WO2001081280A1 - Procede catalytique de fabrication de propylene et d'ethylene - Google Patents

Procede catalytique de fabrication de propylene et d'ethylene Download PDF

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Publication number
WO2001081280A1
WO2001081280A1 PCT/US2001/010009 US0110009W WO0181280A1 WO 2001081280 A1 WO2001081280 A1 WO 2001081280A1 US 0110009 W US0110009 W US 0110009W WO 0181280 A1 WO0181280 A1 WO 0181280A1
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WIPO (PCT)
Prior art keywords
catalyst
range
olefins
ethylene
zeolite
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PCT/US2001/010009
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English (en)
Inventor
Donald H. Powers
Kenneth M. Webber
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Equistar Chemicals, L.P.
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Publication date
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Priority to AU2001251074A priority Critical patent/AU2001251074A1/en
Publication of WO2001081280A1 publication Critical patent/WO2001081280A1/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
    • 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
    • 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 making propylene and ethylene from higher (C4 to C9) olefins using particular zeolite catalysts and, advantageously, a fixed-bed reactor.
  • Propylene and ethylene are produced commercially by a number of methods, including, for example, steam cracking or pyrolysis of paraffinic materials, petroleum refinery cracking, and alkane dehydrogenation.
  • U.S. Pat. No. 5,043,522 explains some of the problems with these methods for making propylene.
  • Disproportionation of olefin mixtures to make ethylene or propylene is also known, and is described, for example, in U.S. Pat. Nos. 4,180,524, 4,499,328, and 4,517,401.
  • These processes generally use amorphous catalysts such as tungsten or molybdenum oxides with other compounds that help to promote the disproportionation.
  • Zeolites are a well-known class of natural and synthetic crystalline aluminosilicates that comprise networks of Si ⁇ 4 and AIO4 tetrahedra in which the silicon and aluminum atoms are crosslinked by shared oxygen atoms. Zeolites contain channels or voids of characteristic dimensions. The channel openings, or "pores,” can be rather circular, but more often they are elliptical or irregular in shape. In some zeolites, the channels are one- dimensional and do not interconnect, as in a series of parallel tunnels. In others, the channels intersect and form large cavities at the intersections.
  • the channels normally contain cations such as sodium, potassium, magnesium, ammonium, or the like, and may contain protons or water molecules. Water can be removed by heating, leaving an active site within the catalyst. The cations can be exchanged, in whole or part, by other different cations, or by protons to make the "H" form of the zeolite.
  • Zeolites have been used for many types of hydrocarbon transformations, including, for example, toluene disproportionation (see, e.g., U.S. Pat. No. 4,160,788), hydrocarbon oil dewaxing (U.S. Pat. No. 5,000,840), selective sorption of hydrocarbons (U.S. Pat. No. 4,423,280), olefin oligomerization (U.S. Pat. No. 4,855,527) or isomerization (U.S. Pat. No. 5,177,281 or 5,817,907), gasoline upgrading (U.S. Pat. No. 5,298,150), desulfurization of hydrocarbons (U.S. Pat. No. 5,401 ,391), and conversion of C5 linear olefins to tert-alkyl ethers (U.S. Pat. No. 5,420,360).
  • toluene disproportionation see, e.g., U.S. Pat. No. 4,160,78
  • Zeolites have also been used in processes for making propylene or ethylene from mixtures of olefins and paraffinic hydrocarbons.
  • U.S. Pat. Nos. 5,043,522 and 5,026,936 describe a process for making propylene in which a mixture of 40-95 wt.% paraffinic hydrocarbons (C4 and higher) and 5-60 wt.% olefins (C4 and higher) are heated in the presence of certain zeolites.
  • the examples use ZSM-5, a zeolite that has interconnecting channels in three dimensions with pore size indices greater than 25.
  • ZSM-5 uses ZSM-5 to make ethylene from higher hydrocarbons (including butenes and/or propylene) by a cracking process.
  • ZSM-5 is not well-suited for use in a fixed-bed process, which requires a prolonged catalyst lifetime, because it tends to "coke up" from aromatic hydrocarbons forming within its channels. ZSM-5, therefore, would require continuous regeneration if it were used in a fixed-bed process.
  • the process could use the C4 to C9 olefin streams that are readily available from steam or catalytic cracking.
  • the process would retard catalyst coking and deactivation, which hampers productivity in many processes that use heterogeneous catalysts such as zeolites.
  • An ideal process would give valuable ethylene and propylene in favorable ultimate conversions, yields, and selectivities, yet would have a long enough catalyst life to be suitable for use with fixed-bed reactors.
  • the invention is a process for making propylene and ethylene.
  • the process comprises heating one or more C4 to C9 olefins with a particular zeolite catalyst under conditions effective to produce propylene and ethylene.
  • the catalyst has a pore diameter of 4.4 to 4.5 A and one- dimensional, non-interconnecting channels having a pore size index within the range of 23 to 25.
  • Well-known zeolites in this class are MTT (ZSM-23) and TON (THETA I).
  • the process of the invention affords high olefin conversions and excellent selectivities to valuable ethylene and propylene. Because catalyst lifetime is long (especially when the catalyst is passivated, as by steam treatment, e.g.), the process is ideal for use with a fixed bed of catalyst. Major by-products are typically higher olefins that can be recycled to further boost ultimate conversion. Proper selection of the zeolite to those having the particular characteristics noted above minimizes coking and aromatic byproducts, and maximizes yields of propylene and ethylene.
  • the hydrocarbon feed used as a starting material for the process of the invention is a mixture that contains one or more C4 to C9 olefins.
  • Suitable olefins are linear or branched isomers that contain four to nine carbons and a single carbon-carbon double bond.
  • the hydrocarbon feed can include linear and branched nonenes, octenes, heptenes, hexenes, and the like.
  • Particularly preferred are streams that contain mixtures of C4 and C5 olefins, such as 1-butene, cis-2-butene, trans-2- butene, isobutene, 1-pentene, cis-2-pentene, trans-2-pentene, 3-methyl-1- butene, 2-methyl-2-butene, 2-methyl-1-butene, and mixtures of these.
  • While the feed can (and often will) contain other types of hydrocarbons, it preferably comprises more than 40 wt.%, more preferably more than 60 wt.%, of C4 to C9 olefins.
  • Hydrocarbon streams suitable for use in the process of the invention include C4 and C5 streams (with or without the isobutene component) from fluid catalytic crackers or hydrocarbon pyrolysis units.
  • a preferred hydrocarbon stream consists essentially of C4 and/or C5 olefins.
  • the C4 to C9 olefin mixture is converted to propylene and ethylene by contacting it with a particular zeolite catalyst. While many varieties of zeolite catalysts are known, only certain types are useful in the invention.
  • Useful zeolites are medium-pore zeolites or zeolite-type materials that have a 10-membered ring channel structure and a pore diameter of 4.4 to 4.5 A.
  • pore diameter we mean the diameter of the ring aperture or pore measured at its narrowest dimension, or the smaller of the two major axes for an elliptical pore.
  • a catalyst that has channels with elliptical apertures measuring 3.3 x 5.0 A does not meet the requirements of the invention because the narrowest dimension (the smaller of the major axes) is not "4.4 to 4.5 A.”
  • Zeolites that have a pore diameter less than 4.4 A are not suitable for use because they are too narrow to permit entry of C4 to C9 olefins into the channels.
  • Zeolites useful in the invention have one-dimensional, non- interconnecting channels.
  • one-dimensional, non-interconnecting channels we mean ones that are more or less parallel and non-intersecting.
  • Zeolite handbooks such as W.M. Meier et al., Atlas of Zeolite Structure Types. 4th Revised Ed. (1996), hereinafter referred to as "the Atlas,” identify such one-dimensional zeolites with a single asterisk ( * ) in their description of the channels.
  • each system of equivalent channels is characterized by (1) the channel direction (relative to the axes of the type structure), (2) the number of either T- (usually Si or Al) or O- atoms, in bold type, that form the rings controlling diffusion through the channels, and (3) the crystallographic free diameters of the channels in Angstroms, based on the atomic coordinates of the type materials and an oxygen radius of 1.35 A.
  • the number of asterisks indicates whether the channel system is one-, two-, or three-dimensional.
  • Interconnecting channels are separated by a double arrow ( ⁇ -->).
  • MTT ZSM-23
  • a zeolite useful in the invention has a one- dimensional channel structure.
  • the Atlas describes its channels as follows: [001] 10 4.5 x 5.2*.
  • the boldface 10 indicates a 10-membered ring structure, the 4.5 and 5.2 refer to pore diameter (in Angstroms; two numbers because of the non-circular apertures), and the asterisk identifies the channels as one-dimensional and non-interconnecting.
  • MFI ZSM-5
  • a zeolite that is not useful in the invention has three-dimensional, interconnecting channels.
  • the Atlas describes its channels as follows: ⁇ [010] 10 5.3 x 5.6 ⁇ --> [100] 10 5.1 x 5.5 ⁇ ** *.
  • the triple asterisk denotes a three-dimensional structure, and the double arrow indicates that the channels interconnect.
  • Zeolites useful in the invention have a pore size index within the range of 23 to 25.
  • pore size index we mean the product of the dimensions (in Angstrom units) of the two major axes of the pores. This is the definition used, e.g., by Haag et al. in U.S. Pat. No. 5,177,281. The pore dimensions are simply multiplied together to get the pore size index.
  • TON THETA 1
  • a zeolite catalyst useful in the invention has elliptical pores measuring 4.4 x 5.5 A. Multiplying these numbers gives a pore size index for TON of 24.2.
  • Cancrinite on the other hand, a catalyst not useful in the invention, has pores measuring 5.9 A, and a pore size index of 34.8 (i.e., greater than the upper limit of 25 for catalysts useful in the invention).
  • Information about many zeolites is now available "online" courtesy of the Structure Commission of the International Zeolite Association. The website address is: www.iza-sc.ethz.ch/IZA-SC.
  • zeolites useful in the process of the invention have in common are channels large enough to admit the C4 to C9 olefins and large enough to allow propylene and ethylene to diffuse out.
  • the channels are generally small enough to minimize formation of hydrocarbon coke precursors within the channels.
  • zeolites are not useful in the process of the invention.
  • MTW ZSM-12
  • MEL ZSM-11
  • MFI ZSM-5
  • Ferrierite pore diameter ⁇ 4.4 A
  • chabazite CHA
  • Linde Type A LTA
  • the zeolites used in the process of the invention are usually powders.
  • the zeolites are optionally combined with one or more binders.
  • Suitable binders are well known in the art and include, for example, natural clays (e.g., montmorillonite, kaolin, bentonite), silicas, aluminas, and the like. Aluminas and silicas are preferred.
  • a binder When a binder is used, it is typically present in an amount within the range of about 0.5 to about 40 wt.% based on the combined amounts of binder and zeolite catalyst.
  • the binders can be used in any convenient form, including powders, slurries, gels, or the like.
  • the catalyst powder and/or binder can be combined with water and mulled using commercial mullers such as the Lancaster Mix Muller to produce a catalyst- containing paste.
  • the zeolite catalyst can be used alone in powder or pelletized form.
  • zeolite catalysts are normally synthesized in the alkali metal form, it is generally preferred to use the hydrogen form of the zeolite in the process of the invention.
  • Zeolites are conveniently converted to the hydrogen form by ion exchange with ammonium halide or nitrate solution, followed by calcination. It has been found that this procedure prolongs catalyst lifetime. Moreover, the amount of aromatics generated from the process tends to decrease with time.
  • the original alkali metal can also be replaced by other suitable metal cations, such as other alkali metals, calcium, magnesium, or the like. These metals can regulate the effective pore size index of the zeolite. For example, converting a zeolite to the hydrogen form generally increases the effective pore size index relative to the alkali metal form of the catalyst, while substituting the alkali metal with a metal tends to decrease the effective pore size index. Whether or not the zeolite catalyst is modified by converting it to the H-form, or by metal substitution, the effective pore size index needs to be within the limits defined herein.
  • the alkali metal can be replaced by a transition metal if desired to improve selectivity or modify the product mixture.
  • the catalysts can be prepared for use by any number of methods, which are now well known in the art.
  • the patent literature provides synthetic methods for MTT (U.S. Pat. Nos. 4,076,842 and 4,490,342) and TON (U.S. Pat. Nos. 4,556,477 and 5,342,596).
  • the zeolites can be used essentially "as is.” Usually, however, the zeolites are calcined prior to use to remove traces of water, preferably by heating them at a temperature within the range of about 200°C to about 750°C, more preferably from about 300°C to about 650°C, and most preferably from about 450°C to about 600°C.
  • a binder e.g., alumina
  • calcination usually follows the pelletization process. Pellets are usually made by extrusion.
  • one or more peptizing acids e.g., nitric acid, citric acid, or acetic acid
  • an extrusion aid e.g., hydroxypropyl methylcellulose
  • an oxidizing metal such as Pd or Pt can be used, if desired, to promote coke removal during catalyst regeneration (see, e.g., U.S. Pat. No. 5,648,585).
  • the zeolites are preferably passivated prior to use; steam treatment is one way to passivate the zeolites. We found that steam treatment significantly prolongs catalyst lifetime. Prolonged catalyst lifetime is important for making the catalyst valuable for a fixed-bed process.
  • Steaming is normally done after preparation, pelletization, and drying of the catalyst. In one convenient procedure, steaming is performed just prior to using the catalyst for hydrocarbon conversion. Water is slowly fed to the reactor by any convenient means while the reactor is at a temperature greater than 100°C, usually from about 110°C to about 200°C, and the temperature is slowly elevated. Steaming is usually performed at elevated temperatures of about 450°C to about 700°C for a time ranging from several hours to several days.
  • the mixture of C4 to C9 olefins is contacted with the zeolite catalyst under conditions effective to produce propylene and ethylene.
  • the process is performed in the vapor phase by bringing a heated olefin mixture into contact with the zeolite catalyst. Either the catalyst or the olefin mixture (or both) can be heated.
  • the reaction is performed at a temperature within the range of about 400°C to about 750°C, more preferably from about 450°C to about 700°C, and most preferably from about 500°C to about 600°C.
  • While the reactor pressure is not usually critical, it is preferred to perform the process at a total reactor pressure within the range of about 0.5 to about 10 atmospheres, more preferably from about 1 to 4 atmospheres. Any suitable feed rate can be used. Generally, it is preferred to use a hydrocarbon weight hourly space velocity (WHSV) within the range of about 0.5 to about 1000 h "1 , more preferably from about 1 to 50 h ⁇ 1 . If desired, hydrogen or a diluent can be added to the feedstock.
  • WHSV hydrocarbon weight hourly space velocity
  • the process of the invention can be practiced in a batch, continuous, semi-batch, or semi-continuous manner.
  • a continuous process is preferred.
  • the catalyst can be regenerated using conventional techniques such as treatment with air diluted with an inert gas such as nitrogen.
  • the process can be used with any desired kind of reactor system, including, for example, a fixed-bed, moving-bed, or fluidized-bed reactor system.
  • the catalysts, when pelletized or combined with a binder and extruded, are particularly useful in a fixed-bed reactor system.
  • the laboratory pilot unit is a semi-automated unit that can control temperature and pressure.
  • the reactor is located within a convection oven to control temperature in the reactor.
  • Hydrocarbon flow is controlled by a flow meter and flow control valve.
  • the pressure of the system is controlled by the vent header pressure at 0-3 psig.
  • Process variable data is collected and stored using software on a Local Area Network.
  • Reactor effluent compositions are measured periodically by an on-line gas chromatograph (GC).
  • GC on-line gas chromatograph
  • the reactor is constructed from Vz stainless steel tubing and fittings.
  • the reactor consists of two zones: a preheat section and a reaction section.
  • the preheat section is 1-2" long and is packed with 8-14 mesh tabular corundum.
  • a layer of glass or quartz wool separates the preheat section from the reaction section.
  • a "tee" fitting is situated at the start of the reaction zone. This fitting allows the radial insertion of a thermocouple to measure fluid temperature as it enters the reaction zone.
  • the reaction section is 3-5" long and contains about 2-4 grams of catalyst.
  • the catalyst is a pressed powder that is broken into pieces and sieved. The pieces that are retained between 12 and 20 mesh screens are used in the reactor.
  • a plug of glass or quartz wool is placed on top of the catalyst bed and the remainder of the reactor is filled with tabular corundum to secure the catalyst in its position and prevent any fluidization during normal operations.
  • the catalyst can be subjected to "conditioning" steps, namely drying and/or steaming.
  • "conditioning" steps namely drying and/or steaming.
  • a stream of nitrogen is passed over the bed, while the oven temperature is slowly ramped from ambient temperature to 104°C and held there for at least one hour.
  • Steaming is done after drying. Water is fed to the reactor via a high pressure syringe pump at a rate less than 1 mlJh while the reactor is at a temperature greater than 100°C.
  • the oven temperature is increased to obtain the desired steaming temperature (as measured by the thermocouple situated at the beginning of the catalyst bed). Steaming lasts from 4 to 60 hours.
  • the reactor temperature is adjusted to run conditions (in the range of 450-750°C) from the steaming conditions while water is flowing. Once reaction temperature is reached, the water flow is terminated and hydrocarbon feed (a mixture of butenes and butanes) is started. Nitrogen head pressure on a liquid reservoir of the feed material is used to drive the feed through the reactor. Once the feed has reached the tubing within the oven, it is vaporized. This vaporized feed passes over the catalyst bed and is reacted. A portion of the vaporous product mixture is directed to a GC sampling valve through a heated transfer line. Periodically, this stream is analyzed for composition by the GC.
  • hydrocarbon feed a mixture of butenes and butanes
  • a sample of MTT zeolite (20.47 g of Na form, 67/1 SiO2/AI2O3) is mixed with 200 mL of a solution of ammonium nitrate (2.23 N, 18.1 eq. of ammonium per eq. of sodium) and 200 mL of deionized water, and the mixture is stirred for 2 h at reflux.
  • the catalyst is filtered to remove the liquid. This exchange process is repeated four more times.
  • the zeolite is washed with 400 mL deionized water and filtered. This washing process is repeated four times.
  • the washed zeolite is transferred to a porcelain crucible, which is placed in an oven at 100°C for 14 h.
  • the oven temperature is increased at 100°C for 14 h.
  • zeolite 100°C per hour to 550°C, and is held at that temperature for an additional 8 hours.
  • the zeolite is removed from the oven and allowed to cool in a dessicator.
  • a portion of the zeolite is pressed into wafers.
  • the wafers are broken into pieces with a mortar and pestle.
  • the pieces are sieved and the portion that is retained between 12 and 20 mesh (U. S. Standard) is used to load the reactor.
  • the reactor is loaded (from bottom to top) with V- ⁇ l pad of quartz wool,
  • thermocouple is inserted axially into the quartz wool pad below the catalyst bed.
  • the reactor is placed in the oven and connected to the feed and effluent sections of the pilot unit. Nitrogen is swept through the reactor as the catalyst is dried by raising the temperature and holding as follows:
  • the zeolite is steamed. With nitrogen flowing and the reactor at 104°C, water is injected into the system at a rate of 0.25 mL/h. The temperature of the reactor is raised to 600°C and is held there for 24 h. The reactor is then cooled to approximately 510°C.
  • Nitrogen and water feeds are discontinued and the hydrocarbon feed is started at approximately 7 g/h.
  • the composition of the feed is given below:
  • the reactor effluent is analyzed periodically (every 2-3 h) by on-line

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

Selon cette invention, du propylène et de l'éthylène sont fabriqués par chauffage d'au moins une oléfine C4 à C9 avec un catalyseur de zéolithe possédant un diamètre de pore compris dans une plage de 4.4 à 4.5 A et des canaux unidimensionnels et non reliés entre eux possédant un indice de taille de pore compris dans une plage de 23 à 25. De préférence, les zéolithes sont TON et MTT. Ce procédé permet de hautes conversions d'oléfines et une excellente sélectivité à l'éthylène et au propylène. Etant donné que la durée de vie du catalyseur est longue, surtout si le catalyseur est traité à la vapeur, un procédé à lit fixe peut être utilisé. Des oléfines supérieures, en général le principal produit dérivé, sont recyclées pour stimuler davantage la conversion finale.
PCT/US2001/010009 2000-04-26 2001-03-28 Procede catalytique de fabrication de propylene et d'ethylene WO2001081280A1 (fr)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007135055A1 (fr) * 2006-05-19 2007-11-29 Shell Internationale Research Maatschappij B.V. Procédé de préparation de polypropylène
WO2007135058A1 (fr) * 2006-05-19 2007-11-29 Shell Internationale Research Maatschappij B.V. Procédé de préparation de propylène à partir d'une charge d'hydrocarbure
US7601663B2 (en) 2004-09-10 2009-10-13 Sk Energy Co., Ltd. Solid acid catalyst for producing light olefins and process using the same
US7799834B2 (en) 2006-05-30 2010-09-21 Starchem Technologies, Inc. Methanol production process and system
US20100256431A1 (en) * 2007-07-31 2010-10-07 Total Petrochemicals Research Feluy Cracking of Olefins on Phosphorus Modified Molecular Sieves
US7932427B2 (en) 2006-05-19 2011-04-26 Shell Oil Company Process for the preparation of propylene and industrial plant thereof
US8049054B2 (en) 2006-05-19 2011-11-01 Shell Oil Company Process for the preparation of C5 and/or C6 olefin
US8168842B2 (en) 2006-05-19 2012-05-01 Shell Oil Company Process for the alkylation of a cycloalkene
US8598398B2 (en) 2006-05-19 2013-12-03 Shell Oil Company Process for the preparation of an olefin
US8822749B2 (en) 2007-11-19 2014-09-02 Shell Oil Company Process for the preparation of an olefinic product
CN113443955A (zh) * 2021-06-28 2021-09-28 江苏斯尔邦石化有限公司 一种c4～c6烯烃的催化裂解制备丙烯的方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5026936A (en) * 1989-10-02 1991-06-25 Arco Chemical Technology, Inc. Enhanced production of propylene from higher hydrocarbons
WO2000026163A1 (fr) * 1998-11-04 2000-05-11 Equistar Chemicals, L.P. Procede de preparation de propylene et d'ethylene

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5026936A (en) * 1989-10-02 1991-06-25 Arco Chemical Technology, Inc. Enhanced production of propylene from higher hydrocarbons
WO2000026163A1 (fr) * 1998-11-04 2000-05-11 Equistar Chemicals, L.P. Procede de preparation de propylene et d'ethylene

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7601663B2 (en) 2004-09-10 2009-10-13 Sk Energy Co., Ltd. Solid acid catalyst for producing light olefins and process using the same
US8168842B2 (en) 2006-05-19 2012-05-01 Shell Oil Company Process for the alkylation of a cycloalkene
WO2007135058A1 (fr) * 2006-05-19 2007-11-29 Shell Internationale Research Maatschappij B.V. Procédé de préparation de propylène à partir d'une charge d'hydrocarbure
US7932427B2 (en) 2006-05-19 2011-04-26 Shell Oil Company Process for the preparation of propylene and industrial plant thereof
AU2007253402B2 (en) * 2006-05-19 2011-06-16 Shell Internationale Research Maatschappij B.V. Process for the preparation of propylene from a hydrocarbon feed
US8049054B2 (en) 2006-05-19 2011-11-01 Shell Oil Company Process for the preparation of C5 and/or C6 olefin
WO2007135055A1 (fr) * 2006-05-19 2007-11-29 Shell Internationale Research Maatschappij B.V. Procédé de préparation de polypropylène
US8598398B2 (en) 2006-05-19 2013-12-03 Shell Oil Company Process for the preparation of an olefin
US7799834B2 (en) 2006-05-30 2010-09-21 Starchem Technologies, Inc. Methanol production process and system
US8143320B2 (en) 2006-05-30 2012-03-27 Starchem Technologies, Inc. Methanol production process and system
US20100256431A1 (en) * 2007-07-31 2010-10-07 Total Petrochemicals Research Feluy Cracking of Olefins on Phosphorus Modified Molecular Sieves
US8822749B2 (en) 2007-11-19 2014-09-02 Shell Oil Company Process for the preparation of an olefinic product
CN113443955A (zh) * 2021-06-28 2021-09-28 江苏斯尔邦石化有限公司 一种c4～c6烯烃的催化裂解制备丙烯的方法

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