WO2012071137A1 - Procédé de préparation de charge de départ de craqueur de gaz - Google Patents

Procédé de préparation de charge de départ de craqueur de gaz Download PDF

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Publication number
WO2012071137A1
WO2012071137A1 PCT/US2011/058599 US2011058599W WO2012071137A1 WO 2012071137 A1 WO2012071137 A1 WO 2012071137A1 US 2011058599 W US2011058599 W US 2011058599W WO 2012071137 A1 WO2012071137 A1 WO 2012071137A1
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Prior art keywords
catalyst
feed
zsm
process according
zeolite
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PCT/US2011/058599
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English (en)
Inventor
Geert Marten Bakker
Saravana Bhavan
Bruce Kaygay
Muralikrishna Venkatacharyulu Khandavilli
Malgorzata Anna Koornneef
Chilkoor Soundararajan Laxmi Narasimhan
Marcello Stefano Rigutto
Ingrid Maria Van Vegchel
Ferry Winter
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Shell Oil Company
Shell Internationale Research Maatschappij B.V.
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Publication of WO2012071137A1 publication Critical patent/WO2012071137A1/fr

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    • 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
    • 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
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/44—Noble metals
    • 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
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • B01J29/7484—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
    • 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
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/18—Crystalline alumino-silicate carriers the catalyst containing platinum group metals or compounds thereof
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
    • C07C2529/44—Noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
    • C07C2529/74—Noble metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • 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 preparing a gas cracker feedstock and a process for producing olefins.
  • hydrocarbon feedstocks is found in the low ethylene yields and high production of heavy by-products such sa pitch.
  • the cracking catalyst used in US4137147 is an acid treated small pore Mordenite zeolite. In the examples of US4137147 a conversion of no more than 38.5wt% 5 of the initial charge to ethane and propane was attained.
  • the present invention provides a process for preparing a gas cracker feedstock, comprising contacting a feed containing one or more paraffins comprising 4 to 12 carbon atoms with a catalyst comprising at least one zeolite having 10-membered ring channels and at least one group VIb, Vllb and/or VIII metal, in the presence of hydrogen at elevated temperatures and elevated pressures and converting at least 40wt% of the paraffins comprising 4 to 12 carbon atoms based on the total weight of
  • paraffins comprising 4 to 12 carbon atoms in the feed to ethane and/or propane to obtain a hydrocracked gas cracker feedstock comprising ethane and/or propane.
  • Reference herein to a zeolite is to a molecular sieve aluminosilicate material.
  • Reference herein to a zeolite having 10-membered ring channels is to a zeolite or aluminosilicate having 10-membered ring channels in one direction, optionally intersected by 8, 9 or 10-membered ring channels in another direction.
  • the process according to the present invention can be operated at high feed conversions, reducing the need to provide a second or further cracking process.
  • the invention provides a process for producing olefins, comprising:
  • a gas cracker feedstock is prepared by hydrocracking a feed containing one or more paraffins comprising 4 to 12 carbon atoms.
  • the feed containing one or more paraffins is hydrocracking a feed containing one or more paraffins comprising 4 to 12 carbon atoms.
  • the obtained gas cracker feedstock may subsequently be thermally cracked in a gas cracker to at least ethylene in the presence of steam.
  • a paraffinic feed can be used directly as feedstock to a gas cracker without any prior hydrocracking step, this typically results in lower ethylene yields and high by ⁇ product formation such as pitch. It is known that high ethylene yields can be obtained when the feedstock to the gas cracker is rich in ethane and/or propane. Therefore, it has been proposed to hydrocrack the paraffinic feed prior to providing the feed to a gas cracker.
  • Gas crackers designed to operate on ethane and or propane are sensitive to the presence of C4 or higher paraffins in the feedstock to the gas cracker.
  • the presence of such paraffins again leads to production of by-products including pitch and methane. Therefore, there is a need to attain a high conversion of the paraffin feedstock, preferably with a high yield in ethane and propane. Otherwise, it may be necessary to treat the hydrocracked feedstock to remove the higher paraffins in order to obtain a suitable gas cracker feedstock.
  • the paraffinic feed is hydrocracked by contacting the paraffinic feed under hydrocracking conditions with a catalyst comprising at least one zeolite having 10- membered ring channels in the presence of hydrogen.
  • Zeolite having 10-membered ring channels as used in the present invention are sleeted from:
  • zeolites or aluminosilicates having only 10 membered ring channels in one direction, which are not intersected by other channels, in particular other 8, 10 or 12-membered ring channels, from another direction.
  • - multi dimensional zeolites or aluminasilicates having intersecting channels in at least two directions, whereby at least the channels in one direction are 10-membered ring channels, intersected by 8, 9 or 10-membered ring channels in another direction.
  • MFI-type zeolites have a three dimensional structure.
  • MFI-type zeolite is ZSM-5.
  • MEL-type zeolites have a three dimensional structure.
  • One preferred MEL-type zeolite is ZSM-11
  • TON-type zeolites are more particularly described in e.g. US-A-4 , 556 , 477.
  • US-A-4 , 556 , 477 For purposes of the present
  • TON is considered to include its isotypes, e.g., ZSM-22, Theta-1, ISI-1, KZ-2 and NU-10.
  • TON type zeolite is ZSM-22.
  • MTT-type zeolites are more particularly described in e.g. US-A-4 , 076 , 842.
  • US-A-4 , 076 , 842 For purposes of the present
  • MTT is considered to include its isotypes, e.g., ZSM-23, EU-13, ISI-4 and KZ-1.
  • MTT type zeolite is ZSM-23.
  • ZSM-48-type zeolites are more particularly described in e.g. US-A-4, 397, 827.
  • ZSM-48 is considered to include its isotypes.
  • Preferred ZSM-48-type zeolites are EU-2 and ZSM-48.
  • ITH-type zeolites have a three dimensional structure.
  • ITH-type zeolite is ITQ-13.
  • FER-type zeolites have a two-dimensional structure.
  • a preffered FER-type zeolite is Ferrierite
  • zeolite types and zeolites are for example defined in Ch . Baerlocher and L.B. McCusker,
  • TON-type, MTT-type, and EU-2-type zeolites are one dimensional zeolites, i.e. they have a one dimensional channel structure, wherein the 10-membered ring channels of the zeolite do not intersect with 8, 10 or 12-membered ring channels in another direction.
  • the FER-type zeolites are two dimensional, i.e. they have a two dimensional channel structure.
  • the 10-membered ring channels of the zeolite intersect with 8-membered ring channels in another direction.
  • the MFI and the MEL-type zeolites are three
  • dimensional zeolites i.e. they have a three dimensional channel structure. Both having intersecting 10-membered ring channels from three directions.
  • the catalyst comprises at least one of ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-48, or Ferrierite. More preferably, ZSM-5, ZSM-11 or ZSM-22.
  • the more preferred zeolites combine a high selectivity to ethane and/or propane with a high conversion of the paraffinic feed.
  • the catalyst may also contain two or more zeolites.
  • the catalyst comprises two or more zeolites it preferably comprises two zeolites having a 10-membered ring channel, of which at least one zeolite has an one dimensional channel structure and at least another zeolite has a multi-dimensional channel structure. More
  • the catalyst comprises ZSM-22 and ZSM-5 or ZSM-22 and ZSM-11.
  • the use of one zeolite having an one dimensional channel structure and one zeolite having a multi-dimensional channel structure has a synergetic effect wherein the multi-dimensional zeolite particularly benefits the cracking of the more refractory paraffins. This results in a higher ethane yield, which is advantageous as ethane can be converted to ethylene with higher yields in a subsequent cracking process in a gas cracker.
  • the catalyst comprises one dimensional channel structure zeolites, having a 10-membered ring channel, and multi-dimensional channel structure zeolites, having a 10-membered ring channel, in a weight ratio of in the range of 10:1 to 1:10, more preferably 3:1 to 1:3, even more preferably 1.5:1 to 1:1.5.
  • the zeolites are at least partly in the hydrogen form, e.g. H-ZSM-5, H-ZSM-11, H- ZSM-22, H-ZSM-23, H-ZSM-48 or H-FER.
  • H-ZSM-5, H-ZSM-11, H- ZSM-22, H-ZSM-23, H-ZSM-48 or H-FER Preferably, at least 50wt%, more preferably at least 90wt%, still more
  • the zeolites When the zeolites are prepared in the presence of organic cations, the zeolites may be activated by heating in an inert or oxidative atmosphere to remove organic cations, for example, by heating at a temperature over 500 °C for 1 hour or more.
  • the zeolite is typically obtained in the sodium or potassium form.
  • the hydrogen form can then be obtained by an ion exchange procedure with ammonium salts followed by another heat treatment, for example in an inert or oxidative atmosphere at a temperature over
  • the zeolites obtained after ion-exchange are also referred to as being in the ammonium form.
  • the silica-to-alumina-ratio is defined as the molar ratio of S1O2/ I2O3 corresponding to the composition of the zeolite, i.e. aluminosilicate molecular sieve.
  • the zeolite has a SAR in the range of from 8 to 500.
  • the zeolite has a SAR in the range of from 10 to 200, more preferably 16 to 150.
  • the zeolite is therefore mixed with a matrix and a binder material and then spray dried or shaped to the desired shape, such as pellets or extrudates.
  • suitable binder material such as pellets or extrudates.
  • materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica, alumina, silica-alumina, titania, zirconia and zeolite.
  • inorganic materials such as clays, silica, alumina, silica-alumina, titania, zirconia and zeolite.
  • materials such as silica and alumina
  • the catalyst used in the process of the present invention comprises, in addition to the zeolite, 2 to 90 wt%, preferably 10 to 85 wt% of a binder material.
  • the catalyst comprises one or more metals.
  • catalyst comprises at least one group VIb, Vllb and/or VIII metal, wherein the group number refers to a group in the Periodic Table of Elements, preferably the catalyst comprises at least one group VIb and or VIII metals, even more preferably at least one group VIII metal.
  • group VIb, Vllb and VIII preferably the incorporation of one or more metals selected from group VIb, Vllb and VIII, optionally in combination with another metal, may reduce the activity of the catalyst towards hydrogenolysis, in particular at temperature above 350 °C, resulting in a reduced methane make .
  • One preferred catalyst comprises one or more group VIII metals, more preferably one or more VIII noble metals such as Pt, Pd, Rh and Ir, even more preferably Pt and/or
  • the catalyst preferably comprises in the range of from 0.05 to 10wt%, more preferably of from 0.1 to 5wt%, even more preferably of from 0.1 to 3wt% of such metals, based on the total weight of the catalyst.
  • Another preferred catalyst comprises at least one group VIb, Vllb and/or VIII metal in combination with one or more other metals, i.e. metals which are not from group VIb, Vllb or VIII.
  • metals which are not from group VIb, Vllb or VIII.
  • Examples of such combinations of a group VIb, Vllb and VIII in combination with another metal include, but are not limited to PtCu, PtSn or NiCu.
  • the catalyst preferably comprises in the range of from 0.05 to 10wt%, more preferably of from 0.1 to 5wt%, even more preferably of from 0.1 to 3wt% of such metals, based on the total weight of the catalyst.
  • Yet another preferred catalyst comprises a combination of a group VIb and a group VIII metal.
  • groups of such combinations of a group VIb and group VIII metal include, but are not limited to, CoMo, NiMo and NiW.
  • the catalyst preferably comprises in the range of from 0.1 to 30wt%, more preferably of from 0.5 to 26wt%, based on the total weight of the catalyst.
  • the feed to the process comprises substantial amounts of sulphur, i.e. sulphur in the form of elemental sulphur or sulphur compounds
  • a catalyst comprising a combination of a group VIb and a group VIII metal.
  • the feed to the process comprises more than lOppmw, more in particular in the range of from lOppmw to 5wt%, of sulphur, based on the weight of the sulphur atoms and the total weight of the feed
  • a catalyst comprising a combination of a group VIb and a group VIII metal more preferably CoMo, NiMo and/or NiW.
  • pre-sulphide the metal or metals in the catalyst may be preferred to pre-sulphide the metal or metals in the catalyst and convert them in a sulfide and/or sulfidic state.
  • Such pre-sulphide pre-treatments are well known in the art and do not need further explanation.
  • the feed to the process comprises little or no sulphur, i.e. sulphur in the form of elemental sulphur or sulphur compounds, it may be preferred to use a
  • catalyst comprising one or group VIII metals, optionally in combination with one or more other metals, i.e. metals which are not from group VIb, Vllb or VIII.
  • the feed to the process comprises in the range of from 0 to 200ppmw, more in particular in the range of from 0 to lOOppmw, of sulphur, based on the weight of the sulphur atoms and the total weight of the feed
  • a catalyst comprising one or group VIII metals, optionally in combination with one or more other metals, i.e. metals which are not from group VIb, Vllb or VIII .
  • the metals may be incorporated into the catalyst by any suitable method known in the art. Examples of such methods include, but are not limited to, impregnation, ion-exchange or other deposition techniques using
  • solutions containing metal salts typically followed by a calcination, reduction step and/or drying step.
  • the metals may be incorporated directly into the zeolite or into the formulated catalyst.
  • the metal-loaded zeolite may be subjected to further calcinations and/or reduction steps directly or may be first be added to a catalyst formulation, thereafter the catalyst formulation, including the metal-loaded zeolite, is subsequently subjected to further calcination and/or reduction steps.
  • metals may be incorporated in the catalyst by a co-mulling process, wherein metal compounds are mixed with the other catalyst ingredients during extrusion of the catalyst.
  • the feed is contacted with the catalyst at elevated temperatures and elevated pressures.
  • the paraffinic feed is contacted with the catalyst at a temperature in the range of from 200 to 650°C, more preferably 250 to 550°C.
  • the exact choice of the temperature will depend on the composition of the feed to the process and the desired product .
  • the paraffinic feed is contacted with the catalyst at a pressure of in the range of from 3 to 100 bar (gauge) , more preferably 5 to 60 bar (gauge) .
  • the paraffinic feed is contacted with the catalyst at a weight hourly space velocity (WHSV) of in the range of from 0.1 to 20 hr _1 , more preferably 0.5 to 10 hr -1 .
  • WHSV weight hourly space velocity
  • Hydrogen may be provided in any suitable ratio to the paraffinic feed.
  • the hydrogen is provided in a molar ratio hydrogen to paraffin feedstock of 1:1 to
  • the process according to the invention to achieve a set conversion of the hydrocarbon feedstock.
  • the ratio of hydrogen to paraffinic feedstock is chosen such that under the process conditions achieving the desired conversion, the hydrogen content in the obtained gas cracker feedstock is no more than lwt%, based on the total weight of the obtained gas cracker feedstock. This is beneficial as hydrogen is an undesired component of the gas cracker feedstock.
  • At least 40wt% of the paraffins comprising 4 to 12 carbon atoms in the paraffinic feed are converted to ethane and/or
  • propane preferably at least 50 wt%, more preferably
  • paraffins in the paraffinic feed are converted to ethane and/or propane.
  • Reference herein to the wt% of paraffins comprising 4 to 12 carbon atoms is to the wt% of paraffins comprising 4 to 12 carbon atoms based on the total weight of paraffins comprising 4 to 12 carbon atoms in the paraffinic feed.
  • the reaction conditions may be selected to obtain a high conversion of the paraffinic feed to ethane.
  • the gas cracker feedstock comprises a high ethane content. More preferably, the gas cracker feedstock comprises ethane and propane in a weight ratio in the range of from 3:2 to 500:1, even more preferably a weight ratio in the range of from 7:3 to 100:1. This may for example be achieved by selecting temperatures at the higher end of the preferred temperature range and/or selecting a WHSV at the lower end of the preferred WVSH range.
  • Ethane is the preferred component in a gas cracker feedstock, however, the high temperature and prolonged residence time may result in an increased undesired methane make .
  • the paraffinic feed is predominantly converted to a mixture of ethane and propane. This may for example be achieved by decreasing the temperature and/or increasing the WHSV relative to the temperature and WHSV used to convert the paraffinic feedstock to predominantly ethane.
  • propane is a lesser preferred component in the gas cracker feedstock, also less undesired methane is produced.
  • the catalyst preferably comprises at least one zeolite having a 10-membered ring channel and a one dimensional channel structure.
  • the catalyst preferably comprises at least one zeolite having a 10-membered ring channel and a multi dimensional channel structure.
  • the paraffinic feed (i.e. the feed containing one or more paraffins comprising 4 to 12 carbon atoms) may be any feed containing one or more paraffins comprising 4 to 12 carbon atom.
  • the paraffinic feed may comprise compounds other than paraffins.
  • the paraffinic feed comprises at least 10wt% of paraffins comprising 4 to 12 carbon atoms, more preferably at least 50wt%, more preferably at least
  • the paraffinic feed comprises in the range of from 10 to 100wt% of paraffins comprising 4 to 12 carbon atoms, more preferably of from 50wt% to 99.5wt%, more preferably of from 60wt% to 99wt of paraffins comprising 4 to 12 carbon atoms.
  • paraffins comprising 4 to 12 carbon atoms in the
  • paraffinic feed is to the wt% of paraffins comprising 4 to 12 carbon atoms based on the total weight the paraffinic feed .
  • the paraffinic feed is or is derived from naphtha.
  • the paraffinic feed may comprise straight run naphtha or naphtha fractions derived from natural gas, natural gas liquids or associated gas.
  • the paraffinic feed may comprise naphtha fractions derived from pyrolysis gas.
  • the paraffinic feed may also comprise naphtha or naphtha fraction obtained from a Fischer-Tropsch process for synthesising hydrocarbons from hydrogen and carbon
  • the feed may also comprise higher paraffins, i.e.
  • paraffins comprising more than 12 carbon atoms. Cracking such higher paraffins typically requires the use of temperatures and pressures which are at the higher end of the preferred temperature and pressure ranges.
  • the paraffinic feed comprises at least one isoparaffin comprising 4 to 12 carbon atoms.
  • the paraffinic feed comprises in the range of from 10 to 90wt% of isoparaffins, more preferably 20 to 60wt% of isoparaffin, based on the total weight of the paraffinic feed .
  • a preferred paraffinic feed comprises isobutane.
  • the paraffinic feed comprises in the range of from 10 to 90wt% of isobutane, more preferably 20 to 60wt% of isobutane, based on the total weight of the paraffinic feed .
  • Another preferred paraffinic feed comprises n-butane.
  • the paraffinic feed comprises in the range of from 10 to 90wt% of n-butane, more preferably 20 to 60wt% of n-butane, based on the total weight of the paraffinic feed .
  • the paraffinic feed comprises at least n-butane and isobutane. More preferably, the paraffinic feed comprises in the range of from 10 to
  • the paraffinic feedstock may comprise olefins.
  • the paraffinic feed comprises in the range of from 0 to 20wt% of olefins, based on the total weight of the
  • paraffinic feed more preferably of from 0 to 10wt% of olefins.
  • the feedstock is subjected to a
  • the present invention provides a process for producing olefins.
  • the gas cracker feedstock is subsequently cracked to obtain olefins, preferably including ethylene.
  • propylene may be formed.
  • Other by-products may be formed such as butylene, butadiene, ethyne, propyne and benzene.
  • the cracking process is performed at elevated
  • temperatures preferably in the range of from 650 to
  • the cracking is performed in the presence of water (steam) as a diluent.
  • the conversion of ethane and propane is typically in the range of from 40 to 75 mol%, based on the total number of moles ethane and propane provided.
  • the un-cracked ethane and propane are recycled back to the cracking zone.
  • Zeolites were used in the ammonium form (NH 4 + ) .
  • the zeolite powders were first pressed into pills, crushed and sieved in a 30-80 mesh sieve fraction. Next, the materials were impregnated with a solution containing Pt (N3 ⁇ 4 ) 4 (NO 3 ) 2 to arrive at a final Pt loading of 0.7 wt%.
  • the catalysts were calcined at for lh 350 °C and for 1 h at 500 °C .
  • Catalyst A 0.7 wt% Pt on zeolite ZSM-22,
  • Catalyst B 0.7 wt% Pt on zeolite ZSM-22/ZSM-5,
  • Comparative catalyst C 0.7 wt% Pt on zeolite Beta
  • the reaction was performed using a stainless steel reactor tube of 1.8 mm internal diameter. About 80 mg of catalyst was placed in the reactor, dried in a nitrogen flow at 100°C, and then reduced in a mixture of 15% hydrogen and 85% nitrogen at atmospheric pressure and 400°C.
  • the catalyst samples were the brought to 250°C after which a mixture consisting of 2.7 vol% n-butane, 7 vol% H 2 , balanced in argon and N 2 was passed over the catalyst at a total pressure of 29 barg (bar gauge) to determine their selectivity towards ethane and propane.
  • the catalysts were tested in the temperature range of 250-550°C.
  • the effluent from the reactor was analyzed by gas chromatography (GC) to determine the product composition.
  • the composition has been calculated on a weight basis of all hydrocarbons analyzed.
  • the selectivity has been defined by the division of the mass of product by the sum of the masses of all C1-C3 products.
  • Table 1 the product distribution is given for experiments conducted with n-butane with all examples having a conversion between 44 and 62wt% conversion of the C4+ fraction, experiments 1 A, IB, 1C and ID.
  • a mixture of hydrogen and isobutane was reacted over the catalysts .
  • the reaction was performed using a stainless steel reactor tube of 1.8 mm internal diameter. About 80 mg of catalyst was placed in the reactor, dried in a nitrogen flow at 100°C, and then reduced in a mixture of 15% hydrogen and 85% nitrogen at atmospheric pressure and
  • the catalyst samples were the brought to 250°C after which a mixture consisting of 2.7 vol% isobutane, 7 vol% 3 ⁇ 4, balanced in argon and 2 was passed over the catalyst at a total pressure of 29 barg (bar gauge) to determine their selectivity towards ethane and propane.
  • the catalysts were tested in the temperature range of 250-550°C.
  • the effluent from the reactor was analyzed by gas chromatography (GC) to determine the product composition.
  • the composition has been calculated on a weight basis of all hydrocarbons analyzed.
  • the selectivity has been defined by the division of the mass of product by the sum of the masses of all C1-C3 products.
  • Table 3 gives the results from experiments performed with iso-butane at 400°C, experiments 1 E, IF, 1G and 1H and 450°C, experiments 1 EE, IFF, 1GG and 1HH.
  • the catalyst A displayed a selectivity of 68wt% to ethane .
  • Catalyst E 0.7 wt% Pt on zeolite ZSM-5
  • Catalyst F 0.7 wt% Pt on zeolite ZSM-11,
  • Comparative catalyst G 0.7 wt% Pt on zeolite ZSM-12,
  • Comparative catalyst H 0.7 wt% Pt on zeolite Y
  • the effluent from the reactor was analyzed by online gas chromatography (GC) to determine the product composition.
  • GC gas chromatography
  • the composition has been calculated on a weight basis of all hydrocarbons analyzed.
  • the selectivity has been defined by the division of the mass of product by the sum of the masses of all Cl-
  • Table 5 compares product distributions obtained from experiments 2A to 2D at high cracking conversions, i.e. a C4+ conversion over 75wt% and a C3+ conversion over 36wt%.
  • Example 3 Integrated process to produce olefins

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Abstract

La présente invention porte sur un procédé de préparation d'une charge de départ de craqueur de gaz, ledit procédé comportant la mise en contact d'une charge, contenant une ou plusieurs paraffines comportant 4 à 12 atomes de carbone, avec un catalyseur, comportant au moins une zéolite ayant des canaux cycliques à 10 chaînons et au moins un métal du groupe VIb, du groupe VIIb et/ou du groupe VIII, en présence d'hydrogène à des températures et des pressions élevées, et la conversion d'au moins 40 % en poids des paraffines comportant 4 à 12 atomes de carbone, sur la base du poids total desdites paraffines présentes dans la charge, en éthane et/ou propane afin d'obtenir une charge de départ de craqueur de gaz d'hydrocraquage comportant de l'éthane et/ou du propane. Sous un autre aspect, l'invention porte également sur un procédé de production d'oléfines.
PCT/US2011/058599 2010-11-01 2011-10-31 Procédé de préparation de charge de départ de craqueur de gaz WO2012071137A1 (fr)

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WO2016102248A1 (fr) 2014-12-22 2016-06-30 Sabic Global Technologies B.V. Procédé de production d'hydrocarbures c2 et c3
WO2016102247A1 (fr) 2014-12-22 2016-06-30 Sabic Global Technologies B.V. Procédé de production d'hydrocarbures c2 et c3
WO2016102249A1 (fr) 2014-12-22 2016-06-30 Sabic Global Technologies B.V. Procédé de production de gpl et de btx
WO2016102250A1 (fr) 2014-12-22 2016-06-30 Sabic Global Technologies B.V. Procédé de production de gpl et de btx
WO2017101985A1 (fr) 2015-12-15 2017-06-22 Sabic Global Technologies B.V. Procédé de production d'hydrocarbures c2 et c3
WO2019162393A1 (fr) 2018-02-22 2019-08-29 Total Research & Technology Feluy Conversion sélective de naphta paraffinique en propylène en présence d'hydrogène
US10899979B2 (en) 2017-08-15 2021-01-26 Sabic Global Technologies, B.V. Light olefin production via an integrated steam cracking and hydrocracking process
US11203558B2 (en) 2018-09-19 2021-12-21 Sabic Global Technologies, B.V. Selective hydrogenolysis integrated with cracking
US11254628B1 (en) 2020-07-28 2022-02-22 Sabic Global Technologies B.V. Methods of butane hydrogenolysis under hydrogen-lean conditions
US11559795B2 (en) 2018-09-19 2023-01-24 Sabic Global Technologies, B.V. Bimetallic catalysts supported on zeolites for selective conversion of n-butane to ethane
US11603344B2 (en) 2018-09-19 2023-03-14 Sabic Global Technologies, B.V. Selective hydrogenolysis integrated with MTBE production
US11773037B2 (en) 2019-03-05 2023-10-03 Sabic Global Technologies B.V. Distribution hub for C4 conversion to ethane/propane feedstock network
WO2023244596A1 (fr) * 2022-06-13 2023-12-21 Uop Llc Procédé de conversion catalytique de naphta en oléfines légères avec des modes prédominants

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WO2015128036A1 (fr) * 2014-02-25 2015-09-03 Saudi Basic Industries Corporation Procédé de valorisation d'hydrocarbures lourds de raffinerie en produits pétrochimiques
EA032758B1 (ru) * 2014-02-25 2019-07-31 Сауди Бейсик Индастриз Корпорейшн Способ облагораживания тяжелых углеводородов нефтепереработки в нефтехимические продукты
US10526551B2 (en) 2014-12-22 2020-01-07 Sabic Global Technologies B.V. Process for producing C2 and C3 hydrocarbons
WO2016102248A1 (fr) 2014-12-22 2016-06-30 Sabic Global Technologies B.V. Procédé de production d'hydrocarbures c2 et c3
WO2016102247A1 (fr) 2014-12-22 2016-06-30 Sabic Global Technologies B.V. Procédé de production d'hydrocarbures c2 et c3
WO2016102249A1 (fr) 2014-12-22 2016-06-30 Sabic Global Technologies B.V. Procédé de production de gpl et de btx
WO2016102250A1 (fr) 2014-12-22 2016-06-30 Sabic Global Technologies B.V. Procédé de production de gpl et de btx
US10087378B2 (en) 2014-12-22 2018-10-02 Sabic Global Technologies B.V. Process for producing LPG and BTX
US10174263B2 (en) 2014-12-22 2019-01-08 Sabic Global Technologies B.V. Process for producing C2 and C3 hydrocarbons
US10287517B2 (en) 2014-12-22 2019-05-14 Sabic Global Technologies B.V. Process for producing C2 and C3 hydrocarbons
US10287518B2 (en) 2014-12-22 2019-05-14 Sabic Global Technologies B.V. Process for producing LPG and BTX
USRE49154E1 (en) 2014-12-22 2022-08-02 Sabic Global Technologies B.V. Process for producing LPG and BTX
WO2017101985A1 (fr) 2015-12-15 2017-06-22 Sabic Global Technologies B.V. Procédé de production d'hydrocarbures c2 et c3
US10899979B2 (en) 2017-08-15 2021-01-26 Sabic Global Technologies, B.V. Light olefin production via an integrated steam cracking and hydrocracking process
WO2019162392A1 (fr) 2018-02-22 2019-08-29 Total Research & Technology Feluy Conversion sélective de naphta paraffinique en propane en présence d'hydrogène
WO2019162393A1 (fr) 2018-02-22 2019-08-29 Total Research & Technology Feluy Conversion sélective de naphta paraffinique en propylène en présence d'hydrogène
US11203558B2 (en) 2018-09-19 2021-12-21 Sabic Global Technologies, B.V. Selective hydrogenolysis integrated with cracking
US11559795B2 (en) 2018-09-19 2023-01-24 Sabic Global Technologies, B.V. Bimetallic catalysts supported on zeolites for selective conversion of n-butane to ethane
US11603344B2 (en) 2018-09-19 2023-03-14 Sabic Global Technologies, B.V. Selective hydrogenolysis integrated with MTBE production
US11773037B2 (en) 2019-03-05 2023-10-03 Sabic Global Technologies B.V. Distribution hub for C4 conversion to ethane/propane feedstock network
US11254628B1 (en) 2020-07-28 2022-02-22 Sabic Global Technologies B.V. Methods of butane hydrogenolysis under hydrogen-lean conditions
WO2023244596A1 (fr) * 2022-06-13 2023-12-21 Uop Llc Procédé de conversion catalytique de naphta en oléfines légères avec des modes prédominants

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