WO2018210827A1 - Procédé de valorisation de mto-ocp pour maximiser la sélectivité en propylène - Google Patents

Procédé de valorisation de mto-ocp pour maximiser la sélectivité en propylène Download PDF

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WO2018210827A1
WO2018210827A1 PCT/EP2018/062550 EP2018062550W WO2018210827A1 WO 2018210827 A1 WO2018210827 A1 WO 2018210827A1 EP 2018062550 W EP2018062550 W EP 2018062550W WO 2018210827 A1 WO2018210827 A1 WO 2018210827A1
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feedstream
oligomerization
ethylene
catalyst
olefins
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PCT/EP2018/062550
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English (en)
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Elena BORODINA
Nikolai Nesterenko
Delphine Minoux
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Total Research & Technology Feluy
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    • 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
    • C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/044—Iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/12—Silica and alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/82—Phosphates
    • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
    • C07C2529/85—Silicoaluminophosphates (SAPO compounds)
    • 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
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Definitions

  • the present invention relates to a Methanol-to-Olefin process (MTO process) based on mesoporous catalyst combined with an Olefin Cracking Process (OCP) to make olefins.
  • MTO process Methanol-to-Olefin process
  • OCP Olefin Cracking Process
  • MTO process Methanol-to-Olefin process
  • selectivity to ethylene and propylene is about 38 to 42 wt% respectively based on the total weight of the composition.
  • the C4+ hydrocarbon fraction in this process is 13 wt% and the rest, corresponding to about 7 wt% based on the total weight of the composition, is a dry gas.
  • Ethylene and propylene are particularly desirable olefins but it has been found that their yields in the MTO process are reduced by the production of medium weight hydrocarbons such as C4, C5 and C6 olefins, as well as some heavier components.
  • MTO-OCP process Several combined MTO process have been developed in order to improve the selectivity of the MTO process toward propylene.
  • An example of such combined MTO process is MTO-OCP process.
  • Addition of the OCP process allows the conversion of the C4+ hydrocarbon fraction into C2- hydrocarbon fraction and C3- hydrocarbon fraction.
  • Combined MTO-OCP process allows a selectivity of propylene yield to 51 wt% based on the total weight of the composition.
  • Another combined MTO process is the DMTO-II process over which both the MTO reaction and a C4+ hydrocarbon cracking reaction can be realized.
  • the C4+ compounds are recycled to the fluidized C4+ cracking reactor to increase the ethylene and propylene yield.
  • the increase of propylene yield to around 50 wt% based on the total weight of the composition.
  • MTO process can be also combined using known methods for the metathesis of C4+.
  • Over MTO-metathesis process propylene yield to 55 wt% based on the total weight of the composition.
  • All above described combined MTO processes produce C2- hydrocarbon as second main product with a selectivity about 31 to 38 wt% based on the total weight of the composition.
  • WO 2016/094174 describes the production of light olefins with a SAPO-18 catalyst operated at a high pressure.
  • WO 2009/098267 describes a dehydration process to convert ethanol into ethylene.
  • US 2013/0165718 describes a process for the preparation of olefins via the conversion of oxygenate in a oxygenate-to-olefins conversion system.
  • the invention provides a process for the production of propylene comprising the following steps: c) providing an effluent from a Methanol-to-Olefin (MTO) process containing ethylene and propylene and olefins having at least four carbon atoms;
  • MTO Methanol-to-Olefin
  • step c) subjecting the MTO effluent of step c) to a fractionation process in a separation system to produce an ethylene feedstream, a propylene feedstream and a first olefin feedstream comprising olefins having at least four carbon atoms;
  • step d) subjecting the ethylene feedstream of step d) to an oligomerization reaction in an oligomerization reactor in presence of an oligomerization catalyst to produce a second olefin feedstream comprising olefins having at least four carbon atoms;
  • OCP Olefin Cracking Process
  • step f) subjecting the OCP effluent of step f) to a fractionation process in a separation system to produce an ethylene feedstream and one or more streams comprising propylene and olefins having at least four carbon atoms;
  • step g) recovering propylene from the streams comprising propylene and olefins having at least four carbon atoms of step g); wherein the oligomerization catalyst used in the oligomerization reaction of step e) consists of one or more metals of group VI 11 B and/or of group VIB deposited on a support being a mesoporous material, and preferably wherein the oligomerization reaction of step e) is performed at a temperature ranging from 80 to 500°C, under a pressure ranging from 0.5 to 2.9 MPa, and at a weight hourly space velocity (WHSV) of the feedstream ranging from 0.1 to 10.0 h- 1 .
  • WHSV weight hourly space velocity
  • the WHSV is determined on the total feed.
  • metals of group VIIIB and of group VIB is made according to the CAS classification. It has been found by the inventors that, surprisingly, catalysts consisting of one or more metals of group VIIIB and/or of group VIB deposited on a support being a mesoporous material can be used in an oligomerization reaction to convert ethylene from diluted stream at low reaction pressure with high carbon efficiency of more than 80% and with a high selectivity to olefin having at least 4 carbons atoms (C4+) of more than 95 %.
  • the improved selectivity of the oligomerization catalyst toward C4 allows an increase of the propylene yield up to 81 wt% as based on the total weight of the products in the inventive MTO- -Oligo-OCP process, with a complete recycling of ethylene.
  • the mesoporous material is an ordered mesoporous material or any type of mesoporous material based on silica.
  • the mesoporous material is an Al-containing material, preferably Al modified silica type.
  • the mesoporous material is a mesoporous material of SBA-15 topology or is a mesoporous material of Al-modified silica type.
  • the one or more metals of group VII IB and/or of group VI B of the catalyst of step b) are selected from nickel, cobalt, chromium, molybdenum, tungsten, palladium and any mixture thereof.
  • the one or more metals of group VIIIB and/or of group VIB is a mixture of nickel with one or more metals of group VIIIB and/or of group VIB selected from cobalt, chromium, molybdenum, tungsten, palladium and any mixture thereof, preferably wherein the mixture comprises more than 50 wt% of nickel as based on the total weight of the mixture, more preferably more than 70 wt% of nickel.
  • the oligomerization catalyst of step e) consists of nickel deposited on a support being a mesoporous material, preferably on a support being an aluminated ordered mesoporous material.
  • the oligomerization catalyst consists of nickel deposited on a support being a mesoporous material, and the catalyst comprises from 0.5 to 10.0 wt% of nickel based on the total weight of the catalyst as determined according to UOP961 -12, preferably from 1 .0 to 5.0 wt% and more preferably from 2.0 to 3.0 wt%.
  • the oligomerization catalyst consists of nickel deposited on a support being a mesoporous material of SBA-15 topology, preferably the catalyst is Ni-AI-SBA-15.
  • the oligomerization catalyst consists of nickel deposited on a support being a mesoporous material of Al-modified silica type, preferably the catalyst is Ni-AI-SiC>2.
  • the oligomerization catalyst comprises a mesoporous material with mesoporous pores having an average diameter of at least 2 nm, preferably of at least 5 nm, more preferably of at least 7 nm, even more preferably of at least 7.5 nm, as determined according to ASTM D 4641 - 94 (reapproved 2006).
  • the oligomerization catalyst comprises a mesoporous material with mesoporous pores having an average diameter ranging from 2 to 50 nm as determined according to ASTM D 4641 - 94 (reapproved 2006), preferably ranging from 5 to 40 nm.
  • the mesoporous material of the catalyst comprises mesoporous pores having an average diameter of at least 2 nm as determined according to ASTM D 4641 - 94 (reapproved 2006) and a mesoporous pore volume of at least 0.1 mL/g as determined according to ASTM D 4641 - 94 (reapproved 2006).
  • the oligomerization catalyst comprises an ordered mesoporous silica material, or any other silica exhibiting a type IV isotherm.
  • the oligomerization catalyst comprises a total surface area ranging from 100 m 2 /g to 1000m 2 /g, preferably 120m 2 /g to 700 m 2 /g, such as from 150 m 2 /g to about 500 m 2 /g measured according to ASTM D 4365 - 95 (reapproved 2008).
  • the oligomerization catalyst has a bulk Si/AI ratio ranging from 5 to 10 preferably from 6 to 8 as determined according to UOP961 -12.
  • the catalyst has a sieve fraction ranging from 0.10 to 0.50 mm, preferably from 0.15 to 0.25 mm; as measured according to ASTM D4513 - 1 1 .
  • the oligomerization reaction of step e) is conducted at a temperature ranging from 150 to 350°C, more preferably at a temperature ranging from 180 to 280°C.
  • the oligomerization reaction of step e) is conducted under a pressure ranging from 1.0 to 2.0 MPa, and most preferably from 1.0 to 1 .5 MPa.
  • the oligomerization reaction of step e) is performed at a weight hourly space velocity (WHSV) of the ethylene feedstream of from 0.5 to 8.0 h "1 , preferably from 1 .0 to 5.0 h ⁇ 1 .
  • WHSV weight hourly space velocity
  • the oligomerization reaction of step e) is carried out during more than 40 hours without replacement or reactivation of the catalyst, preferably more than 50 hours, more preferably more than 60 hours, and even more preferably more than 70 hours without replacement or reactivation of the catalyst.
  • the ethylene feedstream of step d) and/or the ethylene feedstream of step g) comprises from 0.5 to 50 wt% of ethylene, preferably from 5 to 40 wt% of ethylene, more preferably from 10 to 30 wt% of ethylene based on the total weight of the feedstream.
  • MTO Methanol-to-Olefin
  • the MTO effluent containing ethylene and propylene and olefins having at least four carbon atoms of step b) is the MTO effluent of step c), preferably the catalyst of step b) is a SAPO catalyst.
  • the step e) further comprises subjecting the ethylene feedstream of step g) to an oligomerization reaction (OL) in an oligomerization reactor in presence of an oligomerization catalyst to produce a second olefin feedstream comprising olefins having at least four carbon atoms.
  • OL oligomerization reaction
  • the process further comprises the steps of: i) recovering olefins having at least four carbon atoms from the stream comprising propylene and olefins having at least four carbon atoms of step g);
  • step j) recycling at least a portion of the olefins having at least four carbon atoms recovered in step i) in the OCP reactor of step f) to submit them to a further OCP process.
  • the invention provides an installation for producing propylene according to the process defined above, the installation comprising:
  • MTO reactor optionally a MTO reactor to produce a MTO effluent
  • a first separation system adapted to the separation of an effluent, such as a MTO effluent, in an ethylene feedstream, a propylene feedstream and a first olefin feedstream comprising olefins having at least four carbon atoms;
  • a second separation system adapted to the separation of the OCP effluent in an ethylene feedstream and a stream comprising propylene and olefins having at least four carbon atoms.
  • the installation further comprises lines to direct the ethylene feedstream exiting the second separation system to the oligomerization reactor.
  • the invention provides the use of a catalyst consisting of one or more metals of group VI 11 B and/or of group VIB deposited on a support being a mesoporous material, as catalyst in a process for the production of propylene as defined above remarkable in that the process comprises an oligomerization step wherein a feedstream comprising from 0.5 to 50 wt% of ethylene as based on total weight of the feedstream, is put in contact with said catalyst at a temperature ranging from 80 to 500°C, under a pressure ranging from 0.5 to 2.9 MPa, and at a weight hourly space velocity (WHSV) of the feedstream ranging from 0.1 to 10.0 h "1 , preferably the catalyst is nickel deposited on a mesoporous material of SBA-15 topology or nickel deposited on a mesoporous material of Al-modified silica type.
  • WHSV weight hourly space velocity
  • Figure 1 represents an installation to carry out the inventive process.
  • Figure 2 illustrates the conversion and selectivity of ethylene oligomerization for Ni-AI-
  • catalyst refers to a “supported catalyst” which is a catalyst comprising an active phase and a support.
  • the process and the installation will be jointly described in reference to figure 1.
  • the invention provides an installation and a process for the production of propylene comprising the following steps:
  • step c) subjecting the MTO effluent 5 of step c) to a fractionation process (S) in a separation system 7 to produce an ethylene feedstream 9, a propylene feedstream 1 1 and a first olefin feedstream 13 comprising olefins having at least four carbon atoms;
  • step d) subjecting the ethylene feedstream 9 of step d) to an oligomerization reaction (OL) in an oligomerization reactor 15 in presence of an oligomerization catalyst to produce a second olefin feedstream 17 comprising olefins having at least four carbon atoms; f) subjecting said first 13 and second 17 olefin feedstreams to an OCP process in an OCP reactor 19 to produce an OCP effluent 21 containing ethylene and propylene and olefins having at least four carbon atoms;
  • step f) subjecting the OCP effluent 21 of step f) to a fractionation process (S) in a separation system 23 to produce an ethylene feedstream 25 and one or more streams 27 comprising propylene and olefins having at least four carbon atoms;
  • step e) recovering propylene from the streams 27 comprising propylene and olefins having at least four carbon atoms of step g); wherein the oligomerization catalyst used in the oligomerization reaction of step e) consists of one or more metals of group VI 11 B and/or of group VIB deposited on a support being a mesoporous material.
  • the oligomerization reaction of step e) is performed at a temperature ranging from 80 to 500°C, under a pressure ranging from 0.5 to 2.9 MPa, and at a weight hourly space velocity (WHSV) of the feedstream ranging from 0.1 to 10.0 h- 1 .
  • WHSV weight hourly space velocity
  • the process further comprises the steps of:
  • a feedstock 1 preferably comprising methanol
  • a MTO reactor 3 comprising a reaction zone in which the feedstock is contacted with a catalyst, preferably a SAPO catalyst, under conversion conditions to produce a MTO effluent 5 containing ethylene and propylene and olefins having at least four carbon atoms;
  • MTO effluent 5 containing ethylene and propylene and olefins having at least four carbon atoms of step b) is the MTO effluent 5 of step c).
  • MTO processes and reactors 3 are well known and are for example described in US 2006/0235251 , WO 2005/016856, US 2006/0063956, US 2006/0161035, US 6207872, US 2005/0096214, US 6953767 and US 7067095. All of which are herein incorporated by reference.
  • the feedstock 1 is converted to light olefins by the use of silicoaluminophosphate (SAPO) molecular sieve catalysts because of they are selective to the formation of ethylene and propylene.
  • SAPO silicoaluminophosphate
  • Preferred SAPO catalyst are SAPO-17, SAPO-18, SAPO-34, SAPO-35, SAPO-44, the substituted forms thereof and mixtures thereof.
  • other catalysts may be considered by the person skilled in the art.
  • the feedstock 1 may comprise one or more aliphatic containing compounds, including alcohols, amines, carbonyl compounds, for example, aldehydes, ketones and carboxylic acids, ethers, halides, mercaptans, sulfides, and the like and mixtures thereof.
  • suitable feedstocks include methanol, ethanol, methyl mercaptan, ethyl mercaptan, methyl sulfide, methyl amine, di-methyl ether, di-ethyl ether, methyl ethyl ether, methyl chloride, ethyl chloride, dimethyl ketone, formaldehyde, acetaldehyde and various acids such as acetic acid.
  • the feedstock 1 comprises one or more alcohols having from 1 to four carbon atoms and most preferably methanol.
  • the feedstock 1 is contacted with a MTO catalyst and is converted to a MTO effluent being a stream of light olefins comprising ethylene, propylene and olefins having at least four carbon atoms; said MTO effluent 5 of step b) is subjected to a fractionation process in step d) to produce a first ethylene feedstream 9, a first propylene feedstream 1 1 and a first olefin feedstream 13 comprising olefins having at least four carbon atoms.
  • the first olefin feedstream of step d) i.e. the heavy hydrocarbon fraction produced in the MTO reactor
  • OCP reactor olefin cracking reactor
  • the OCP process in the OCP reactor is known per se. It has been described in EP1036133, EP1035915, EP 1036134, EP1036135, EP1036136, EP1036138, EP1036137, EP1036139, EP1 194502, EP1 190015, EP1 194500 and EP1363983. The content of which are incorporated in the present invention.
  • Preferred catalysts for the OCP reaction can be selected from the MFI-type crystalline silicate (with a bulk Si/AI of at least 300) or a phosphorous modified zeolite of MFI, MEL, FER, MOR, Clinoptilolite.
  • the OCP reactor 19 can be a fixed bed reactor, a moving bed reactor or a fluidized bed reactor.
  • a typical fluid bed reactor is one of the FCC type used for fluidized-bed catalytic cracking in the oil refinery.
  • a typical moving bed reactor is of the continuous catalytic reforming type.
  • the cracking process is endothermic; therefore, the reactor should be adapted to supply heat as necessary to maintain a suitable reaction temperature. Online or periodic regeneration of the catalyst may be provided by any suitable means known in the art.
  • the OCP reactor effluent 21 comprises methane, light olefins and hydrocarbons having four carbon atoms or more.
  • OCP reactor effluent 21 is sent to a separation system 23 and subjected to a fractionation process in step g) to produce an ethylene feedstream 25 and a stream 27 comprising propylene and olefins having at least four carbon atoms.
  • the stream 27 comprising propylene and olefins having at least four carbon atoms is subjected to a further fractionation process in a separation system 29 to produce a propylene feedstream and a stream 31 olefins having at least four carbon atoms.
  • the stream 31 of hydrocarbons having four carbon atoms or more are recycled at the inlet of the OCP reactor 19, optionally mixed with the heavy hydrocarbon recovered from the effluent 5 of the MTO reactor 3 (i.e. with the first olefin feedstream 13 comprising olefins having at least four carbon atoms).
  • said hydrocarbons having four carbon atoms or more are sent to a further separation system (not represented) to purge the heavies.
  • the light olefins i.e.
  • the step e) of oligomerization further comprises subjecting the ethylene feedstream 25 of step g) to an oligomerization reaction (OL) in an oligomerization reactor 15 in presence of an oligomerization catalyst to produce a second olefin feedstream 17 comprising olefins having at least four carbon atoms.
  • OL oligomerization reaction
  • the step e) of oligomerization comprises subjecting both the ethylene feedstream 9 of step d) and the ethylene feedstream 25 of step g) to an oligomerization reaction (OL) in an oligomerization reactor 15 in presence of an oligomerization catalyst to produce a second olefin feedstream 17 comprising olefins having at least four carbon atoms.
  • OL oligomerization reaction
  • the process further comprises the steps of:
  • step j) recycling at least a portion 31 of the olefins having at least four carbon atoms recovered in step i) in the OCP reactor 19 of step f) to submit them to a further OCP process.
  • the installation for producing propylene according to the inventive process defined above comprises:
  • MTO reactor 3 optionally a MTO reactor 3 to produce a MTO effluent 5;
  • an oligomerization reactor 15 to produce a second olefin feedstream 17 ; an OCP reactor 19 to produce an OCP effluent 21 ,
  • a first separation system 7 adapted to the separation of an effluent, such as a MTO effluent 5, in an ethylene feedstream 9, a propylene feedstream 1 1 and a first olefin feedstream 13 comprising olefins having at least four carbon atoms,
  • a second separation system 23 adapted to the separation of the OCP effluent 21 in an ethylene feedstream 25 and a stream 27 comprising propylene and olefins having at least four carbon atoms;
  • a third separation system 29 adapted to the separation of the stream 27 comprising propylene and olefins having at least four carbon atoms into a propylene stream, and a stream 31 of olefins having at least four carbon atoms.
  • the installation further comprises lines to direct the ethylene feedstream 25 exiting the second separation system 23 to the oligomerization reactor 15.
  • the installation further comprises lines to direct the stream 31 of olefins having at least four carbon atoms exiting the third separation system 29 to the OCP reactor 19.
  • the present invention contemplates the use of a catalyst being a supported catalyst in oligomerization reaction to convert ethylene into olefins having at least four carbon atoms (C4+) wherein ethylene is diluted in the feedstream.
  • the catalyst used in the invention is a calcined supported catalyst thus any reference to the catalyst includes a reference to a calcined supported catalyst.
  • the catalyst consists of one or more metals of group VIIIB and/or of group VI B deposited on a support being a mesoporous material.
  • the one or more metals of group VIIIB and/or of group VIB are preferably selected from nickel, cobalt, chromium, tungsten, palladium, molybdenum and any mixture thereof.
  • the active phase is a mixture of nickel with one or more metals of group VIIIB and/or of group VIB selected from cobalt, chromium, tungsten, palladium, molybdenum and any mixture thereof, preferably wherein the mixture comprises more than 50 wt% of nickel as based on the total weight of the mixture, more preferably more than 70 wt% of nickel.
  • nickel is the active phase of the catalyst.
  • the mesoporous material is obtained from a zeolitic material of the FAU, MFI, MOR or FER type framework by various post-treatment procedures.
  • the mesoporized zeolites possesses a residual network of micropores (ie pores ⁇ 2nm in diameter) and contains mesopores (pores with diameter in the range 2-50 nm) connected to the micropores, and a ratio of the volume of the mesopores to the volume of the micropores in the range 0.2 to 3. Further the said materials may be shaped with a binder.
  • the preferred zeolite is FAU (zeolite Y).
  • the mesoporization may include steaming followed by a leaching procedure to remove the extra framework aluminum.
  • the mesoporisation of zeolite porosity may include the following steps:
  • a zeolite or a composite material comprising it in a basic aqueous solution comprising at least one strong base, e.g NaOH or KOH, and/or a weak base, in particular, sodium carbonate, sodium citrate, ammonium hydroxide etc., for example, at a concentration ranging from 0.001 to 2 M, at room or elevated temperature (25-200 °C), optionally an organic base may be present together with inorganic,
  • strong base e.g NaOH or KOH
  • a weak base in particular, sodium carbonate, sodium citrate, ammonium hydroxide etc., for example, at a concentration ranging from 0.001 to 2 M, at room or elevated temperature (25-200 °C)
  • an organic base may be present together with inorganic
  • the mesoporous material is an ordered mesoporous material or any type of mesoporous material based on silica.
  • the mesoporous silicas or silica-alumina have a large specific surface area (preferably above 600 m 2 /g) and a mesoporous structure with pores of uniform size which would overcome the constraints related to the diffusion of coarse particles molecules.
  • the mesoporous silicas with ordered structures are obtained by synthesis from a silicic precursor in the presence of structuring agents which are micelles of surface-active agents.
  • An amorphous silica is obtained having a porous structure ordered on the scale of a few nanometers.
  • structured mesoporous silicas developed by the different surfactant crosslinks / silica precursors.
  • the mesoporous silicas of the M41 S family which comprise MCM-41 type materials with hexagonal 2D crystallographic structure (p6mm group), MCM-48 type materials having a cubic structure (Ia3d) and MCM-50 materials having a lamellar structure; the mesoporous silicas of type SBA (Santa Barbara Amorphous).
  • MCM-41 type materials with hexagonal 2D crystallographic structure (p6mm group)
  • the mesoporous silicas of type SBA solda Barbara Amorphous.
  • SBA-1 cubic
  • SBA-15 hexagonal
  • SBA-16 cubic
  • SBA-14 lamellar
  • the mesoporous silicas of the MCF type (Mesostructured Cellular Foam) , which are obtained by adding swelling agents such as TMB (1 ,3,5-trimethylbenzene) to the synthesis of SBA-15, which leads to enlargement of the micelles. This makes it possible to obtain a structure consisting of uniform large pores. These materials have high thermal stability.
  • MSU-type mesoporous silicas (Michigan State University), these materials are obtained from non-ionic surfactants or from tri-block copolymers.
  • the mesoporous silica matrices are not acidic, it is necessary to provide them with acidity and a metallic function (Ni) for use in ethylene's oligomerization.
  • the acidity can be provided either by inserting aluminum dispersed in the silica network by direct synthesis [C.T. Kresge, M. E. Leonowicz, W.J. Roth, J.C. Vartuli, J.S. Beck, Nature 1992, 359, 710; A. Corma, V. Fornes, T. Navarro, J.
  • Alumination can be done by the following process:
  • at least one aluminum reagent for example selected from AICI3, NaAI0 4 , Al (NC AI(OR)3 where R is Chosen from linear or branched C1 - C6 alkyl groups, in order to obtain a compound whose bulk Si/AI ratio is comprised between 0.1 and 1000.
  • step (B) may also comprise the addition of one or more doping metals selected from the group of rare earths or group IVB or IB and/or the addition of one or more other doping elements, for example chosen from chlorine, fluorine, boron or phosphorus.
  • the addition of chlorine can increase the acidity of the material.
  • the preferred metals of groups IVB and IB are Ti and Cu.
  • steps of the above process are carried out in the order (A), (B), (C).
  • steps (A) and (B) it is possible to envisage a simultaneous implementation of steps (A) and (B), or even an implementation of step (B) before step (A).
  • deposition of alumina in step (A) is accomplished by grafting.
  • the deposition of alumina in the silica is carried out by grafting according to the following steps:
  • Step (v) Calcining of the washed and dried product. Step (i) corresponds to the reaction (1 ): I ⁇ OR
  • the stirring for step (i) is carried out for a period of 1 to 4 hours at a temperature of 20 to 95 °C, preferably 45 to 90 °C.
  • the solvent of step (i) can be chosen from hydrophobic solvents (i.e. apolar solvents), such as one or more selected from benzene, toluene, xylene, cyclohexane, n-hexane, pentane, isopropyl benzene, or any mixture thereof.
  • the solvent is toluene.
  • the solvent is dehydrated by drying on a molecular sieve before use.
  • the deposition of alumina on the mesoporous solid will be carried out using aluminum tri-sec-butoxide as a source of aluminum and toluene containing triethylamine as solvent.
  • the silanol group-activation agent of the silica will be chosen from organic basic compounds, for example amines, preferably triethylamine, nitriles, etc.
  • the role of this agent consists in activating the protons of the surface silanol groups and thus accelerating the reaction (1 ). It is thus possible to reduce the reaction temperature, which may be 85 °C.
  • Step (iii) corresponds to the reaction: 7 OR ⁇ , OH
  • the hydrolysis step (iii) will preferably be carried out at ambient temperature for a period of from 0.1 to 48 hours, preferably from 1 to 36 hours.
  • ambient temperature is meant a temperature ranging from 18 to 25 °C, and in particular a temperature of 20 °C.
  • the quantity of water required in step (iii) can for example be calculated by considering that AI(OC4Hg)3 completely adsorbs on the solid, taking into account an amount of stoichiometric water (duration less than 2 h).
  • the drying of step (iv) can be carried out at a temperature of 80 to 130 °C. for 1 to 25 hours, optionally under air or nitrogen flow or even under vacuum.
  • the calcination step (v) can be carried out at a temperature of 400 to 600 °C, preferably 400 to 550 °C, for a period of 0.5 to 8 hours, for example 1 to 6 hours, under a flow of gas.
  • the step (A) for depositing alumina, for example by grafting according to steps (i) to (iv), can be repeated several times, generally from 2 to 10 times, in order to obtain a layer of alumina on the surface of the mesoporous solid.
  • the grafting method consists in sodium aluminate.
  • silica is suspended under stirring in an aqueous solution containing sodium aluminate (with a concentration calculated to have the required Si/AI ratio after graphting) for 15h, at room temperature.
  • the sample which results in the sodium form (Na-AI-SBA-15) is filtered, washed with water, dried at 80°C, and calcined for 6h under air at 550°C.
  • the mesoporous material is an Al-containing material, preferably Al modified silica type.
  • the mesoporous material of the catalyst is a mesopourous material of SBA- 15 topology or is a mesopourous material of Al-modified silica type, preferably of a IV isotherm type.
  • the catalyst is selected from Ni-AI-SBA-15 or Ni-AI-SiC>2.
  • the mesoporous material of the catalyst is a mesoporous material is COK- 12.
  • the catalyst consists of nickel deposited on a support being a mesoporous material, and the nickel content of the catalyst is at least 0.5 wt%, preferably at least 1.0 wt%, more preferably at least 1.5 wt%, and even more preferably at least 2.0 wt% based to the total weight of the catalyst.
  • the nickel content is determined according to UOP961 -12.
  • the catalyst consists of nickel deposited on a support being a mesoporous material, and the nickel content of the catalyst is at most 10.0 wt%, preferably at most 5.0 wt%, more preferably at most 4.0 wt%, even more preferably of at most 3.5 wt%, and most preferably of at most 3.0 wt% based to the total weight of the catalyst.
  • the nickel content is determined according to UOP961 -12ln an embodiment, the catalyst shows large mesoporous pore of at least 2.0 nm, preferably at least 5.0nm, more preferably of at least 7.0 nm, even more preferably of at least 7.5 nm.
  • the size of the pore is determined by the surfactant used during the synthesis.
  • a pore size of at least 7.0 nm can be obtained using (EO)2o(PO)7o(EO)2o triblock copolymer (Pluronic P123, Aldrich) as surfactant during the synthesis of the catalyst.
  • the pore size can be determined according to ASTM D 4641 - 94 (reapproved 2006).
  • the catalyst shows mesoporous pores having a mesoporous pore volume of at least 0.1 mL/g as determined according to ASTM D 4641 - 94 (reapproved 2006), preferably at least 0.2 mL/g.
  • the catalyst has a bulk Si/AI ratio ranging from 5 to 10 preferably from 6 to 8 as determined according to UOP961 -12.
  • the catalyst has preferably a BET surface area in the range of about 100 m 2 /g to about 1000 m 2 /g, preferably from 120 m 2 /g to 700 m 2 /g, such as from 150 m 2 /g to about 500 m 2 /g as measured according to ASTM D 4365 - 95.
  • the catalyst has a sieve fraction ranging from 0.10 to 0.50 mm, preferably from 0.15 to 0.25 mm as measured according to ASTM D4513 - 1 1 .
  • the above catalyst is useful for the conversion of ethylene into olefins having at least four carbon atoms by oligomerization reaction.
  • the solids of the present invention can be used as itself as a catalyst. In another embodiment it can be formulated into a catalyst by combining with other materials that provide additional hardness or catalytic activity to the finished catalyst product.
  • Materials which can be blended with can be various inert or catalytically active materials, or various binder materials. These materials include compositions such as kaolin and other clays, various forms of rare earth metals, phosphates, alumina or alumina sol, titania, zirconia, quartz, silica or silica sol, and mixtures thereof. These components are effective in densifying the catalyst and increasing the strength of the formulated catalyst.
  • the catalyst may be formulated into pellets, spheres, extruded into other shapes, or formed into a spray-dried particles.
  • the amount of mesoporous material which is contained in the final catalyst product ranges from 10 to 90 weight percent of the total catalyst, preferably 20 to 70 weight percent of the total catalyst.
  • the metals can be introduced either in the power form or to the extruded form.
  • the oligomerization reaction of step e) is conducted at a reaction temperature of at least 100°C, preferably of at least 150°C, more preferably of at least 180°C and even more preferably of at least 200°C.
  • the temperature is kept below 500°C, preferably below 450°C, more preferably below 400°C and even more preferably below 350°C.
  • the preferred range for the reaction temperature is between 200 to 300°C.
  • the person skilled in the art may increase the temperature to increase the conversion rate to C4+ olefin. However the stability of the catalyst is better around 200°C as demonstrated in the examples.
  • the oligomerization reaction of step e) is conducted under a pressure of at least 0.5 MPa, preferably at least 1 .0 MPa, more preferably at least 1.2 MPa and even more preferably at least 1.4 MPa.
  • the pressure is at most 3.0 MPa, preferably at most 2.8 MPa, more preferably at most 2.5 MPa and even more preferably at most 2.0 MPa.
  • the process is carried out at an ethylene partial pressure of at most 1 .0 MPa, preferably of at most 0.8 MPa, more preferably of at most 0.5 MPa and even more preferably of at most 0.4 MPa.
  • each gas has a partial pressure which is the hypothetical pressure of that gas if it alone occupied the entire volume of the original mixture at the same temperature.
  • the total pressure of an ideal gas mixture is the sum of the partial pressures of each individual gas in the mixture.
  • ⁇ fof is the total pressure of the gas mixture
  • n x is the amount of substance of gas (X)
  • ntot is the total amount of substance in gas mixture
  • the low WHSV combined with the dilution of ethylene and the use of the Ni-AI-SBA-15 catalyst has been shown to have an effect on the product distribution of C4 and C6. Indeed, it has been shown that low WHSV increases the contribution of C4 over C6 (see examples).
  • the weight hourly space velocity (WHSV) is the quotient of the mass flow rate of the reactants divided by the mass of the catalyst in the reactor.
  • the oligomerization reaction is performed at a WHSV of at most 10.0 h "1 , preferably ranging from 0.2 to 9.0 h -1, more preferably ranging from 0.5 to 8.0 h "1 , and even more preferably ranging from 1.0 to 5.0 h "1 .
  • the oligomerization reaction of step e) can be carried out with a stable performance with respect to activity and selectivity during more than 40 hours, preferably more than 50 hours, more preferably more than 60 hours, and even more preferably more than 70 hours without the need of reactivation or replacement of the supported catalyst.
  • the oligomerization reaction is carried out in a fixed bed or in a fluidized bed reactor comprising at least one catalytic bed.
  • a fluidized bed reactor comprising at least one catalytic bed.
  • Such reactors are well-known from the person skilled in the art and for instance described in EP2257366 or in US7279138.
  • purification section can be added optionally to remove CO, CO2, H2.
  • the following units can be introduced: amine absorber to remove H2S, water wash unit to remove amine from amine adsorber and decrease content of NH3 and CO2.
  • a guard bed can be implemented to remove impurities such as CO, CO2, H2S and/or NH3.
  • a drying section can be added to remove H2O, which can have a negative effect on catalyst performance.
  • the oligomerization reaction is carried out with a diluted ethylene feedstream
  • the ethylene feedstream of step d) and/or the ethylene feedstream of step g) comprise at least 5 wt% of ethylene as based on the total weight of the feedstream, preferably at least 10 wt%, more preferably at least 15 wt%.
  • the feedstream comprises at most 50 wt% of ethylene as based on the total weight of the feedstream, preferably at most 45 wt%, more preferably at most 40 wt%, even more preferably at most 35 wt% and most preferably at most 30 wt%.
  • the ethylene feedstream of step d) and/or the ethylene feedstream of step g) comprise ethylene diluted into inert component such as a mixture of CH4, C2H6, C3H8, N2.
  • the feedstream can have a typical composition of an FCC off gases i.e. the feedstream can comprise ethylene diluted into a mixture of CH4, C2H6, C3H8, N2 together with C3 and C4 olefins.
  • the ethylene feedstream of step d) and/or the ethylene feedstream of step g) may also comprise some contaminants such as carbon oxide (CO) and hydrogen (H2).
  • the ethylene feedstream of step d) and/or the ethylene feedstream of step g) preferably comprise less than 1 wt% of CO based on the total weight of the feedstream.
  • the feedstream also comprises less than3 wt% of C02 and/or less than 4 wt% of H2 based on the total weight of the feedstream.
  • the ethylene feedstream of step d) and/or the ethylene feedstream of step g) comprise less than 1 wt% of H2 based on the total weight of the feedstream.
  • the step e) further comprises a step i) of recycling at least a part of the ethylene feedstream 25 of step g) to the oligomerization reactor 15 of step e) to submit it to an oligomerization reaction.
  • Pore diameter and pore volume were determined according to D4641 -94 (reapproved 2006). Bulk Si/AI ratio and Ni content were determined according to ASTM UOP961 -12. Sieve fraction can be determined by ASTM D4513 - 1 1
  • Example 1 synthesis of a Ni-AI-SBA-15 catalyst
  • the catalyst can be prepared according to the procedure described in "Heterogeneous oligomerization of ethylene over highly active and stable Ni-AI-SBA-15 mesoporous catalysts" by Andrei, R. D. et al, Journal of catalysis, 323 (2015) 76-84.
  • Al-containing material (AI-SBA-15) is obtained from SBA-15 silica by grafting with sodium aluminate. For this, 3.8 g of SBA-15 is suspended under stirring in 400 mL of aqueous solution containing 1.03 g of sodium aluminate for 15 h, at room temperature. The sample which results in sodium form (Na-AI-SBA-15) is filtered, washed with water, dried at 80°C in air and calcined for 6 hours in air at 550°C.
  • 2g of Na-AI-SBA-15 is contacted three times, for 2 hours at 30°C, under constant agitation, with 100 cm 3 of 0.5 M aqueous solution of NH4NO3 to obtain the ammonium form, NH4-AI-SBA-I 5.
  • the sample in ammonium form is subjected to successive nickel-ion exchanges with a 0.5 M aqueous solution of nickel nitrate, following the same procedure as above.
  • the exchanged sample is dried and then calcined for 5 hours at 550°C to obtain the catalyst Ni-AI-SBA-15 of the invention.
  • the ethylene oligomerization reaction was performed in a stainless fixed bed reactor using 2 g of catalyst.
  • the pressure was regulated via a back pressure regulator.
  • Thermocouple was placed on the top of the catalyst bed.
  • Gas chromatography was connected on-line with the outlet of the reactor.
  • the catalyst Ni-AI-SBA-15 Prior the reaction, the catalyst Ni-AI-SBA-15, was activated in a reactor either in N2 flows (5 NL/h), at 550°C for 8 hours, applying 60°C/h heating rate. After the activation the catalyst was cooled down to 150°C. The temperature was then increased gradiently up to a final reaction temperature of 200 or 250°C for the oligomerization reaction. For all tests, the reaction was conducted at a pressure of 1 .5 MPa.
  • the feedstream comprised C2H4 and N2 at a ratio 17-29 wt% (C2H4): 83- 71 wt% (N2) as based on the total weight of the feedstream. Conversion and selectivity was calculated based on the results of gas chromatography, making sure that all the peaks were integrated. Regeneration of Ni-AI-SBA-15 was carried out after every test. The catalyst was regenerated in a reactor in air flows (5 NL/h), at 550°C for 2 hours, applying 60°C/h heating rate and then in N2 flows (5 NL/h) during 8 hours.
  • Example 3 Ethylene oligomerization: Conversion and selectivity with Ni-AI-SBA-15 catalyst
  • the conversion and selectivity with TOS for the test of example 2 are presented in Fig. 2.
  • the catalyst is active, showing the conversion of more than 90% after a time of 40 hours on stream.
  • the catalyst is stable for at least for 70 hours.
  • Product composition consists of about 90 wt% of butene (C4-) - octane (C8-) fraction, about 5 wt% of ethane and about 5 wt% of C5+ paraffins including traces of uneven olefins.
  • butene fraction is prevailing (about 60 wt% as based on the total weight of the products), where mainly internal olefins are formed.
  • Example 4 Ethylene oligomerization: Influence of the temperature with Ni-AI-SBA-15 catalyst
  • the activity for two reaction temperatures can be considered the same (the difference is within the error margin).
  • the catalyst is more stable, showing lower deactivation rate, i.e, 2.9 * 10 "4 vs. 1.6 * 10-3 IT 1 (250 °C).
  • Example 5 Ethylene oligomerization: Influence of the WHSV with Ni-AI-SBA-15 catalyst
  • the WHSV of the feed was increased from 1 .75 up to 3.5 h "1 , which gives WHSV of ethylene equal to 0.5 and 1 h "1 , respectively.
  • the results are presented in Fig.5.
  • ethylene partial pressure is about 3.0 MPa.
  • Fig. 5 shows space time yield for each case for the highest tested WHSV (3.5 h "1 ).
  • Example 6 synthesis of a Ni-AI-Si02 catalyst
  • the catalyst can be prepared according to the procedure described in "Nickel and molybdenum containing mesoporous catalysts for ethylene oligomerization and metathesis" by Andrei, R. D. et al, New J. Chem 40 (2016) 4146-4152.
  • S1O2 was synthetized according to the conventional method, using (EO)2o(PO) 7 o(EO)2o triblock copolymer (Pluronic P123, Aldrich), Tetraethyl orthosilicate (TEOS, Aldrich) and HCI 2 M (Aldrich) with a molar ratio of 1 TEOS/0.016 P123/ 4.9 HCI/40.5 H2O.
  • the mixture is stirred for 24 hours at 40°C, and then it is maintained for 48 hours at 100°C in a Teflon-lined autoclave under static conditions.
  • the solid product is filtered, washed with water and dried in an oven at 80°C overnight.
  • AI-S1-O2 is obtained from S1O2 by grafting with sodium aluminate (54+/- 1 % AI2O3 Carlo Erba). For this, 4.0 g of silica was suspended under stirring in 400 mL of aqueous solution containing 1 .1 g of sodium aluminate for 15 h, at 25 °C, corresponding to a bulk Si/AI ratio of 5.
  • Na-AI-SiC>2 The sample which results in sodium form (Na-AI-SiC>2) was subjected to successive ion exchange with NH4NO3 (99+%, Acros Organics) and Ni(N0 3 )2 ⁇ 6H 2 0 (98%, Alfa Aesar). Typically 2 g of Na-AI-SiC>2 were contacted three times, for 2 h at 25°C, under constant agitation, with 100 cm 3 of the 0.5 M aqueous solution of NH4NO3 to obtain the ammonium form NH4-AI-SiC>2. The sample in ammonium form was subjected to successive nickel-ion exchanges with a 0.5 M aqueous solution of nickel nitrate, following the same procedure as above.
  • the exchanged sample is dried and then calcined for 5 hours at 550°C to obtain the catalyst Ni-AI-Si02 of the invention.
  • the S1O2 used in the catalyst had a pore diameter of 10-12 nm, and total surface area was ranging from 160-250 m 2 /g.
  • Example 7 Ethylene oligomerization: Conversion and selectivity with Ni-AI-Si02 catalyst
  • the conversion and selectivity was studied with a time on stream of 75 hours.
  • the conversion of ethylene was more than 80 % after a time of 40 hours on stream for both fresh and regenerated catalyst.
  • the catalyst is stable for at least 75 hours.
  • Product composition showed a C4- fraction of about 75 wt% as based on the total weight of the product composition.
  • the tests were conducted in a flow mode using a fixed-bed reactor with a time on stream (TOS) of 75 hours, at a temperature of 250°C, under a pressure of 1.5 MPa with a feed of 1 L/h of N2 and 0.2 L/h of ethylene (corresponding to 17 wt% C2 in N2 stream as based on the total weight of the feedstream and to a WHSV (feed) of 1.1 rr 1 ).
  • TOS time on stream
  • Comparison of inventive and comparative examples shows an increase of the selectivity toward C4- products according to the inventive process.
  • Example 8 propylene yield on the MTO-oligomerization- OCP process according to the invention
  • This example was simulated and based on the oligomerization results.
  • An MTO effluent is fractionated in a separation system to produce a first ethylene feedstream comprising 38 wt% of C2, a propylene feedstream comprising 42 wt% of C3 and a first olefin feedstream comprising 13 wt% of olefins having at least four carbon atoms.
  • the first ethylene feedstream is submitted to an oligomerization reaction in an oligomerization reactor to produce a second olefin feedstream comprising 32 wt% of olefins having at least four carbon atoms. Both the first and the second olefin feedstream are subjected to an OCP process in an OCP reactor.
  • the OCP effluent is fractionated to produce a second ethylene feedstream comprising 14 wt% of C2. This second ethylene feedstream is recycled in the oligomerization reactor.
  • the content of olefins having at least four carbon atoms in the second olefin feedstream is increased to about 33.6 wt%.
  • the OCP effluent is also fractionated into a second propylene stream. The total content of propylene in the whole products MTO-oligo-OCP process yield 81 wt%.

Abstract

L'invention concerne un procédé de production de propylène à l'aide d'une étape de conversion de méthanol en oléfine (MTO), d'une étape d'oligomérisation et d'un processus OCP ; le catalyseur d'oligomérisation utilisé dans l'étape d'oligomérisation constitué d'un ou de plusieurs métaux du groupe VIIIB et/ou du groupe VIB déposés sur un support étant un matériau mésoporeux.
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