EP1127039A1 - Procede de preparation de propylene et d'ethylene - Google Patents

Procede de preparation de propylene et d'ethylene

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Publication number
EP1127039A1
EP1127039A1 EP99954851A EP99954851A EP1127039A1 EP 1127039 A1 EP1127039 A1 EP 1127039A1 EP 99954851 A EP99954851 A EP 99954851A EP 99954851 A EP99954851 A EP 99954851A EP 1127039 A1 EP1127039 A1 EP 1127039A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
channels
olefins
range
ethylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99954851A
Other languages
German (de)
English (en)
Inventor
Donald H. Powers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Equistar Chemicals LP
Original Assignee
Equistar Chemicals LP
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Equistar Chemicals LP filed Critical Equistar Chemicals LP
Publication of EP1127039A1 publication Critical patent/EP1127039A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C07C2529/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
    • 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

Definitions

  • the invention relates to a process for making propylene and ethylene from higher (C4 and C5) olefins using zeolite catalysts that have particular channel dimensions.
  • 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 SiO 4 and AIO 4 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.
  • 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 ), 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. 4,160,788), hydrocarbon oil
  • 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 and a pore size index greater than 28.
  • U.S. Pat. No. 5,026,935 uses ZSM-5 to make ethylene from higher hydrocarbons (including butenes and/or propylene) by a cracking process.
  • the process could use the C4 and C5 olefin streams that are readily available from steam 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 yields and selectivities, yet would be suitable for use with fixed-bed reactor systems.
  • the invention is a process for making propylene and ethylene.
  • the process comprises heating a mixture of C4 and/or C5 olefins with a particular zeolite catalyst under conditions effective to produce propylene and ethylene.
  • the catalyst has a pore diameter greater than 3.5 A and one-dimensional, non-interconnecting channels having a pore size index within the range of 14 to 28.
  • zeolite catalysts that have one or more interconnecting channels, including (1 ) a primary channel that has a pore diameter greater than 3.5 A and a pore size index within the range of 14 to 28, and (2) a secondary channel interconnected therewith that has a pore size index less than 20.
  • Catalysts used in the process of the invention are uniquely well suited to the production of propylene and ethylene from C4 and/or C5 olefin streams.
  • they have channels large enough to admit the C4 and/or C5 olefins and large enough to allow propylene and ethylene to diffuse out.
  • the channels are also small enough to retard diffusion of dimerized products from the channels and small enough to minimize formation of hydrocarbon coke precursors within the channels.
  • the hydrocarbon feed used as a starting material for the process of the invention is a mixture that contains C4 and/or C5 olefins.
  • C4 and/or C5 olefins we mean linear or branched isomers that contain four or five carbons and a single carbon-carbon double bond. These include the various butene and pentene isomers, 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.
  • 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 and/or C5 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 fall into the general category of medium or intermediate pore zeolites, which typically have a 10-membered ring or puckered 12-membered ring channel structure (see Table 1 below), although numerous 8-membered ring zeolites will also be suitable (see especially Table 2 below).
  • Useful zeolites have a pore diameter greater than 3.5 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 A x 5.0 A would not meet the requirements of the invention because the narrowest dimension (the smaller of the major axes) is not “greater than 3.5 A.”
  • Zeolites that have a pore diameter less than or equal to 3.5 ⁇ are not suitable for use because they are too narrow to permit entry of C4 and/or C5 olefins into the channels.
  • Preferred zeolites have a pore diameter greater than 3.7 A; most preferred are zeolites that have a pore diameter greater than 4.0 A.
  • 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.
  • MTT ZSM-23
  • a zeolite useful in the invention has a one-dimensional channel structure.
  • the Atlas describes its channels as follows: [001] 104.5 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 14 to 28.
  • 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 teachings of which are incorporated herein by reference. The pore dimensions are simply multiplied together to get the pore size index.
  • TON ZSM-22
  • 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.
  • 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 28 for catalysts useful in the invention).
  • the channels have a pore size index within the range of 16 to 25.
  • Table 1 summarizes examples of zeolite catalysts useful in the process of the invention, along with their channel descriptions (from the Atlas), minimum pore diameters, and pore size indices.
  • the channel descriptions follow the notation used in the Atlas.
  • 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 ( ⁇ ->).
  • ) means that there is no direct access from one channel system to another.
  • useful zeolites include the topological equivalents of these materials, which are described in the Atlas and on the website listed below. All of the above information about these zeolites is now available "online” courtesy of the Structure Commission of the International Zeolite Association. The website address is: http://www-iza-sc.csb.yale.edu
  • the process of the invention can be performed using certain zeolites that have one or more interconnecting channels.
  • Such zeolites must have: (1 ) a primary channel that has a pore diameter greater than 3.5 A and a pore size index within the range of 14 to 28; and (2) a secondary channel interconnected with the primary channel that has a pore size index less than 20.
  • Table 2 lists examples of zeolites that meet these criteria.
  • Ferrierite is a good example of a zeolite having interconnecting channels, yet still suitable for use in the process of the invention.
  • Table 2 shows, ferrierite has interconnecting channels, as indicated by the double arrow.
  • the primary channels have a pore diameter of 4.2 A (i.e., greater than 3.5 A) and a pore size index of 22.7 (i.e., within the range of 14 to 28).
  • the secondary channels have a pore size index of 16.8 (i.e., less than 20).
  • zeolites useful in the process of the invention have in common are channels large enough to admit the C4 and/or C5 olefins and large enough to allow propylene and ethylene to diffuse out.
  • the channels are generally small enough to retard diffusion of dimerized products from the channels and small enough to minimize formation of hydrocarbon coke precursors within the channels.
  • Table 3 lists some zeolites that are not useful in the process of the invention.
  • MTW ZSM-12
  • ZSM-12 has a one-dimensional, non-interconnecting channel structure, but it has a pore size index of 32.5 (i.e., greater than 28).
  • MEL ZSM-11
  • MFI ZSM-5
  • MFI ZSM-5
  • the zeolites used in the process of the invention are usually powders. To facilitate their use in fixed-bed reactors, 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. If desired, 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. In the alternative, the zeolite catalyst can be used alone in powder or pelletized form.
  • the zeolite catalysts are normally synthesized in the alkali metal form. They are conveniently converted to the hydrogen form by ion exchange with ammonium halide solution, followed by calcination.
  • 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 are generally included to 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.
  • the effective pore size index needs to be within the limits defined herein.
  • Rare earth metals such as lanthanum can be included, if desired, for the purpose of improving yield or selectivity to propylene and ethylene.
  • Trace amounts of 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 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 ZSM-23 (U.S. Pat. Nos. 4,076,842 and 4,490,342), ZSM-22 or TON (U.S. Pat. Nos. 4,556,477 and 5,342,596), and ZSM-35 (U.S. Pat. No. 4,016,245).
  • 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 200°C to about 650°C, and most preferably from about 300°C to about 600°C. When the zeolites are combined with a binder, calcination usually follows the pelletization process. Pellets are usually made by extrusion.
  • one or more peptizing acids e.g., nitric acid, acetic acid
  • an extrusion aid e.g., hydroxypropyl methylceilulose
  • the mixture of C4 and/or C5 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 200°C to about 750°C, more preferably from about 400°C to about 650°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 3 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 ' ⁇ more preferably from about 1 to 50 h '1 .
  • 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.

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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

Du propylène et de l'éthylène sont produits par chauffe d'un mélange d'oléfines C4 et/ou C5 avec un catalyseur zéolite qui possède des canaux suffisamment grands pour accueillir les oléfines C4 et C5 et pour permettre au propylène et à l'éthylène de se diffuser vers l'extérieur, mais suffisamment petits pour retarder la diffusion de produits dimérisés depuis lesdits canaux et pour réduire à un minimum la formation de précurseurs de coke d'hydrocarbure dans les canaux. Le catalyseur possède des pores d'un diamètre supérieur à 3,5 Å et des canaux à une seule dimension non interconnectés présentant un indice de taille des pores dans la plage de 14 à 28. Le présent procédé peut également reposer sur l'utilisation de catalyseurs zéolite ayant un ou plusieurs canaux interconnectés, dont (1) un canal primaire ayant des pores d'un diamètre supérieur à 3,5 Å et un indice de taille des pores dans la plage de 14 à 28, et (2) un canal secondaire interconnecté avec le canal primaire, ayant un indice de taille des pores inférieur à 20.
EP99954851A 1998-11-04 1999-10-12 Procede de preparation de propylene et d'ethylene Withdrawn EP1127039A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US18586598A 1998-11-04 1998-11-04
US185865 1998-11-04
PCT/US1999/023695 WO2000026163A1 (fr) 1998-11-04 1999-10-12 Procede de preparation de propylene et d'ethylene

Publications (1)

Publication Number Publication Date
EP1127039A1 true EP1127039A1 (fr) 2001-08-29

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EP (1) EP1127039A1 (fr)
AU (1) AU1109600A (fr)
WO (1) WO2000026163A1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001081280A1 (fr) * 2000-04-26 2001-11-01 Equistar Chemicals, L.P. Procede catalytique de fabrication de propylene et d'ethylene
WO2007135055A1 (fr) * 2006-05-19 2007-11-29 Shell Internationale Research Maatschappij B.V. Procédé de préparation de polypropylène
US7932427B2 (en) 2006-05-19 2011-04-26 Shell Oil Company Process for the preparation of propylene and industrial plant thereof
EP2024307A1 (fr) * 2006-05-19 2009-02-18 Shell Internationale Research Maatschappij B.V. Procede de preparation d'une olefine
CN101448766A (zh) 2006-05-19 2009-06-03 国际壳牌研究有限公司 C5和/或c6烯烃的制备方法
AU2007253389B2 (en) 2006-05-19 2011-06-23 Shell Internationale Research Maatschappij B.V. Process for the preparation of an olefin
WO2007135047A1 (fr) 2006-05-19 2007-11-29 Shell Internationale Research Maatschappij B.V. Procédé d'alkylation d'un cycloalcène
CN100586908C (zh) * 2006-08-11 2010-02-03 中国石油化工股份有限公司 丙烯的生产方法
CA2705423A1 (fr) 2007-11-19 2009-05-29 Shell Internationale Research Maatschappij B.V. Procede de preparation d'un produit olefinique
CN101906010B (zh) * 2010-07-29 2012-11-21 中国石油大学(北京) 炼厂催化裂化碳四物料催化裂解制乙烯和丙烯的工艺
CN104557397B (zh) * 2013-10-23 2017-03-22 中国石油化工股份有限公司 一种正丁烯生产丙烯的方法
CN104557396B (zh) * 2013-10-23 2017-10-27 中国石油化工股份有限公司 一种正丁烯催化裂解生产丙烯的方法

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Also Published As

Publication number Publication date
AU1109600A (en) 2000-05-22
WO2000026163A1 (fr) 2000-05-11

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