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WO2006022731A1 - Catalyseurs de friedel-crafts récyclables, leur utilisation, et leur régénération - Google Patents

Catalyseurs de friedel-crafts récyclables, leur utilisation, et leur régénération Download PDF

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Publication number
WO2006022731A1
WO2006022731A1 PCT/US2004/027136 US2004027136W WO2006022731A1 WO 2006022731 A1 WO2006022731 A1 WO 2006022731A1 US 2004027136 W US2004027136 W US 2004027136W WO 2006022731 A1 WO2006022731 A1 WO 2006022731A1
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WO
WIPO (PCT)
Prior art keywords
mixture
reaction zone
improvement
anhydrous sodium
tetrachloroferrate
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Ceased
Application number
PCT/US2004/027136
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English (en)
Inventor
Thanikavelu Manimaran
A. E. Harkins, Jr.
Ronny W. Lin
Jeffrey L. Broeker
Hao V. Pahn
Steven L. Wiker
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Albemarle Corp
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Albemarle Corp
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Priority to PCT/US2004/027136 priority Critical patent/WO2006022731A1/fr
Publication of WO2006022731A1 publication Critical patent/WO2006022731A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/009—Compounds containing iron, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/46—Friedel-Crafts reactions
    • 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
    • Y02P20/584—Recycling of catalysts

Definitions

  • Friedel-Crafts catalysts are widely used in a variety of Friedel-Crafts reactions such as acylation, alkylation, and sulfonylation.
  • Friedel-Crafts catalysts such as aluminum chloride and ferric chloride, are not reusable and are thus converted into other chemical forms or discharged into the environment.
  • the purpose of this invention is to provide Friedel-Crafts catalysts that have these advantageous properties and characteristics.
  • NaFeCl 4 sodium tetrachloroferrate
  • LiFeCl 4 lithium tetrachloroferrate
  • Friedel-Crafts reactions are substitution reactions in which a hydrogen atom on an aromatic ring is replaced by a functional group or an alkyl group.
  • lithium tetrachloroferrate and especially sodium tetrachloroferrate are used as a Friedel-Crafts catalyst component in Friedel-Crafts reactions whereby various types of aromatic compounds are formed, including without limitation ketones, aldehydes, indanones, sulfones, carboxylic acids, amides, and esters, as well as alkylated and thioalkylated aromatic compounds, and brominated aromatics including carbonyl and sulfonyl compounds which require stoichiometric amounts of Lewis acid for the bromination.
  • a "Friedel-Crafts catalyst component” is a molecule that, when used in conducting a Friedel-Crafts reaction, may form in situ one or more active complexes or other catalytic species that facilitate the desired reaction.
  • LiFeCl 4 or NaFeCl 4 is typically charged to the reactor as one of the components but it need not remain as such when other components are present and/or reaction begins to take place.
  • an equimolar complex between an acylating agent and sodium tetrachloroferrate including for example a complex of this type where the acylating agent forming the complex is acetic anhydride or acetyl chloride, or is a mixture of complexes in which (i) one complex is an equimolar complex between acetic anhydride and sodium tetrachloroferrate and in which (ii) another complex is an equimolar complex between acetyl chloride and sodium tetrachloroferrate.
  • Fig. 1 shows infrared absorbance spectra comparing the spectrum of an equimolar complex of acetyl chloride (the upper spectrum) with that of 98% pure acetyl chloride (the lower spectrum).
  • Fig. 2 shows infrared absorbance spectra comparing the spectrum of an equimolar complex of acetic anhydride (the upper spectrum) with that of over 99% pure acetic anhydride (the lower spectrum).
  • this invention in one of its embodiments provides a substantial improvement in the conduct of chemical reactions that involve replacement of a hydrogen atom on the ring of an aromatic reactant by a functional group, and in which reaction a Friedel-Crafts catalyst is used.
  • the improvement comprises introducing anhydrous sodium tetrachloroferrate into the reaction zone as a Friedel-Crafts catalyst component.
  • Methods for producing anhydrous alkali metal tetrachloroferrate are known and reported in the literature. See for example, U.S. Pat. No. 3,729,543 to Wendell E. Dunn, Jr., EP 1,198,417 published April 2002, and Cerisier et al., European Journal of Solid State and Inorganic Chemistry, 1988, 25(1), 35-52.
  • Friedel-Crafts reactions are typically conducted under anhydrous conditions, and thus it is desirable to introduce anhydrous sodium tetrachloroferrate into the reaction zone in molten liquid form, in the form of finely-divided solids, or in both such forms, hi this invention, it is possible to introduce the anhydrous sodium tetrachloroferrate and/or anhydrous lithium tetrachloroferrate into the reaction zone before, during and/or after the introduction of the other reaction components.
  • anhydrous sodium tetrachloroferrate is introduced into the reaction zone in molten liquid form during and/or after the introduction of at least an aromatic hydrocarbon reactant and/or another liquid reaction component, or a solvent or diluent, and the resultant mixture is agitated so that the sodium tetrachloroferrate is well dispersed throughout the mixture.
  • the following workup procedure is preferably employed.
  • the reaction mixture is subjected to hydro lytic conditions so that an aqueous phase and an organic phase are formed, these liquid phases are separated from each other, typically by a liquid- liquid separation procedure such as decantation or draining, and then all water including water of hydration is removed from the aqueous phase to thereby regenerate anhydrous sodium tetrachloroferrate suitable for reuse as a Friedel-Crafts catalyst component.
  • a liquid- liquid separation procedure such as decantation or draining
  • a preferred way of removing all water including water of hydration is a procedure which comprises (a) distilling off distillable free water from the aqueous phase, (b) heating the resultant mixture to remove the water of hydration, and (c) passing anhydrous hydrogen chloride into or through the mixture from (b), to thereby regenerate said anhydrous sodium tetrachloroferrate.
  • solids may also be present in the resultant mixture from (a), and such solids typically are melted during the conduct of (b). If desired, this water removal operation can be conducted at reduced pressure.
  • a suitable temperature can be in the range of about 150 0 C to about 300 ° C, and preferably is in the range of about 230 ° C to about 270 ° C.
  • the temperature and pressure at which the operation is conducted should be such as to ensure removal of the water of hydration.
  • a gaseous oxidant can be passed into or through the liquid melt after the anhydrous hydrogen chloride has been passed into or through said liquid, hi this way any divalent iron is oxidized to the trivalent state.
  • Suitable gaseous oxidants include chlorine, oxygen, or air, any of which can be diluted with an inert gas such as nitrogen, argon, or the like.
  • This operation can be performed at any temperature at which the anhydrous sodium tetrachloroferrate remains in the liquid (molten) state or in solution (e.g., from about 20° C to about 300 0 C and preferably at temperatures in the range of about 12O 0 C to about 27O 0 C.
  • the regenerated anhydrous sodium tetrachloroferrate while in the form of a liquid is introduced into the reaction zone as a Friedel-Crafts catalyst component.
  • a Friedel-Crafts catalyst component This enables the Friedel-Crafts reaction to be performed on a continuous basis, with the periodic inclusion of fresh anhydrous sodium tetrachloroferrate when and as needed.
  • the anhydrous sodium tetrachloroferrate is introduced into the reaction zone in molten liquid form after the introduction into the reaction zone of aromatic hydrocarbon reactant or inert liquid solvent, and after the reaction is completed and a reaction mixture has been formed, a procedure comprising the following steps is used: a) the reaction mixture is subjected to hydrolytic conditions so that an aqueous phase and a liquid organic phase are formed, b) these liquid phases are separated from each other, and c) all water including water of hydration is removed from the aqueous phase, to thereby regenerate anhydrous sodium tetrachloroferrate suitable for reuse as a Friedel-Crafts catalyst component.
  • the removal of such water is preferably carried out by a procedure which comprises (1) distilling off distillable free water from the aqueous phase, (2) heating the resultant mixture to remove water of hydration, and (3) passing anhydrous hydrogen chloride into or through the mixture from (2) while raising the temperature of the mixture high enough so that water of hydration is removed from the mixture to thereby regenerate anhydrous sodium tetrachloroferrate. Passing a gaseous oxidant into or through the mixture after the anhydrous hydrogen chloride treatment is also desirable, as noted above. Thereafter in a preferred mode of operation the regenerated anhydrous sodium tetrachloro ferrate while in the form of a liquid is introduced into the reaction zone as a Friedel-Crafts catalyst component.
  • a Friedel-Crafts acylation process is carried out. Such reactions involve introducing into a reaction zone at least an aromatic reactant having a position on the aromatic ring to be acylated, an acylating agent, and a Friedel-Crafts catalyst component, and effecting reaction the acylation in the reaction zone.
  • the reaction is performed under inert, anhydrous reaction conditions.
  • the Friedel-Crafts catalyst component introduced into the reaction zone is anhydrous sodium tetrachloroferrate or anhydrous lithium tetrachloro ferrate, or both of them, to serve as Friedel-Crafts catalyst component(s).
  • the Friedel-Crafts catalyst component and the reaction agent such as the acylating agent, the alkylating agent, the sulfonylating agent, and the like, react mole per mole, preferably at least an equimolar amount of the Friedel-Crafts catalyst component, as compared to the reaction agent, is added to the reaction zone.
  • the Friedel-Crafts catalyst component and the reaction agent are added to the reaction zone. Because of its superior activity, use of anhydrous sodium tetrachloroferrate as the Friedel-Crafts catalyst component is preferred.
  • the reaction is conducted in a liquid phase which typically is an excess of the aromatic reactant when a liquid, or an inert solvent, to dissolve reactants that are in the solid state.
  • the anhydrous sodium tetrachloroferrate is preferably introduced into the acylation reaction zone in molten liquid form, but can be added as solids, for example as a slurry in one of the reactants or in a solvent, hi either case, the anhydrous sodium tetrachloroferrate is preferably introduced into the reaction zone (i) during and/or after the introduction into the reaction zone of at least a portion of the aromatic reactant to be acylated and before commencing the introduction of the acylating agent into the reaction zone.
  • the workup and regeneration procedures as described above, and preferably also the recycle procedure as described above, are conducted.
  • Another embodiment of this invention is a process of regenerating anhydrous sodium tetrachloroferrate catalyst from an aqueous phase containing hydrated sodium tetrachloroferrate catalyst.
  • This process comprises (a) distilling off distillable free water from the aqueous phase, (b) heating the resultant mixture to remove the water of hydration, and (c) passing anhydrous hydrogen chloride into or through the mixture from (b) to thereby regenerate said anhydrous sodium tetrachloroferrate.
  • a gaseous oxidant e.g., chlorine, oxygen, air, or the like
  • the process comprises introducing into a reaction zone components comprised of (i) an acylatable aromatic compound, (ii) anhydrous sodium tetrachloroferrate or anhydrous lithium tetrachloroferrate, or both of them, and (iii) an acylating agent, and employing reaction conditions in said reaction zone that effect reaction such that an aromatic ketone is formed.
  • a reaction zone components comprised of (i) an acylatable aromatic compound, (ii) anhydrous sodium tetrachloroferrate or anhydrous lithium tetrachloroferrate, or both of them, and (iii) an acylating agent, and employing reaction conditions in said reaction zone that effect reaction such that an aromatic ketone is formed.
  • i), (ii), and (iii) are introduced into the reaction zone in the order named.
  • Component (i) is preferably an acylatable mononuclear aromatic compound, an acylatable binuclear non- fused ring aromatic compound, or an acylatable binuclear fused ring aromatic compound.
  • Preferred acylating agents are carboxylic acid anhydrides and acyl halides, especially acetic anhydride or acetyl chloride, or both of them, hi the acylation of isobutylbenzene to form isobutylacetophenone, which is an intermediate for the production of ibuprofen, it is preferred to use a combination of acetic anhydride and acetyl chloride.
  • a still further embodiment of this invention is the provision as a new composition, of an equimolar complex between an acylating agent and sodium tetrachloroferrate, including for example a complex of this type where the acylating agent forming the complex is acetic anhydride or acetyl chloride, or is a mixture of complexes in which (i) one complex is an equimolar complex between acetic anhydride and sodium tetrachloroferrate and in which (ii) another complex is an equimolar complex between acetyl chloride and sodium tetrachloroferrate.
  • complexes can be formed by interaction between sodium tetrachloroferrate and an acylating agent such as an acyl chloride or bromide such as acetyl chloride or an acid anhydride such as acetic anhydride or propionic anhydride.
  • an acylating agent such as an acyl chloride or bromide such as acetyl chloride or an acid anhydride such as acetic anhydride or propionic anhydride.
  • Such complexes can be preformed by interaction between sodium tetrachloroferrate and one or more acylating agents typically in an inert organic solvent (e.g., dichloromethane) with the application of heat if necessary, and used in an acylation reaction. Alternatively, they can be formed, and typically will be formed, in situ when conducting an acylation reaction. Figs.
  • 1 and 2 provide infrared absorbance spectra of complexes of sodium tetrachloroferrate with acetyl chloride and acetic anhydride, respectively.
  • the lower portions of these figures give the infrared absorbance spectra of acetyl chloride and acetic anhydride, respectively, for comparison.
  • NaCl (Aldrich, 45.6g) and FeCl 3 (Aldrich, 127g) were mixed and heated to 150°C to form NaFeCl 4 .
  • the material was cooled to ambient temperature and the solids were ground to powder (olive colored) under N 2 .
  • a portion of the NaFeCl 4 (75g) was mixed with commercially produced IBB (9Og) and acetyl chloride (AcCl; 27g) was added dropwise at 10-16° C over 40 minutes. The reaction was allowed to ride at 5-10° C for an additional 60 minutes.
  • the reaction mixture was maintained at 5-10° C for one hour and GC analysis showed 42% IBAP, 55% IBB, 3% DBPE.
  • FeCl 3 (Aldrich, 135g) and NaCl (Aldrich, 49g) were mixed with aqueous HCl (2.7%, 229g). The mixture was heated to 110-120°C and condensate was removed (150 g) by flash distillation. Dodecane (Aldrich 30Og) was added and the resulting mixture was heated and the dodecane and water were removed at from 90 to 155 0 C under 25-50 mmHg. The remaining solids (166 g) were ground by mortar and pestle under N 2 . [0028] A portion of the recovered NaFeCl 4 (6Ig) was mixed with commercially produced IBB (75 g) and cooled to 5-10° C.
  • Example 5 Hydrolysis solution from Example 5 and from two additional runs similar to Example 5 were combined and the water was removed by flash distillation at ambient temperature ranging from 100- 130° C and at 20 mmHg over the range of from 70-200 0 C. The material was maintained at 200 ° C for 40 minutes. The remaining solids were ground via mortar and pestle under N 2 .
  • NaFeCl 4 (319g) was prepared as in Example 4 except that it was heated to 220 0 C for 2 hr.
  • the NaFeCl 4 was mixed with commercially produced IBB (197g) and commercially produced acetic anhydride (Ac 2 O; 97g) was added over 40 minutes at 25-30° C.
  • the reactor temperature was increased to 45 ° C and maintained at that temperature for a total of 300 minutes.
  • GC analysis showed 62.6% ⁇ -IBAP, 1.26% m-IBAP, and 35.6% IBB.
  • reaction mixture was quenched with 80Og OfH 2 O, 300g of hexanes, and 17Og of 37% aqueous HCl and the layers were separated by decantation.
  • the aqueous phase was washed with hexanes (203g).
  • Example 8 The aqueous solution from Example 8 (1704 g) was heated and the water removed by flash distillation at ambient pressure from 106 to 112°C. The remaining water was removed at ca. 13.33 kPa (100 mmHg) from 70-220 0 C while bubbling anhydrous HCl (380 g) into the solution. The reaction was then heated to 250-280 ° C under atmospheric pressure while bubbling anhydrous HCl (50g) into the solution.
  • reaction mixture was quenched with 1090 H 2 O, the layers were separated by decantation, and the aqueous phase was washed with hexanes (180 g).
  • Example 9 The aqueous solution in Example 9 (1424 g) and HCl (aqueous, 37%, 133g) were mixed and the water was removed by flash distillation at ambient pressure from 105 to 112°C. The remaining water was removed at ca. 13.33 kPa (100 mmHg) from 70-220 0 C while bubbling anhydrous HCl (250 g) into the solution. The reaction was then heated to 250-280 0 C under atmospheric pressure while bubbling anhydrous HCl (150g) into the solution. The solids were ground (283g).
  • Part A the process of this invention gave a substantially superior result as compared to use of a catalyst system of the prior art (Part B).

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

Abstract

La présente invention a pour objet un procédé selon lequel une réaction de Friedel-Crafts est menée dans une unité de réaction en utilisant un catalyseur de Friedel-Crafts. L’invention inclut plus particulièrement l’introduction de tétrachloroferrate de sodium anhydre dans l’unité de réaction, ce composé servant de catalyseur de Friedel-Crafts. Le tétrachloroferrate de sodium anhydre est un catalyseur de Friedel-Crafts recyclable. Un système catalytique particulièrement efficace est formé in situ lorsque le tétrachloroferrate de sodium anhydre est utilisé dans une réaction d’acylation, ladite réaction employant un agent d’acylation, préférentiellement le chlorure d’acétyle, l'anhydride acétique, ou une combinaison des deux.
PCT/US2004/027136 2004-08-19 2004-08-19 Catalyseurs de friedel-crafts récyclables, leur utilisation, et leur régénération Ceased WO2006022731A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2794942C1 (ru) * 2022-01-12 2023-04-25 Федеральное государственное бюджетное образовательное учреждение высшего образования "Уфимский государственный нефтяной технический университет" Способ получения легких газообразных и жидких углеводородов путем каталитической конверсии бензина термического крекинга

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3729543A (en) * 1971-01-21 1973-04-24 Dunn Inc Wendell E Process for preparing alkali-metal tetra-chloroferrate
US3872174A (en) * 1968-06-27 1975-03-18 Du Pont Production of dichloroethylene using melt chlorination process
EP0325784A2 (fr) * 1987-12-31 1989-08-02 BASF Aktiengesellschaft Procédé pour la préparation de cétones
EP0493023A1 (fr) * 1990-12-21 1992-07-01 Neste Oy Production de chlorure ferrique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3872174A (en) * 1968-06-27 1975-03-18 Du Pont Production of dichloroethylene using melt chlorination process
US3729543A (en) * 1971-01-21 1973-04-24 Dunn Inc Wendell E Process for preparing alkali-metal tetra-chloroferrate
EP0325784A2 (fr) * 1987-12-31 1989-08-02 BASF Aktiengesellschaft Procédé pour la préparation de cétones
EP0493023A1 (fr) * 1990-12-21 1992-07-01 Neste Oy Production de chlorure ferrique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ARATA K ET AL: "Friedel-Crafts acylation of toluene catalyzed by solid superacids", APPLIED CATALYSIS A: GENERAL, ELSEVIER SCIENCE, AMSTERDAM, NL, vol. 197, no. 2, 1 May 2000 (2000-05-01), pages 213 - 219, XP004272315, ISSN: 0926-860X *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2794942C1 (ru) * 2022-01-12 2023-04-25 Федеральное государственное бюджетное образовательное учреждение высшего образования "Уфимский государственный нефтяной технический университет" Способ получения легких газообразных и жидких углеводородов путем каталитической конверсии бензина термического крекинга
RU2841364C1 (ru) * 2024-10-16 2025-06-06 Ольга Владимировна Баширова Лабораторный реактор для моделирования процессов коксообразования на его стенках

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