Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
  • C07C15/02—Monocyclic hydrocarbons
  • C07C15/085—Isopropylbenzene
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
  • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
  • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
  • C07C2/66—Catalytic processes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
  • C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
  • C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
  • C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon
• • 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
  • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
• • 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
  • C07C2529/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
• • 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 present invention relates to a process for producing cumene.
• Cumene is a valuable commodity chemical which is used industrially for the production of phenol and acetone. Cumene has for many years been produced commercially by the alkylation of benzene with propylene over a Friedel-Craft catalyst, particularly solid phosphoric acid or aluminum chloride. More recently, however, zeolite-based catalyst systems have been found to be more active and selective for propylation of benzene to cumene. For example, U.S. Pat. No. 4,992,606 describes the use of MCM-22 in the alkylation of benzene with propylene.
• the zeolite catalysts employed in hydrocarbon conversion processes are in the form of cylindrical extrudates.
• shaped catalyst particles having a high surface to volume ratio such as those having a polylobal cross-section, can produce improved results in processes which are diffusion limited, such as the hydrogenation of resid.
• Example 8 of the '990 patent discloses that hollow trilobal and quadrilobal ZSM-5 catalysts are more active and selective for the ethylation of benzene at 770° F. and 300 psig pressure than solid cylindrical catalysts of the same length. Under these conditions, the reagents are necessarily in the vapor phase.
• the present invention resides in a process for producing cumene which comprises the step of contacting benzene and propylene under at least partial liquid phase alkylating conditions with a particulate molecular sieve alkylation catalyst, wherein the particles of said alkylation catalyst have a surface to volume ratio of about 80 to less than 200 inch ⁇ 1 .
• the particles of said alkylation catalyst have a surface to volume ratio about 100 to about 150 inch ⁇ 1 .
• the molecular sieve of the alkylation catalyst is selected from MCM-22, PSH-3, SSZ-25, MCM-36, MCM-49, MCM-56, faujasite, mordenite and zeolite beta.
• said alkylating conditions include a temperature of about 10° C. to about 125° C., a pressure of about 1 to about 30 atmospheres, and a benzene weight hourly space velocity (WHSV) of about 5 hr ⁇ 1 to about 50 hr ⁇ 1 .
• WHSV weight hourly space velocity
• the present invention relates to a process for producing cumene which comprises the steps of:
• the particles of at least said alkylation catalyst have a surface to volume ratio of about 80 to less than 200 inch ⁇ 1 .
• the molecular sieve of the transalkylation catalyst is selected from MCM-22, PSH-3, SSZ-25, MCM-36, MCM-49, MCM-56, ZSM-5, faujasite, mordenite and zeolite beta.
• said transalkylating conditions include a temperature of about 100° C. to about 200° C.; a pressure of 20 to 30 barg, a weight hourly space velocity of 1 to 10 on total feed and benzene/polyisopropylbenzene weight ratio 1:1 to 6:1.
• the present invention is directed to a process for producing cumene by reacting benzene with propylene under at least partial liquid phase conditions in the presence of a particulate molecular sieve alkylation catalyst, wherein the particles of the alkylation catalyst have a surface to volume ratio of about 80 to less than 200 inch ⁇ 1 , preferably, about 100 to about 150 inch ⁇ 1 .
• the liquid phase propylation of benzene unlike the liquid phase ethylation of benzene, is sensitive to intraparticle (macroporous) diffusion limitations.
• intraparticle diffusion distance can be decreased without excessively increasing the pressure drop across the first catalyst bed.
• the activity of the catalyst for the propylation of benzene can be increased, while at the same time the selectivity of the catalyst towards undesirable polyalkylated species, such as diisopropylbenzene (DIPB) can be reduced.
• DIPB diisopropylbenzene
• Producing the alkylation catalyst with the desired surface to volume ratio can readily be achieved by controlling the particle size of the catalyst or by using a shaped catalyst particle, such as the grooved cylindrical extrudate described in U.S. Pat. No. 4,328,130 or a hollow or solid polylobal extrudate as described in U.S. Pat. No. 4,441,990, the entire contents of both of which are incorporated herein by reference.
• a cylindrical catalyst particle having a diameter of ⁇ fraction (1/32) ⁇ inch and a length of ⁇ fraction (3/32) ⁇ inch has a surface to volume ratio of 141, whereas a quadralobal solid extrudate having the external shape disclosed in FIG. 4 of U.S. Pat. No.
• a hollow tubular extrudate having an external diameter of ⁇ fraction (1/10) ⁇ inch, an internal diameter of ⁇ fraction (1/30) ⁇ inch and a length of ⁇ fraction (3/10) ⁇ inch has a surface to volume ratio of 136.
• the alkylation catalyst used in the process of the invention comprises a crystalline molecular sieve selected from MCM-22 (described in detail in U.S. Pat. No. 4,954,325), PSH-3 (described in detail in U.S. Pat. No. 4,439,409), SSZ-25 (described in detail in U.S. Pat. No. 4,826,667), MCM-36 (described in detail in U.S. Pat. No. 5,250,277), MCM-49 (described in detail in U.S. Pat. No. 5,236,575), MCM-56 (described in detail in U.S. Pat. No.
• the molecular sieve can be combined in conventional manner with an oxide binder, such as alumina, such that the final alkylation catalyst contains between 2 and 80 wt % sieve.
• the alkylation process of the invention is conducted under conditions such that both the benzene and propylene are under at least partial liquid phase conditions.
• Suitable conditions include a temperature of up to about 250° C., e.g., up to about 150° C., e.g., from about 10° C. to about 125° C.; a pressure of about 250 atmospheres or less, e.g., from about 1 to about 30 atmospheres; a benzene to propylene ratio of about 1 to about 10 and a benzene weight hourly space velocity (WHSV) of from about 5 hr ⁇ 1 to about 250 hr ⁇ 1 , preferably from 5 hr ⁇ 1 to 50 hr ⁇ 1 .
• WHSV weight hourly space velocity
• the alkylation process of the invention is particularly selective towards the production of the desired monoalkylated species, cumene, the alkylation step will normally produce some polyalkylated species.
• the process preferably includes the further steps of separating the polyalkylated species from the alkylation effluent and reacting them with additional benzene in a transalkylation reactor over a suitable transalkylation catalyst.
• the transalkylation reaction is conducted in a separate reactor from the alkylation reaction.
• the transalkylation catalyst is preferably a molecular sieve which is selective to the production of the desired monoalkylated species and can, for example employ the same molecular sieve as the alkylation catalyst, such as MCM-22, PSH-3, SSZ-25, MCM-36, MCM-49, MCM-56 and zeolite beta.
• the transalkylation catalyst may be ZSM-5, zeolite X, zeolite Y, and mordenite, such as TEA-mordenite.
• the transalkylation catalyst is also arranged to have a surface to volume ratio of about 80 to less than 200 inch ⁇ 1 , and more preferably about 100 to about 150 inch ⁇ 1 .
• the transalkylation reaction of the invention is conducted in the liquid phase under suitable conditions such that the polyalkylated aromatics react with the additional benzene to produce additional cumene.
• suitable transalkylation conditions include a temperature of 100 to 200° C., a pressure of 20 to 30 barg, a weight hourly space velocity of 1 to 10 on total feed and benzene/PIPB weight ratio 1:1 to 6:1.
• the alkylation and transalkylation steps of the process of the invention can be conducted in an suitable reactor, such as a fixed or moving bed or a catalytic distillation unit.
• catalyst performance is defined by reference to the kinetic rate constant which is determined by assuming second order reaction kinetics.
• kinetic rate constant which is determined by assuming second order reaction kinetics.
• reference is directed to “Heterogeneous Reactions: Analysis, Examples, and Reactor Design, Vol. 2: Fluid-Fluid-Solid Reactions” by L. K. Doraiswamy and M. M. Sharma, John Wiley & Sons, New York (1994) and to “Chemical Reaction Engineering” by 0. Levenspiel, Wiley Eastern Limited, New Delhi (1972).
• Benzene alkylation with propylene was conducted using a conventionally prepared MCM-49 catalyst.
• the catalyst was prepared by extruding a mixture of 80 wt % MCM-49 crystal and 20 wt % alumina into solid cylindrical extrudates having a diameter of ⁇ fraction (1/16) ⁇ inch and a length of 1 ⁇ 4 inch.
• the resultant catalyst particles had a surface to volume ratio of 72.
• Example 1 The process of Example 1 was repeated with the catalyst being produced by extruding the mixture of 80 wt % MCM-49 crystal and 20 wt % alumina into solid quadralobal extrudates having a maximum cross-sectional dimension of ⁇ fraction (1/20) ⁇ inch and a length of 1 ⁇ 4 inch.
• the resultant catalyst particles had a surface to volume ratio of 120.
• Example 2 When tested for the propylation of benzene under the conditions used in Example 1, the catalyst of Example 2 gave the results shown in Table 1. TABLE 1 Catalyst Kinetic Rate Constant DIPB/Cumene (wt %) Example 1 185 14.6 Example 2 240 12.8

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• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 2001
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