking unit (c) produces, after separation in a distillation column (d 1 ):
- a light cut (7) rich in ethylene an effluent (6) rich in propylene
- the recycle (8) from the distillation column (d ') constitutes a stream (5 1 ) which is sent to the inlet of the selective oligomerization unit (b) .
- a variant in which part of the fraction (8) would be recycled by the flow (5) at the inlet of the oligocracking unit and another part would be recycled by the flow (5 1 ) to the The entry of the oligomerization unit remains perfectly within the scope of the invention.
- the crude feedstock from a steam cracker or FCC generally contains diene compounds (diolefins), which are poisons with respect to the catalysts used in the oligomerization and oligocracking units.
- the filler is treated by selective hydrogenation to reduce the impurity content.
- this step of selective hydrogenation of the dienes and acetylenic mono-olefins is mandatory.
- This selective hydrogenation can either treat the raw steam cracker cut or the C4 cut after it has been previously treated in a unit for extracting diolefin type compounds by absorption in a solvent.
- This type of butadiene extraction process is known to those skilled in the art.
- the selective hydrogenation step is optional, but it facilitates the implementation of the downstream process.
- step (1) a C4 / C5 olefinic steam-cracking cut is processed and in step (2) at least part of the effluent from step (1) and a C4 / C5 olefinic catalytic cracking cut.
- the main purpose of this first step of selective hydrogenation is to convert the diolefins (or dienes) to mono-olefins. Indeed, only the mono-olefins can be converted into propylene according to the process of the invention. It is therefore important to maximize the mono-olefin content in the feed to be treated.
- Another objective of this first step is to purify the charge of the other impurities present, in particular the acetylenic compounds, which are poisons with respect to the catalysts used in the downstream stages.
- the transformation is carried out using two reactors in series, with optional recycling of a fraction of the effluent at the inlet of the selective hydrogenation unit. This recycling also helps to control global warming of the reaction.
- the unsaturated content of the effluent at the end of the selective hydrogenation stage is at most 1000 ppm, preferably at most 300 ppm, often between 10 ppm and 1000 ppm. preferably between 50 ppm and 300 ppm.
- the catalysts used in this selective hydrogenation step generally consist of a Group VIII metal (typically Ni Pd) deposited on a non-acid alumina or refractory oxide support. Indeed, the external acid surface should not be too important to limit the polymerization reactions on the surface of the catalyst.
- the preferred support is alumina.
- the metal content preferentially palladium, must be between 0.1% and 5% by weight and preferably between 0.2% and 0.6% by weight.
- nickel When nickel is used as the metal, its content is between 5% and 25% by weight, preferably between 7% and 20% by weight.
- the operating conditions are chosen so that the effluent remains in the liquid state, ie typically from 20 ° C. to 150 ° C., at pressures ranging from 5 bars to 40 bars.
- the amount of catalyst used for the reaction is typically between about 2 m ⁇ and about 8 m ⁇ of catalyst per m3 of fresh feed being treated.
- Hydrogen is generally introduced at a level of from 5% to 30% by mole above stoichiometry and preferably from 10% to 20% above the stoichiometric amount.
- the reaction is conducted in a generally downflow fixed bed reactor for the main reaction, (this is the case when there is more than 1.5% by weight of diolefins present in the effluent to be converted) and with a preferably a catalyst consisting of Pd deposited on alumina, generally in ascending cocurrent with hydrogen for the finishing phase of the reaction, preferably with a catalyst consisting of Pd / Ag deposited on alumina.
- This arrangement has the advantage of increasing the conversion.
- the second step of the process according to the invention consists in a selective oligomerization of the iso-olefins (isobutene, isopentene) of all the effluent from the first step, taking place in two phases.
- the selective oligomerization of isobutene is described in detail in patent FR-B-2 492 365.
- the first phase of the selective oligomerization consists of drying and desulphurizing the feedstock.
- Both drying and desulfurization functions are performed within the same reactor and use sieves. These sieves generally consist of a series of zeolites having different pore size (zeolites 3A, 4A, 5A, 13X) or optionally activated alumina. The sieves used to carry out the drying and the desulfurization are generally carried out according to an alternating reaction-regeneration cycle.
- the drying and desulfurization phase is generally carried out in the liquid phase, at a temperature close to ambient (20 ° C. to 70 ° C.), at low pressures of between 1 bar and 15 bars.
- the regeneration phase consists in sending to the reactor a dry and hot gas, for example nitrogen, at a temperature of between 20 ° C. and 400 ° C.
- a dry and hot gas for example nitrogen
- the second phase of the oligomerization step consists of a selective oligomerization of iso-olefins (isobutenes, isopentenes).
- the selectivity of the operation consists precisely in oligomerizing the isobuthes without oligomerizing the n-olefins (n-butenes, n-pentenes).
- the catalyst used in this step is an acid catalyst, for example a silica-alumina type catalyst, a resin or a solid phosphoric acid type catalyst.
- the catalyst used in this step is a silica alumina type catalyst as described in patent FR-B-2 463 802, the silica content of which is between 60 and 95% by weight, preferably between 70 and 90%. % by weight, and having as an additive between 0.1 and 5% by weight of zinc oxide.
- the 100% complement is usually alumina.
- the operating conditions are generally (and in particular in the case of the catalyst above):
- the selective oligomerization step is generally carried out in a series of N fixed bed reactors, each of which is followed by a cooler.
- the number N is chosen according to the targeted n-butene selectivity. It is typically from 2 to 4. External recycling at the inlet of these N reactors is optionally used to maintain a constant isobutene level at the inlet of the process. This recycling consists either of the effluent taken directly at the outlet of the reactor, or of the oligomerate recovered at the bottom of the distillation column.
- the temperature of each of the chillers N is adjusted during the operation to compensate for the loss of activity of the catalyst system used.
- a separation by distillation is carried out in order to separate a gasoline fraction essentially comprising hydrocarbons ranging from C6 to C16, often predominantly composed of C8 hydrocarbons, and thus comprising C6-C16 or C8 oligomers.
- -C16 for example, and recovering one or more C4 and C5 cuts remaining essentially comprising paraffins and n-olefins and C5 iso-olefins.
- This remaining C4 / C5 cut typically contains from 20% to 80% by weight of olefins, predominantly light olefins of 4 and / or 5 carbon atoms.
- the remainder of the cut consists of isoolefins, essentially C5 isoolefins, and paraffins.
- the content of iso-olefins C4 is generally less than 10% by weight.
- At least one C4 / C5 cut produced at the end of the selective oligomerization step (and preferably all the remaining cut) is sent to a catalytic oligocracker unit operating in one step.
- the catalyst used in the one-step oligocracking unit comprises at least one zeolite having a shape selectivity, this zeolite having an Si / Al atomic ratio of between 50 and 500, preferably between 60 and 160, and even better between 75 and 150.
- the zeolite having a shape selectivity may belong to a first group consisting of one of the following structural types: MEL, MFI, NES, EUO, FER, CHA, MFS and MWW.
- MFI such as ZSM-5
- MEL t ⁇ 1 q ⁇ i ⁇ ZSM-11
- the shape-selective zeolite may also belong to a second group consisting of the following zeolites: NU-85, NU-86, NU-88 and IM-5.
- ZSM-5 commercial zeolites can be used:
- CBV 28014 Si / Al ratio: 140
- CBV 1502 Si / Al: 75 atomic ratio
- the zeolite or zeolites may be dispersed in a matrix based on silica, zirconia, alumina or silica-alumina, the proportion of zeolite often being between 15% and 90% by weight, preferably between 30% and 80%. weight.
- Si / Al atomic ratios included in the preferred range within the scope of the invention can be obtained at the time of manufacture of the zeolite or by subsequent dealumination.
- the preferred catalysts are those consisting of zeolite and matrix.
- the catalyst is generally used in a moving bed, preferably in the form of balls of diameter generally between 1 mm and 3 mm.
- the catalyst can also be used in the fixed bed state, in which case the reactor or reactors used work alternately in reaction, then in regeneration according to the well known technique called "swing".
- the regeneration phase typically comprises a combustion phase of the carbonaceous deposits formed on the catalyst, for example using an air / nitrogen mixture, oxygen depleted air (for example by flue gas recirculation) or simply by air.
- the regeneration may optionally comprise other phases of catalyst treatment and regeneration which will not be developed here not being a characteristic aspect of the invention.
- the catalytic oligocracking unit is usually carried out in one step at a temperature of about 450 ° C. to about 580 ° C., with a space velocity generally ranging from 0.5 to 6 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 effluent produced by the oligocracking is distilled to separate the propylene and the gasoline fraction; a residual C4 / C5 fraction is also obtained. Propylene is therefore separated directly by distillation from the effluent.
- a distillation column called superfractionation column, may be added to treat the distilled propylene.
- the yield per propylene pass relative to the amount of olefins contained in the fresh batch of the process is greater than 19%, preferably greater than 22% by weight.
- the residual C4-C5 fraction may advantageously be recycled at least partly to the inlet of the oligocracking unit, and / or to the inlet of the selective oligomerization unit. Preferably, it is recycled at least in the oligocracking step.
- the rate of recycling of said C4 / C5 cut based on the feed rate entering the selective oligomerization unit may advantageously vary in a ratio of 1 to 5 and preferably of 3 to 5.
- the distribution of the recycle flow of the C4 / C5 cut from the oligocracking unit to, on the one hand, the oligocracking unit and, on the other hand, the selective oligomerization unit, is made according to the wishes of the operator.
- the entire recycle flow rate may be sent to the input of the selective oligomerization unit, and in other cases, the entire recycle flow rate may be sent to the recycling unit. entry of the oligocracking unit.
- the gasoline fraction produced by the one-step oligocracking unit is an aromatic gasoline which can be mixed in whole or in part with the olefin gasoline fraction produced by the selective oligomerization unit (rich in multi-branched olefins), advantageously to form a gasoline of octane number at least equal to 94 of RON, or to be sent partly or wholly to an aromatics extraction complex to preferably be subsequently mixed with the gasoline pool.
- the charge (1) is a C4 crude steam cracking cut.
- the charge (2 1 ) is a crude C4 cut of FCC.
- the selective hydrogenation unit uses two reactors:
- the first reactor uses a Pd / Al 2 O 3 catalyst at 0.3 wt% Pd, on an alumina of 69 m 2 / g surface area. It operates at 50 ° C. in an adiabatic manner in a descending through bed at 30 bars absolute. In order for the reaction to remain in the liquid phase, a recycling equal to 20 times the mass flow rate of charge is used.
- the overall H2 / butadiene ratio is 1.05 mol / mol.
- the second reactor called “finishing reactor” is an upflow reactor, using a Pd + Ag catalyst deposited on alumina, it is 0.2% by weight of Pd, and 0.1% of Ag deposited on an alumina of 69 m ⁇ / g of BET surface.
- the temperature is set at 35 ° C, the pressure at 26 bar.
- the raw load of the FCC and the charge from the selective hydrogenation are mixed.
- the resulting mixture is dried and desulfurized on 3A and 13X molecular sieves, sold by Axens.
- the mixture thus treated is sent to the selective oligomerization unit of isobutenes.
- This unit operates at an overall VVH of 1, on a catalyst consisting of 90% silica and 10% alumina at a temperature of between 30 ° C. and 50 ° C. pressure of 20 bar.
- a distillation column (d) separates a C4 / C5 rich cut from a gasoline cut rich in C8 - C16 oligomers.
- a fraction of the C4 / C5 cut (recycling rate of 1 ton / ton treated, ie 50% by weight) is used as thermal diluent.
- the oligocracking is carried out in a reactor operating at 2.8 bar absolute, at 510 ° C., with a PPH of 3.5 h -1 relative to the feedstock entering the reactor.
- a single adiabatic downflow gas phase reactor is used.
- the cycle time between two successive regenerations is 48 h.
- the catalyst used is composed of 30% ZSM-5 zeolite with a Si / Al atomic ratio of 140 and 70% gamma alumina. It is prepared in the form of beads 3 mm in diameter shaped by the technique of "oil drop" and it flows in a moving bed.
- the C4 cut from the oligocracking unit is recycled in the oligocracking process, according to the material balance of Table 1.
- the gasoline cut from the oligomerization unit has an RON of 96.5 and a MON of 84.
- the petrol cut from the oligocracker unit has a RON of 96.5 and a MY of 88.5.
- the mixture of these two species leads to an essence of RON equal to 96.5 and a MON of 85.
- the yield of the C3 cut is 19%. This C3 cut contains 95% propylene.
- the overall efficiency of the petrol cut is 43%.
- the charge (1) is a C4 crude steam cracking cut.
- the load (2 1 ) is a crude C4 cut of FCC.
- the RON of the oligomer is always 96.5.
- the overall C3 cut yield is 22%.
- the overall efficiency of the petrol cut is 38%.
- Example 3 The data of Example 3 are the same as those of Example 1 except for the following:
- the charge (1) is a crude C4 cut of steam cracking.
- the load (2 1 ) is a crude C4 cut of FCC.
- Recycling (5 ') is returned to the selective oligomerization unit.
- the overall C3 cut yield is 22%.
- the degree of conversion of C4 olefins in C3 section is 47%.
- Example 4 The data of Example 4 are the same as those of Example 1 except for the following:
- the charge (1) is a C4 crude steam cracking cut.
- the feedstock (2 1 ) is a mixture of a crude C4 cut of FCC, a crude C5 cut of FCC and a C5 cut of steam cracking which has been further treated to remove dienes similar to that described for cutting C4.
- the cycle time of the oligocracking unit is 48 h. This recycling (5) now concerns a fraction of the C4 and C5 cuts as defined in the material balance of Table 4.
- the cycle time of the oligocracking unit is 48 h.
- the overall C3 cut yield is 28%.
- the degree of conversion of olefins C4-C5 in C3 section is 42%.
- the RON of the oligomerate increases to 94.5 and the MON to 82.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0713207A GB2437203B (en) | 2004-12-21 | 2005-12-13 | Method for direct conversion of a feedstock comprising C4/C5 olefins for producing propylene with co-production of gasoline |
JP2007547561A JP5140819B2 (ja) | 2004-12-21 | 2005-12-13 | ガソリンの共製造を伴ってプロピレンを製造するための、4個および/または5個の炭素原子を有するオレフィンを含む装入原料の直接転化方法 |
US11/722,300 US9193922B2 (en) | 2004-12-21 | 2005-12-13 | Process of direct conversion of a charge comprising olefins with four and/or five carbon atoms, for the production of propylene with co-production of gasoline |
DE112005003177.2T DE112005003177B4 (de) | 2004-12-21 | 2005-12-13 | Verfahren zur direkten Umwandlung einer Beschickung, die Olefine mit vier und/oder fünf Kohlenstoffatomen umfasst, zur Produktion von Propylen mit einer Koproduktion von Benzin |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0413680 | 2004-12-21 | ||
FR0413680A FR2879620B1 (fr) | 2004-12-21 | 2004-12-21 | 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 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006067305A1 true WO2006067305A1 (fr) | 2006-06-29 |
Family
ID=34953596
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2005/003141 WO2006067305A1 (fr) | 2004-12-21 | 2005-12-13 | 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 |
Country Status (7)
Country | Link |
---|---|
US (1) | US9193922B2 (fr) |
JP (1) | JP5140819B2 (fr) |
CN (2) | CN103333714A (fr) |
DE (1) | DE112005003177B4 (fr) |
FR (1) | FR2879620B1 (fr) |
GB (1) | GB2437203B (fr) |
WO (1) | WO2006067305A1 (fr) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008081437A (ja) * | 2006-09-27 | 2008-04-10 | Mitsubishi Chemicals Corp | プロピレンの製造方法 |
EP2404980A1 (fr) | 2010-07-08 | 2012-01-11 | Total Raffinage Marketing | Augmentation de la masse moléculaire moyenne de produits de départ d'hydrocarbure |
WO2012089716A1 (fr) | 2010-12-28 | 2012-07-05 | Total Raffinage Marketing | Charge d'hydrocarbures contenant des nitriles, son procédé de fabrication et son utilisation |
WO2013104614A1 (fr) | 2012-01-09 | 2013-07-18 | Total Raffinage Marketing | Procédé pour la conversion d'une charge de départ d'hydrocarbures contenant des oléfines de faible point d'ébullition |
EP2636661A1 (fr) * | 2012-02-15 | 2013-09-11 | IFP Energies nouvelles | Procédé de conversion d'une charge lourde, mettant en oeuvre une unité de craquage catalytique et une étape d'hydrogénation sélective de l'essence issue du craquage catalytique |
Families Citing this family (27)
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 |
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 |
FR2942796B1 (fr) * | 2009-03-09 | 2011-05-27 | 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 |
CN102517073B (zh) * | 2011-12-09 | 2014-07-23 | 大庆华科股份有限公司 | 一种裂解碳五分离工艺中采用精馏和加氢耦合脱除碳四的方法 |
FR2984916B1 (fr) * | 2011-12-23 | 2014-01-17 | IFP Energies Nouvelles | Procede ameliore de conversion d'une charge lourde en distillat moyen faisant appel a un pretraitement en amont de l'unite de craquage catalytique |
US9434891B2 (en) | 2012-11-12 | 2016-09-06 | Uop Llc | Apparatus for recovering oligomerate |
US9914673B2 (en) | 2012-11-12 | 2018-03-13 | Uop Llc | Process for oligomerizing light olefins |
US10508064B2 (en) * | 2012-11-12 | 2019-12-17 | Uop Llc | Process for oligomerizing gasoline without further upgrading |
US9567267B2 (en) | 2012-11-12 | 2017-02-14 | Uop Llc | Process for oligomerizing light olefins including pentenes |
US9522373B2 (en) | 2012-11-12 | 2016-12-20 | Uop Llc | Apparatus for oligomerizing light olefins |
US9441173B2 (en) | 2012-11-12 | 2016-09-13 | Uop Llc | Process for making diesel by oligomerization |
US9644159B2 (en) | 2012-11-12 | 2017-05-09 | Uop Llc | Composition of oligomerate |
US9663415B2 (en) | 2012-11-12 | 2017-05-30 | Uop Llc | Process for making diesel by oligomerization of gasoline |
US9522375B2 (en) | 2012-11-12 | 2016-12-20 | Uop Llc | Apparatus for fluid catalytic cracking oligomerate |
US9278893B2 (en) | 2012-11-12 | 2016-03-08 | Uop Llc | Process for making gasoline by oligomerization |
US9834492B2 (en) * | 2012-11-12 | 2017-12-05 | Uop Llc | Process for fluid catalytic cracking oligomerate |
US9670425B2 (en) | 2013-12-17 | 2017-06-06 | Uop Llc | Process for oligomerizing and cracking to make propylene and aromatics |
US9732285B2 (en) | 2013-12-17 | 2017-08-15 | Uop Llc | Process for oligomerization of gasoline to make diesel |
JP2015218312A (ja) * | 2014-05-20 | 2015-12-07 | Jx日鉱日石エネルギー株式会社 | オレフィンを含む炭化水素混合物の脱硫方法 |
US10544068B2 (en) | 2016-08-16 | 2020-01-28 | Iran Polymer And Petrochemical Institute | Catalytic process for producing olefins |
US10745328B2 (en) * | 2018-03-27 | 2020-08-18 | Phillips 66 Company | Catalytic activation and oligomerization of isopentane-enriched mixtures |
US10815438B2 (en) * | 2018-03-27 | 2020-10-27 | Phillips 66 Company | Catalytic activation and alkylation of isopentane-enriched mixtures |
US10774017B2 (en) * | 2018-03-27 | 2020-09-15 | Phillips 66 Company | Catalytic activation of isopentane-enriched mixtures |
CN112703176B (zh) | 2018-09-20 | 2023-12-19 | 沙特基础工业全球技术公司 | 使用混合c4链烷烃进料生产轻质烯烃(乙烯+丙烯)和btx的方法 |
CN111718753B (zh) | 2019-03-22 | 2021-10-08 | 中国石油化工股份有限公司 | 一种多产丙烯的催化转化方法和系统 |
US10865168B2 (en) * | 2019-04-24 | 2020-12-15 | Phillips 66 Company | Isomerization, catalytic activation and oligomerization of pentane-enriched hydrocarbon mixtures |
US10870808B2 (en) * | 2019-04-24 | 2020-12-22 | Phillips 66 Company | Isomerization and catalytic activation of pentane-enriched hydrocarbon mixtures |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2492365A1 (fr) * | 1980-10-16 | 1982-04-23 | Inst Francais Du Petrole | Procede de valorisation des coupes c4 olefiniques |
EP0109059A1 (fr) * | 1982-11-10 | 1984-05-23 | MONTEDIPE S.p.A. | Procédé pour convertir des oléfines ayant de 4 à 12 atomes de carbone en propène |
US6049017A (en) * | 1998-04-13 | 2000-04-11 | Uop Llc | Enhanced light olefin production |
FR2837199A1 (fr) * | 2002-03-15 | 2003-09-19 | Inst Francais Du Petrole | Procede de conversion en plusieurs etapes d'une charge comprenant des olefines a quatre, cinq atomes de carbone ou plus, en vue de produire du propylene |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2603895B1 (fr) * | 1986-09-15 | 1989-09-01 | Inst Francais Du Petrole | Procede d'obtention de supercarburant a partir des butanes et/ou des coupes a quatre atomes de carbone issus d'un craquage ou d'un reformage catalytique |
US4795844A (en) * | 1987-07-20 | 1989-01-03 | Uop Inc. | Process for conversion of light olefins to LPG and aromatics |
FR2755958B1 (fr) * | 1996-11-19 | 1999-01-08 | Inst Francais Du Petrole | Zeolithe nu-86 desaluminee et son utilisation en conversion des hydrocarbures |
IT1318527B1 (it) * | 2000-05-19 | 2003-08-27 | Enichem Spa | Procedimento per la produzione di propilene da correnti olefiniche. |
FR2810991B1 (fr) * | 2000-06-28 | 2004-07-09 | Inst Francais Du Petrole | Procede pour l'hydrogenation de coupes contenant des hydrocarbures et notamment des molecules insaturees contenant au moins deux doubles liaisons ou au moins une triple liaison |
EP1195424A1 (fr) * | 2000-10-05 | 2002-04-10 | ATOFINA Research | Procédé pour le craquage de charges hydrocarbonées riches en oléfines |
EP1388528B1 (fr) * | 2002-08-06 | 2015-04-08 | Evonik Degussa GmbH | Procédé pour l'oligomérisation d'isobutène contenu dans des courants d'hydrocarbures contenant du n-butène |
US6867341B1 (en) | 2002-09-17 | 2005-03-15 | Uop Llc | Catalytic naphtha cracking catalyst and process |
FR2859994B1 (fr) * | 2003-09-19 | 2005-10-28 | Inst Francais Du Petrole | Procede de conversion directe d'une charge comprenant des olefines a quatre, et/ou cinq atomes de carbone ou plus, pour la production de propylene |
-
2004
- 2004-12-21 FR FR0413680A patent/FR2879620B1/fr active Active
-
2005
- 2005-12-13 US US11/722,300 patent/US9193922B2/en active Active
- 2005-12-13 CN CN2013102381291A patent/CN103333714A/zh active Pending
- 2005-12-13 JP JP2007547561A patent/JP5140819B2/ja active Active
- 2005-12-13 GB GB0713207A patent/GB2437203B/en active Active
- 2005-12-13 DE DE112005003177.2T patent/DE112005003177B4/de active Active
- 2005-12-13 WO PCT/FR2005/003141 patent/WO2006067305A1/fr active Application Filing
- 2005-12-13 CN CNA2005800437597A patent/CN101084291A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2492365A1 (fr) * | 1980-10-16 | 1982-04-23 | Inst Francais Du Petrole | Procede de valorisation des coupes c4 olefiniques |
US4392002A (en) * | 1980-10-16 | 1983-07-05 | Institut Francais Du Petrole | Process for upgrading olefinic C4 cuts |
EP0109059A1 (fr) * | 1982-11-10 | 1984-05-23 | MONTEDIPE S.p.A. | Procédé pour convertir des oléfines ayant de 4 à 12 atomes de carbone en propène |
US6049017A (en) * | 1998-04-13 | 2000-04-11 | Uop Llc | Enhanced light olefin production |
FR2837199A1 (fr) * | 2002-03-15 | 2003-09-19 | Inst Francais Du Petrole | Procede de conversion en plusieurs etapes d'une charge comprenant des olefines a quatre, cinq atomes de carbone ou plus, en vue de produire du propylene |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008081437A (ja) * | 2006-09-27 | 2008-04-10 | Mitsubishi Chemicals Corp | プロピレンの製造方法 |
EP2404980A1 (fr) | 2010-07-08 | 2012-01-11 | Total Raffinage Marketing | Augmentation de la masse moléculaire moyenne de produits de départ d'hydrocarbure |
WO2012004328A1 (fr) | 2010-07-08 | 2012-01-12 | Total Raffinage Marketing | Augmentation du poids moléculaire moyen d'une charge d'hydrocarbures |
WO2012089716A1 (fr) | 2010-12-28 | 2012-07-05 | Total Raffinage Marketing | Charge d'hydrocarbures contenant des nitriles, son procédé de fabrication et son utilisation |
WO2013104614A1 (fr) | 2012-01-09 | 2013-07-18 | Total Raffinage Marketing | Procédé pour la conversion d'une charge de départ d'hydrocarbures contenant des oléfines de faible point d'ébullition |
EP2636661A1 (fr) * | 2012-02-15 | 2013-09-11 | IFP Energies nouvelles | Procédé de conversion d'une charge lourde, mettant en oeuvre une unité de craquage catalytique et une étape d'hydrogénation sélective de l'essence issue du craquage catalytique |
Also Published As
Publication number | Publication date |
---|---|
CN103333714A (zh) | 2013-10-02 |
DE112005003177T5 (de) | 2008-01-24 |
JP2008524421A (ja) | 2008-07-10 |
GB0713207D0 (en) | 2007-08-15 |
US20100036182A1 (en) | 2010-02-11 |
CN101084291A (zh) | 2007-12-05 |
FR2879620A1 (fr) | 2006-06-23 |
DE112005003177B4 (de) | 2016-03-10 |
JP5140819B2 (ja) | 2013-02-13 |
GB2437203A (en) | 2007-10-17 |
US9193922B2 (en) | 2015-11-24 |
FR2879620B1 (fr) | 2007-02-23 |
GB2437203B (en) | 2009-07-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
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 | |
EP1487768B1 (fr) | Procede de conversion en plusieurs etapes d'une charge comprenant des olefines a quatre, cinq atomes de carbone et plus, en vue de produire du propylene | |
EP2321385B1 (fr) | Procédé de conversion d'une charge lourde en essence et en propylène présentant une structure de rendement modulable | |
EP0742195B1 (fr) | Procédé et installation pour la conversion de coupes C4 et C5 oléfiniques en éther et en propylène | |
EP0838449B1 (fr) | Nouveau procédé de production d'isobutène et de propylène à partir de coupes d'hydrocarbures à quatre atomes de carbone | |
WO2003078547A2 (fr) | Procede de production conjointe de propylene et d'essence a partir d'une charge relativement lourde | |
EP1110934B1 (fr) | Production d'isobutène de haute pureté et de propylène à partir de coupes d'hydrocarbures à quatre atomes de carbone | |
EP1777284B1 (fr) | Procédé de conversion directe d'une charge comprenant des oléfines à quatre, et/ou cinq atomes de carbone, pour la production de propylène avec une co-production d'essence désulfurée à haut indice d'octane | |
FR2733986A1 (fr) | Procede et installation pour la conversion de coupes c4 olefiniques en polyisobutenes et en propylene | |
EP2636661B1 (fr) | Procédé de conversion d'une charge lourde, mettant en oeuvre une unité de craquage catalytique et une étape d'hydrogénation sélective de l'essence issue du craquage catalytique | |
EP1668094B1 (fr) | Procede de conversion directe d'une charge comprenant des olefines a quatre, et/ou cinq atomes de carbone ou plus, pour la production de propylene | |
EP0132172A1 (fr) | Procédé de production de supercarburant par polymérisation des coupes C4 | |
FR2968010A1 (fr) | Procede de conversion d'une charge lourde en distillat moyen | |
EP1892229B1 (fr) | Procédé de production de propylène en presence d'un catalyseur macroporeux se presentant sous forme de billes spheriques | |
FR2984916A1 (fr) | Procede ameliore de conversion d'une charge lourde en distillat moyen faisant appel a un pretraitement en amont de l'unite de craquage catalytique | |
FR2942796A1 (fr) | Procede de conversion directe d'une charge comprenant des olefines a quatre et/ou cinq atomes de carbone pour la production de propylene | |
EP0233169A2 (fr) | Procédé de traitement des gasoils | |
WO2014041285A1 (fr) | Procédé de production de kérosène à partir de butanols | |
WO2012153011A2 (fr) | Procede de production de coupes kerosene ou gazole a partir d'une charge olefinique ayant majoritairement de 4 a 6 atomes de carbone | |
EP1110933B1 (fr) | Procédé de production sélective de propylène à partir de coupes d'hydrocarbures à quatre atomes de carbone | |
FR2983208A1 (fr) | Procede de production de distillat moyen a partir d'une charge lourde conventionnelle incluant une etape d'hydrogenation selective de la coupe hco ex fcc |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KN KP KR KZ LC LK LR LS LT LU LV LY MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 200580043759.7 Country of ref document: CN Ref document number: 1120050031772 Country of ref document: DE Ref document number: 2664/CHENP/2007 Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2007547561 Country of ref document: JP |
|
ENP | Entry into the national phase |
Ref document number: 0713207 Country of ref document: GB Kind code of ref document: A Free format text: PCT FILING DATE = 20051213 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 0713207.9 Country of ref document: GB |
|
REG | Reference to national code |
Ref country code: GB Ref legal event code: 789A Ref document number: 0713207 Country of ref document: GB |
|
RET | De translation (de og part 6b) |
Ref document number: 112005003177 Country of ref document: DE Date of ref document: 20080124 Kind code of ref document: P |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 05826566 Country of ref document: EP Kind code of ref document: A1 |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 5826566 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 11722300 Country of ref document: US |