WO2020260237A1 - Procédé de préparation d'éthylbenzène - Google Patents

Procédé de préparation d'éthylbenzène Download PDF

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Publication number
WO2020260237A1
WO2020260237A1 PCT/EP2020/067426 EP2020067426W WO2020260237A1 WO 2020260237 A1 WO2020260237 A1 WO 2020260237A1 EP 2020067426 W EP2020067426 W EP 2020067426W WO 2020260237 A1 WO2020260237 A1 WO 2020260237A1
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WO
WIPO (PCT)
Prior art keywords
source
toluene
ethylbenzene
methanol
bara
Prior art date
Application number
PCT/EP2020/067426
Other languages
English (en)
Inventor
Sandeep Negi
Kartick Chandra Mondal
Sonal Sant SANT
Vikram BHIDE
Hyacinth Mary Bastian
Puneet Gupta
Original Assignee
Shell Internationale Research Maatschappij B.V.
Shell Oil Company
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 Shell Internationale Research Maatschappij B.V., Shell Oil Company filed Critical Shell Internationale Research Maatschappij B.V.
Publication of WO2020260237A1 publication Critical patent/WO2020260237A1/fr

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Classifications

    • 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
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
    • 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

Definitions

  • the present invention relates to a method of preparing ethylbenzene by reaction of toluene and methanol.
  • Various methods of preparing ethylbenzene by reaction of toluene and methanol are known in the art.
  • Alkyl styrenes including ethylbenzene, are important starting materials for the organic chemical industry, mainly used for producing polystyrenes, ABS resins, SBR rubbers, and unsaturated resins.
  • styrene-based resins rank worldwide only after PEs and PVCs in terms of production.
  • alkylating agent As much alkylating agent as possible be converted into ethyl benzene and styrene by reacting with toluene, rather than unnecessarily consumed by the decomposition into CO and 3 ⁇ 4.
  • alkyl benzenes or alkylating agents e.g. dimethoxy methane
  • ethylbenzene is prepared by bringing a gaseous mixture of methanol and toluene in contact with a catalyst composed of a carrier of activated carbon or alumina supporting potassium and either one or both of zinc and copper.
  • a molar ratio of toluene/methanol of 3.95/1 was passed through a reaction tube filled with catalyst and kept at a temperature of 425 °C.
  • the present invention provides a process for making ethylbenzene including reacting toluene with a C1 source in the presence of a zeolite catalyst in one or more reactor zones to form a product comprising ethylbenzene and maintaining a molar ratio of toluene: C1 source ranging from 3: 1 to 30:1 throughout the one or more reactor zones.
  • the reacting is performed at a pressure of from 1 to 10 bara and the partial pressure of the C1 source ranges from about 0.04 to about 0.5 bara.
  • Figure 1 is a flow diagram showing an aspect of an exemplary, but non-limiting, embodiment of a process described herein.
  • any references to“one embodiment” or“an embodiment” means that a particular element, feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment.
  • the appearances of the phrase “in one embodiment” in various places in the specification are not necessarily referring to the same embodiment.
  • Embodiments of the invention provide a process for making ethylbenzene by reacting toluene with a C1 source in the presence of a zeolite catalyst in one or more reactor zones to form a product comprising ethylbenzene.
  • a molar ratio of toluene:C1 source is maintained between from 3:1 to 30: 1 throughout the one or more reactor zones, reactor zones are at a pressure ranging from 1 to 10 bara; and the partial pressure of the C1 source is maintained in the range from about 0.04 to about 0.5 bara.
  • C1 source a carbon source
  • the C1 source includes methanol, formaldehyde, formalin, trioxane, methylformcel, paraformaldehyde and methylal and combinations thereof.
  • the C1 source is methanol.
  • the reaction has a 1:1 molar ratio of toluene to the C1 source, the ratio of the feedstream is not limited within the present invention and can vary depending on operating conditions and the efficiency of the reaction system. If excess toluene or C1 source is fed to the reaction zone, the unreacted portion can be subsequently separated and recycled back into the process.
  • the molar ratio of toluene:C1 source can range between from 100:1 to 1:100, from 50:1 to 1:50; from 20:1 to 1:20; from 10:1 to 1:10; from 5:1 to 1:5; from 2:1 to 1:2, and from 3: 1 to 30:1.
  • the ratio of toluene:methanol can range between from 50: 1 to 1:50; from 20:1 to 1:20; from 10:1 to 1:10; from 5:1 to 1:5; from 2:1 to 1:2, and from 3: 1 to 30:1.
  • the molar ratio for toluene: C1 source in all reaction zones is maintained above 3:1, preferably above 10:1, more preferably above 15:1.
  • a molar ratio for toluene: C1 source is maintained below 30:1 throughout the reaction zones.
  • reaction conditions can vary depending on the feedstream composition and the desired composition of the product streams. In some embodiments, reactions occur at elevated temperatures and pressures and occur in the presence of a basic catalyst system.
  • a zeolite is generally a porous, crystalline alumino-silicate, and it can be formed either naturally or synthetically.
  • the inclusion of various metal oxides can lead to several different zeolite compositions.
  • zeolite is commonly altered through a variety of methods to adjust characteristics such as pore size, structure, activity, acidity, and silica/alumina molar ratio. Thus, a number of different forms of zeolite are available.
  • Zeolite materials suitable for this invention may include silicate-based zeolites or amorphous compounds such as faujasites, mordenites, etc.
  • Silicate-based zeolites are made of alternating Si04- and MOx tetrahedra, where M is an element selected from the Groups 1 through 16 of the Periodic Table (new IUPAC). These types of zeolites have 4, 6, 8, 10, or 12- membered oxygen ring channels.
  • the zeolite-based catalyst comprises a zeolite selected from an X-type zeolite, a Y- type zeolite or a combination thereof.
  • zeolites Another method of altering zeolites is by ion-exchange.
  • Ion exchange may be performed by conventional ion exchange methods in which sodium, hydrogen, or other inorganic cations that may be typically present in a substrate are at least partially replaced via a fluid solution.
  • the zeolite- based catalyst has been ion-exchanged with an alkali metal, preferably selected from the group consisting of Na, K, Cs, Rb and Fr and a combination thereof.
  • the zeolites for use according to the present invention may include one or more metal oxides, such as Cs20.
  • the metal oxide(s) may be present within the structure of the zeolite, or support.
  • the metal oxide present within the structure of the zeolite may be loosely contained within the structure of the zeolite.
  • the metal oxide is not physically attached to the zeolite, but physically trapped within the zeolite cage structure, which can be referred to herein as‘occluded metal oxide.’
  • the occluded metal oxide present in the structure of the zeolite can electrically influence the zeolite and alter its catalytic abilities.
  • the prepared catalyst can be ground, pressed, sieved, shaped and/or otherwise processed into a form suitable for loading into a reactor.
  • the reactor can be any type known in the art which uses catalyst particles, such as a fixed bed, fluidized bed, or swing bed reactor.
  • an inert material such as quartz chips, can be used to support the catalyst bed and to place the catalyst within the bed.
  • a pre-treatment of the catalyst may, or may not, be necessary.
  • the reactor can be heated to elevated temperatures (i.e, the desired reaction temperature), such as 200° C to 900° C with an inert gas flow, such as 100 mL/min, and held at these conditions for a length of time, such as 1 to 3 hours.
  • the reactor can be brought to the operating temperature of the reactor, for example 300° C to 550° C, or optionally down to atmospheric or other desired temperature.
  • the reactor can be kept under an inert purge, such as under a nitrogen or helium purge.
  • the temperature can range in a non-limiting example from 250° C to 750° C, from 300° C to 500° C, from 325° C to 450° C, preferably below 400° C.
  • the pressure can range in a non-limiting example from 1 bara to 20 bara, from 1 bara to 10 bara, from 1 bara to 5 bara.
  • the partial pressure of MeOH about 0.04 bara to about 0.5 bara, from about 0.06 bara to about 0.3 bara, and from 0.9 bara to 0.15 bara.
  • the method according to the present invention is not limited to a certain space velocity, it is preferred that the reaction is performed at a space velocity (WHSV) of from 0.1 to 10.0 h-1, preferably below 5.0 h-1, more preferably below 3.0 h-1, even more preferably below 2.0 h-1, yet even more preferably below 1.0 h-1.
  • WHSV space velocity
  • the person skilled in the art is aware with how to determine or calculate the space velocity.
  • the space velocity has been based on standard calculations (mass flow rate of feed/reactant pass through per gram of catalyst per hour).
  • the ethylbenzene selectivity based on methanol is above 40%, preferably above 50%, more preferably above 60%. This high ethylbenzene selectivity based on methanol reflects that the methanol is converted to the desired product rather than decomposing into CO and H2.
  • the ethylbenzene-enriched product mixture obtained comprises at least 30 mol% ethylbenzene, preferably at least 10 mol%.
  • the ethylbenzene-enriched mixture comprises at most 4 mol% ethylbenzene.
  • Figure 1 is a simplified flow chart of an embodiment of the ethylbenzene process 100 discussed above.
  • a C1 source containing feed stream 102 and a feed stream of toluene 104 are fed into reactor 105 to produce ethylbenzene/styrene.
  • Embodiments of reactor 105 that can be used with the present invention can include, but not limited to: fixed bed reactors; fluid bed reactors; and entrained bed reactors. Reactors capable of the elevated temperature and pressure as described herein, and capable of enabling contact of the reactants with the catalyst, can be considered within the scope of the present invention. Embodiments of the reactor system may be determined based on the design conditions and throughput, as by one of ordinary skill in the art, and are not meant to be limiting on the scope of the present invention.
  • An example of a suitable reactor can be a fluid bed reactor having catalyst regeneration capabilities.
  • This type of reactor system employing a riser can be modified as needed, for example by insulating or heating the riser if thermal input is needed, or by jacketing the riser with cooling water if thermal dissipation is required. These designs can also be used to replace catalyst while the process is in operation, by withdrawing catalyst from the regeneration vessel from an exit line or adding new catalyst into the system while in operation. In some embodiments, there may one or more reactors 105.
  • the one or more reactors may include one or more catalyst beds 107a, 107b, 107c, 107d and 107e.
  • an inert material layer can separate each bed.
  • the inert material can comprise any type of inert substance, including quartz.
  • a reactor includes between 1 and 10 catalyst beds.
  • the reactor includes between 2 and 5 catalyst beds.
  • the C1 source is injected into each catalyst bed and the toluene feed 104 is injected into the bottom of the reactor.
  • a portion of the C1 source containing feed stream 102 is fed into each of the one or more catalyst beds 107a, 107b, 107c, 107d and 107e.
  • the C1 source 102 and toluene 104 may be injected into a catalyst bed, an inert material layer, or both.
  • at least a portion of the C1 source 102 is injected into a catalyst bed(s) and at least a portion of the toluene feed 104 is injected into an inert material layer(s).
  • the entire C1 source 102 is injected into a catalyst bed(s) and all the toluene feed 104 is injected into an inert material layer(s).
  • at least a portion of the toluene feed 104 is injected into a catalyst bed(s) and at least a portion of the C1 source 102 is injected into an inert material layer(s).
  • all the toluene feed 104 is injected into a catalyst bed(s) and the entire C1 source 102 is injected into an inert material layer(s).
  • the product 106 of the reactor 105 may then be sent to an optional separation unit 109 where a recycle stream 108 including any unreacted C1 source, unreacted methanol, unreacted formaldehyde is separated from the ethylbenzene 110 and the styrene 112.
  • the recycle stream 108 can be recycled back into the reactor 105.
  • the styrene product stream 112 can be removed from the separation unit 109 and subjected to further treatment or processing if desired.
  • a toluene and methanol containing mixture was prepared by mixing 20 moles of toluene (Sigma Aldrich) with 1 mol of methanol (Sigma Aldrich).
  • a NaX zeolite was sourced from (Sigma Aldrich) and the“Na” form was exchanged with“Cs” from a CsOH precursor by a liquid ion exchange method, wherein the molecular sieve and the alkali metal ion source contact each other in the presence of a solvent (i.e., water) so as to conduct the ion exchange.
  • the content of the alkali metal ion (i.e., Cs ion) in the aqueous solution may be between 0.5 - 2.5 mol/L.
  • the ion-exchange can be conducted at temperatures between 50-90 °C, for between 1-3 hours, and the weight ratio of the molecular sieve to the aqueous solution for each contacting could be 1:5 to 1:10.
  • the contacting could be conducted for one or more times depending upon the require loading of alkali metals.
  • Table 1 lists the reaction conditions and the results of the reaction.
  • the present invention surprisingly provides a method for preparing ethylbenzene by reaction of toluene and methanol, wherein a relatively high ethylbenzene selectivity (higher than 40% based on methanol) can be obtained.
  • the high methanol conversion helps to reduce costs for downstream separation processes by eliminating the need for typically expensive 3-phase separation processes.
  • Examples 1-5 demonstrate the effect of the temperature at the same WHSV.
  • Example 1 is comparative. It is hypothesized that ethylbenzene (EB) selectivity based on toluene conversion improves with temperature, as shown below EB selectivity based on methanol conversion increases between 375 °C to 390 °C temp and decreases thereafter.
  • EB ethylbenzene
  • Examples 4-11 demonstrate the effect of WHSV at different temperatures. It is hypothesized that EB selectivity based on toluene & methanol conversion improve with more residence time (lower space velocity). Dimethyl ether (DME) is observed as a major by-product at higher space velocity.
  • DME Dimethyl ether
  • Examples 12-16 demonstrate the effect of the molar toluene/methanol ratio at different temperatures. Examples 15 and 16 are comparative. It is hypothesized that EB selectivity based on toluene & methanol conversion improves with higher T/M molar ratio. DME is observed as a major by-product from methanol at lower T/M ratio.
  • Examples 17-22 show the effect of the methanol partial pressure at different temperatures. Higher ethylbenzene (and styrene) selectivity is observed based on toluene & methanol conversion. DME is observed as major methanol decomposition by-product other than CO at higher MeOH partial pressure. With higher methanol partial pressure, one of ordinary skill would have expected higher methanol conversion. However, contrary to expectations, the examples show higher methanol conversion at lower methanol partial pressures, resulting in higher methanol utilization at lower methanol partial pressures.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'éthylbenzène comprenant la réaction de toluène avec une source de C1 en présence d'un catalyseur de zéolite dans une ou plusieurs zones de réacteur pour former un produit comprenant de l'éthylbenzène et le maintien d'un rapport molaire toluène:C1 allant de 3:1 à 30:1 dans l'ensemble de la ou des zones de réacteur. La réaction est effectuée à une pression de 1 à 10 bars et la pression partielle de la source C1 varie d'environ 0,04 à environ 0,5 bars.
PCT/EP2020/067426 2019-06-28 2020-06-23 Procédé de préparation d'éthylbenzène WO2020260237A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19183420 2019-06-28
EP19183420.9 2019-06-28

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Publication Number Publication Date
WO2020260237A1 true WO2020260237A1 (fr) 2020-12-30

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4371729A (en) 1981-02-17 1983-02-01 Agency Of Industrial Science And Technology Method for the preparation of ethylbenzene
US8258359B2 (en) * 2010-04-20 2012-09-04 Fina Technology, Inc. Alkylation of toluene to form styrene and ethylbenzene
US8318999B2 (en) * 2010-04-20 2012-11-27 Fina Technology Inc. Method of coupling a carbon source with toluene to form a styrene ethylbenzene

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4371729A (en) 1981-02-17 1983-02-01 Agency Of Industrial Science And Technology Method for the preparation of ethylbenzene
US8258359B2 (en) * 2010-04-20 2012-09-04 Fina Technology, Inc. Alkylation of toluene to form styrene and ethylbenzene
US8318999B2 (en) * 2010-04-20 2012-11-27 Fina Technology Inc. Method of coupling a carbon source with toluene to form a styrene ethylbenzene

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