SYNTHESIS OF BISPHENOLS
The present invention relates to the preparation of bisphenols by condensation of a phenolic compound with a carbonyl-containing compound using metal oxide catalysts.
Bisphenols are compounds that are frequently used in the manufacture of plastic materials. Of particular utility is bisphenol A, or 2,2-bis(4- hydroxyphenyl)propane, which is commonly used in the production of polycarbonates, polyarylates, and copolyestercarbonates. These plastic materials are used in many consumer products including household appliances, components of electrical devices, automotive applications, and reusable bottles and containers. Bisphenol A is also a starting material for epoxy resins which comprise coatings, electrical laminants, composites, and adhesives. Average annual production of bisphenol A has been estimated to be over 5 billion pounds.
Bisphenols can be synthesized by the condensation reaction between phenol and a carbonyl-containing compound in the presence of an acid catalyst. The reaction of phenol with acetone to form bisphenol A is depicted in the chemical equation below. Numerous types of acid catalysts have been used in this type of condensation reaction including hydrochloric acid, perchloric acid, and borontrifluoride. Solid acid catalysts, which include zeolites, acid clays, heteropoly acids and ion-exchange resins, are also effective and facilitate purification of the bisphenol product. Ion- exchange resins composed of styrene-divinylbenzene copolymer or polystyrene polysuifonic acids are widely used in the commercial synthesis of bisphenol A.
Significant effort has been directed toward the optimization of reaction conditions for the preparation of bisphenols. Particular emphasis has been given to the development of various types of catalyst materials suitable for the condensation reaction which yields bisphenol A. For instance, zeolites are shown to effectively catalyze this condensation reaction in Singh, A.P. Catalysis Letters 1992, 16, 431. Additionally, U.S. Pat. No. 4,052,466 discloses the use of acid catalysts such as mineral acids (HCI), Lewis acids (BF
3), zeolites, acid clays, and ion-exchange resins in combination with an organic co-catalyst promoter compound. Furthermore, U.S. Pat. Nos. 4,424,283; 4,375,567; and 4,346,247 focus on the use of ion-exchange resins and modifications thereof for the synthesis of bisphenol A. A comparative study between ion-exchange resins and heteropoly acids for the synthesis of bisphenol A has also been completed and is presented in Yadav, G.D. and Kirthivasan, N. Applied Catalysis A: General 1997, 154, 29. Similarly, the preparation of bisphenols by condensation of ketones with phenols over a heteropoly acid is disclosed in Japanese Pat. No. 2045439.
In view of the ever-increasing demand for plastic materials made with bisphenols (e.g., bisphenol A), it is desirable to improve processes for production of these compounds to enhance efficiency and safety of large-scale preparations. Many of the known catalysts for synthesis of bisphenol A suffer from one or more deficiencies such as having poor regenerability, instability at high temperatures, low conversions and selectivities, as well as toxic properties and difficult disposal procedures. Thus, there is a need for new catalysts with improved qualities such as greater stability towards regeneration, higher selectivity for preferred bisphenol isomers, and decreased toxicity for safer handling and easier disposal.
The present invention is directed to a process for the preparation of bisphenols, specifically bisphenol A, by contacting a phenolic compound with a carbonyl-containing compound in the presence of a condensation catalyst comprising a Group IV metal. Suitable condensation catalysts include Sn02, oxides of a Group IVB metal, and oxides of a Group IVB metal modified with an anion. Anions of the present invention encompass oxyanions of Group VIB metals, cerium, and sulfur. In a
preferred embodiment, the bisphenol product is bisphenol A formed by the condensation of phenol and acetone in the presence of catalyst comprising zironia modified with tungstate.
The present invention is directed to catalysts and processes for the preparation of bisphenols. According to the methods of the present invention, at least two types of catalysts may be used for the synthesis of bisphenols. One type of catalyst is a metal oxide, preferably titanium(IV) oxide (Ti02) or tin(IV) oxide (SnO2). This metal oxide catalyst will be herein referred to as "unmodified catalyst" or "unmodified metal oxide catalyst." The other type of catalyst is a metal oxide of a Group IVB metal, preferably zirconium or titanium modified with an anion. The anion may be an oxyanion of a Group VIB metal such as tungsten or an oxyanion of a lanthanide (e.g., cerium). Further, the anion may be an oxyanion of sulfur such as sulfate or sulfite. This type of a catalyst will be herein referred to as "modified catalyst" or "modified metal oxide catalyst." As used herein, "catalyst" or "condensation catalyst" refers to either the unmodified or modified catalysts described above.
Without intending to be bound by any particular theory, it is believed that modification of the Group IVB metal oxide with the oxyanion of the Group VIB metal may impart acid functionality to the material. The modification of a Group IVB metal oxide, particularly zirconia, with a Group VIB metal oxyanion, particularly tungstate, is described in U.S. Patent No. 5,113,034; in Japanese Kokai Patent Application No. Hei 1 [1989]-288339; and in an article by Arata and Hino in Proceedings 9th International Congress on Catalysis, Volume 4, pages 1727-1735 (1988), the entire disclosures of these publications are incorporated herein by reference.
As used herein, the expression "Group IVB metal oxide modified with an anion" is intended to connote a material comprising, by elemental analysis, a Group IVB metal, oxygen, and an element selected from the group consisting of a Group VIB metal, cerium or sulfur. The present Group IVB metal oxide, e.g., zirconium oxide (or zirconia) modified with an anion is believed to result from a chemical interaction between a source of a Group IVB metal oxide and a source of an anion. This
chemical interaction is discussed in the aforementioned article by Arata and Hino in Proceedings 9th International Congress on Catalysis, Volume 4, pages 1727-1735 (1988). In this article, it is suggested that solid superacids are formed when sulfates are reacted with hydroxides or oxides of certain metals, e.g., Zr. Such a superacid is believed to be a bidentate sulfate ion coordinated to the metal, e.g., Zr. Further, it is suggested that a superacid can also be formed when tungstates are reacted with hydroxides or oxides of Zr. The resulting tungstate-modified zirconia materials are believed to have an analogous structure to the aforementioned superacids comprising sulfate and zirconium, wherein tungsten atoms replace sulfur atoms in the bidentate structure.
Although it is believed that the present catalysts may comprise the bidentate structure suggested in the aforementioned article by Arata and Hino, the particular structure of the catalytically active site in a modified catalyst has not yet been confirmed, and it is not intended that this catalyst component should be limited to any particular structure.
Other elements, such as alkali (Group IA) or alkaline earth (Group IIA) compounds may optionally be added to the condensation catalysts to alter catalytic properties. Surprisingly, it has been discovered that the addition of such alkali or alkaline earth compounds to the present catalyst may enhance the catalytic properties of components thereof.
According to the present invention, Group IVB metals (i.e., Ti, Zr or Hf), Group VIB metals, cerium, or sulfur species of the modified catalyst are not limited to any particular valence state for these species. These species may be present in the modified catalyst in any possible positive oxidation state for these species. For example, subjecting a tungsten-containing catalyst to reducing conditions, believed to be sufficient to reduce the valence state of the tungsten, may enhance the overall catalytic ability of the catalyst to catalyze certain reactions.
Suitable sources of the Group IVB metal oxide used for preparing modified catalysts of the present invention include compounds capable of generating such
oxides, such as oxychlorides, chlorides and nitrates, particularly of zirconium or titanium. Alkoxides of such metals may also be used as precursors or sources of the Group IVB metal oxide. Examples of such alkoxides include zirconium π-propoxide and titanium /-propoxide. Preferred sources of a Group IVB metal oxide are zirconium hydroxide, i.e., Zr(OH)4, and hydrated zirconia. The expression "hydrated zirconia" is intended to connote materials comprising zirconium atoms linked to other zirconium atoms via bridging oxygen atoms, i.e., Zr-O-Zr. As suggested in the aformentioned article by Arata and Hino in Proceedings 9th International Congress on Catalysis, Volume 4, pages 1727-1735 (1988), precalcination of Zr(OH)4 at a temperature of from 100°C to 400°C results in a species which interacts more favorably with tungstate. Without intending to be bound by any particular theory, this precalcination is believed to result in the condensation of Zr(OH) groups to form a polymeric zirconia species with surface hydroxyl groups. This polymeric species is referred to herein as a form of a hydrated zirconia.
According to the present invention, treatment of hydrated zirconia with a base solution prior to contact with a source of tungstate may be preferable. Particularly, refluxing hydrated zirconia in an NH4OH solution having a pH of greater than 7 may be preferable. While not being bound by theory, it is believed that the base-treated, hydrated zirconia is preferable because of its high surface area. It is also possible that the base treatment alters surface hydroxyl groups on the hydrated zirconia, possibly in a manner which promotes a more desirable interaction with the source of tungstate later used.
Suitable sources for the oxyanion of the Group VIB metal, preferably molybdenum or tungsten, include, but are not limited to, ammonium metatungstate or ammonium metamolybdate, tungsten or molybdenum chloride, tungsten or molybdenum carbonyl, tungstic or molybdic acid and sodium tungstate or molybdate. A preferred source for the oxyanion of sulfur is sulfuric acid.
The present catalyst may be prepared, for example, by impregnating the hydroxide or oxide of the Group IVB metal, particularly the hydrated oxide, with an aqueous solution containing an anion of the Group VIB metal, preferably tungstate or
molybdate, followed by drying. Calcination of the resulting material may be carried out, preferably in an oxidizing atmosphere, at temperatures from 500°C to 900°C, preferably from 700°C to 850°C, and more preferably from 750°C to 825°C. The time duration for calcination may be up to 48 hours, preferably 0.5 to 24 hours, and more preferably 1 to 10 hours. In one preferred embodiment, calcination is carried out at 800°C for 1 to 3 hours.
When a source of the hydroxide or hydrated oxide of zirconium is used, calcination of the combination of this material with a source of an oxyanion of tungsten at temperatures greater than 500°C may be preferable. However, when more reactive sources of zirconia are used, it is possible that such calcination may be carried out at lower temperatures.
According to the modified catalyst of the present invention, zirconium oxide is a preferred Group IVB oxides. Further, it is preferred that the oxyanion of the Group VIB metal be tungstate.
The modified catalyst according to the present invention comprises oxygen, a Group IVB metal, and an element selected from the group consisting of a Group VIB metal, cerium or sulfur. Elemental analysis may be used to determine the composition of the catalyst. The amount of oxygen measured in such an analysis depends on a number of factors, including the valence state of the metals or sulfur, and moisture content of the catalyst. Accordingly, in characterizing the composition of the present catalyst, it is best not to be restricted by any particular quantities of oxygen. In functional terms, the amount of anion in the modified catalyst may be expressed as that amount which increases the acidity of the Group IVB oxide. This amount is referred to herein as an acidity increasing amount. Elemental analysis of the present catalyst may be used to determine the relative amounts of Group IVB metal and Group VIB metal, cerium or sulfur in the catalyst. From these amounts, mole ratios in the form of X02AO3 may be calculated, wherein X is said Group IVB metal, believed to be in the form X02, and Y is said Group VIB metal, cerium or sulfur, believed to in the form of Y03. It will be appreciated, however, that these forms of oxides, i.e., Y03 and XO2, may not actually exist, and are referred to herein simply for the purposes of
calculating relative quantities of X and Y in the catalyst of the present invention. The present catalysts may have calculated mole ratios, expressed in the form of XO2/YO3, where X is at least one Group IVB metal (i.e., Ti, Zr, and Hf) and Y is at least one Group VIB metal (i.e., Cr, Mo, or W) or cerium or sulfur, of up to 1000. In one preferred embodiment of the present invention, the molar ratio is up to 300. In a further preferred embodiment the molar ratio is 2 to 100. In a still further preferred embodiment the molar ratio is from 4 to 30.
It may be desirable to incorporate the modified and unmodified catalysts with another material to improve its properties. Such materials include active and inactive materials and synthetic or naturally-occurring zeolites as well as inorganic materials such as clays, silica and metal oxides. The inorganic materials may be either naturally-occurring, or may be in the form of gelatinous precipitates, sols or gels, including mixtures of silica and metal oxides.
The condensation catalysts of the present invention may be subjected to a final calcination process under conventional conditions to convert the metal component to the oxide form and to confer the required mechanical strength on the catalyst. Prior to use, the catalysts of the present invention may be subjected to presulfiding (i.e., treating with hydrogen sulfide).
The condensation catalysts of the present invention may be used as exclusive catalysts in single or multiple catalyst beds, or may be used in combination with other catalysts. For example, a feed may be first contacted with a catalyst bed comprising a first catalyst, followed by contact with a second catalyst bed comprising a different catalyst. The temperatures of the catalyst beds may differ.
The modified and unmodified catalysts of the present invention may be prepared in a wide variety of particle sizes. Generally speaking, the particles may be in the form of a powder, a granule, or a molded product, such as an extrudate having particle size sufficient to pass through a 2 mesh (Tyler) screen and which can be retained on a 400 mesh (Tyler) screen. When the catalyst is molded, such as by extrusion, the catalyst may be first extruded before it is dried, or may be partially dried
and then extruded. The catalyst of the present invention may contain a matrix material which comprises the finished form of the catalyst. Conventional matrix materials include, but are not limited to, alumina, silica-alumina and silica. Silica is preferred as a non-acidic binder. Other binder materials may be used, for example, titania, zirconia and other metal oxides or clays. The active catalyst may contain the matrix material in catalyst: matrix material ratios of from 80:20 to 20:80 by weight. In one preferred embodiment, the catalyst: matrix material ratio is from 80:20 to 50:50. A composite of the catalyst and matrix material may be prepared by conventional means such as mulling the materials together, followed by extrusion of pellets into the desired finished catalyst particles. The catalyst may also be treated by conventional presulfiding treatments, e.g., by heating in the presence of hydrogen sulfide to convert oxide forms of the metal components to their corresponding sulfides.
The catalysts of the present invention are used in the process for preparing bisphenols, in particular, bisphenol A. The process of the present invention comprises the step of contacting a phenolic compound with a carbonyl-containing compound in the presence of at least one of the catalysts described herein.
The phenolic compound employed as the starting material in the production of bisphenols is a compound containing at least one hydroxyl group linked to a carbon atom of an aromatic group. Suitable phenolic compounds include, but are not limited to, phenols and substituted phenols. Phenolic compounds of the present invention include, but are not limited to, phenol, cresols, xylenols, chlorophenols, thymol, carvacrol, cumenol, 2-methyl-6-ethylphenol, 2,4-dimethyl-3-ethylphenol, 4- ethylphenol, 2-ethyl-4-methylphenol, 2,3,6-trimethylphenol, 2-methyl-4-f-butylphenol,
2,4-di-f-butyl-phenol, 4-methyl-2- -butylphenol, 2-f-butyl-4-methy I phenol, 2,3,5,6- tetramethylphenol, 2,6-dimethylphenol, 2,6-di-f-butylphenol, 3,5-dimethylphenol, 3,5- diethylphenol, 2-methyl-3,5-diethylphenol, o-phenylphenol, p-phenylphenol, tetraphenolethane, naphthols, phenanthrol, their homologues and analogues. Suitable phenolic compounds also include those containing one or more phenolic groups.
Carbonyl-containing compounds employed as the starting material for the bisphenols of the present invention include compounds containing ketone or aldehyde groups. Examples of suitable ketones include, but are not limited to, acetone, 1 ,3- dichloroacetone, dimethyl ketone, methyl ethyl ketone, diethyl ketone, dibutyl ketone, methyl isobutyl ketone, cyclohexanone, fluorenone, propionylphenone, methyl amyl ketone, mesityl oxide, cyclopentanone, acetophenone. Examples of suitable aldehydes include, but are not limited to, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde and benzaldehyde.
The specific phenolic compound and carbonyl-containing compound employed as starting materials will depend upon the specific bisphenol compound being synthesized, and may be governed to some extent by specific operating conditions employed. In a preferred embodiment, the process of the present invention is used for the synthesis of bisphenol A. For this process, the carbonyl-containing compound is acetone and the phenolic compound is phenol. Typically, excess phenol is used for the condensation reaction. The preferred ratio of phenol to carbonyl-containing compound ranges from 20:1 to 2:1. A preferred ratio is 10:1 to 2:1. Optionally, the condensation reaction may be carried out in the presence of an added promoter. Any known promoter for the acid-catalyzed condensation of a phenolic compound and a carbonyl-containing compound, or for the acid-catalyzed isomerzation/reversion of bisphenol by-products, is suitable. Suitable promoters include, but are not limited to, glycolic acids, hydroxy substituted aromatics and derivatives thereof, and mercaptans which are either free or bound to a polymer. Alkyl mercaptans and bis-mercapto ethanolamine are examples of suitable mercaptan promoters for the processes of the present invention. Hydroxy substituted aromatics and derivatives thereof suitable as promoters include, but are not limited to, catechol, resorcinol, hydroquinone and the mono- and di-methyl and the mono- and di-ethyl ethers thereof, p-ethylphenol, o- cresol, p-cresol, orcinol (3,5-dihydroxytoluene) and the mono- and di-lower alkyl ethers thereof, pyrogallol (1 ,2,3-trihydroxybenzene) and the mono-, di- and tri-lower- alkyl ethers thereof, phloroglucinol (1 ,3,5-trihydroxybenzene) and the mono-, di- and tri-lower-alkyl ethers thereof, thymol (2-isopropyl-5-methylphenol),α-naphthol, 5- methyl-α-naphthol, 6-isobutyl-α-naphthol, 1 ,4-dihydroxynaphthalene, 6-hexyl-1,4- dihydroxynaphthalene, 6-methyl-4-methoxy-α-naphthol, and the like.
Upon completion of the reaction, the bisphenol product may be purified and recovered by methods known in the art. Suitable means for recovery of bisphenols include, but are not limited to, distillation, solvent extraction, stratification, extractive distillation, adsorption, crystallization, filtration, centrifugation and thermal liberation. Bisphenol A is typically recovered by crystallization in which crystals of bisphenol A or bisphenol A adducts are separated from the remaining solution by filtration or centrifugation.
Those skilled in the art will appreciate that numerous changes and modifications may be made to the preferred embodiments of the present invention, and that such changes and modifications may be made without departing from the spirit of the invention. It is, therefore, intended that the appended claims cover all such equivalent variations as fall within the true spirit and scope of the present invention.
EXAMPLES
Example 1
Preparation of a tungstate modified zirconia catalyst.
One part by weight of zirconyl chloride, ZrOCLxδH^O, was added to 3 parts by weight of a 10 M NH4OH solution. The resulting slurry, Zr(OH)4, was filtered and washed with 5 parts of distilled deionized water, then air dried at 140°C for 8 hours. Approximately 7.5 parts by weight of the resulting Zr(OH)^, were impregnated via incipient wetness with 2.2 parts of an aqueous solution containing 1 part of ammonium metatungstate, (NH^JgHgW-^O^. The resulting material was dried for 2 hours at
120°C and then calcined at 800°C in flowing air for 2 hours. The sample was calcined at 500°C for 1 hour under flowing nitrogen prior to catalytic testing. This sample had a calculated mole ratio of Zr02/W03 of 11.6.
Example 2
Preparation of a hydrous ZrO∑ support.
One part by weight of zirconyl chloride, ZrOCl2 8H2θ, was dissolved in 10 parts H2O and concentrated NH4OH added until the solution pH was -9. The resulting slurry, Zr(OH)4, was filtered and washed with 10 parts of distilled, deionized water. The solid was air dried at 130°C for 16 hours.
Example 3
Preparation of a W0x/ZrO2 catalyst from the support described in Example 2.
Approximately 5.6 parts by weight of the dried product from Example 2 was impregnated via incipient wetness with 4.2 parts of an aqueous solution containing 1 part of ammonium metatungstate,
The resulting material was dried in air and then calcined at 825°C in air for 3 hours.
Example 4 Preparation of a WOx/ZιO2 catalyst from the support described in Example 2.
Approximately 2.4 parts by weight of the dried product from Example 2 was impregnated via incipient wetness with 2.6 parts of an aqueous solution containing 1 part of ammonium metatungstate. The resulting material was dried in air and then calcined at 825°C in air for 3 hours.
Example 5
Preparation of base-treated zirconia support.
One part by weight of the filtered wet cake from Example 2 was mixed with 10 parts of distilled, deionized water and the pH of the mixture set to pH -9 with concentrated aqueous NH4OH. This mixture was refluxed for 16 hours, cooled, filtered, and washed with 10 parts of water. The solid was air dried at 130°C for 16 hours.
Example 6
Preparation of a WOx/ZrO2 catalyst from the support described in Example 5.
Approximately 5.6 parts by weight of the dried product from Example 5 was impregnated via incipient wetness with 4.2 parts of an aqueous solution containing 1 part of ammonium metatungstate. The resulting material was dried in air and then calcined at 825°C in air for 3 hours.
Example 7
Preparation of a zirconia support.
One part by weight of zirconyl chloride, ZrOCl2_8H20, was dissolved in 10 parts H20 and concentrated aqueous NH4OH added until the solution pH was ~9. The resulting slurry, Zr(OH)4, was filtered and washed with 10 parts of distilled, deionized water. The solid was mixed with 10 parts of distilled, deionized water, and the pH of the mixture set to pH ~9 with aqueous NH4OH. This mixture was refluxed for 16 hours, cooled, filtered, and washed with 10 parts of water. The solid was air dried at 130°C for 16 hours.
Example 8
Preparation of a WOx/ZrO2 catalyst from the support described in Example 7.
Approximately 3.3 parts by weight of the dried product from Example 7 was impregnated via incipient wetness with 2.6 parts of an aqueous solution containing 1 part of ammonium metatungstate. The resulting material was dried in air and then calcined at 825°C in air for 3 hours.
Example 9
Data from the synthesis of bisphenol A using a WOx/ZrO2 catalyst and comparative data using an ion-exchange catalyst.
Phenol and acetone were reacted to form bisphenal A (BPA)in the presence of a WOχ/Zrθ2 catalyst. Twenty-one runs over a range of experimental conditions were made. Data from a typical run are shown in Table 1 , which also contains comparative data for runs using an Amberlite® resin catalyst.
Table 1
Catalyst Amberlite® 118 WOx/Zr0 Reactor fixed-bed stirred tank
Temperature, °C 75 125 Pressure, atm 1 1 Residence time, hr 1 Feed molar ratio
(phenol:acetone) 10 10 Conversion per pass,% phenol 10 7 acetone 50 35 Selectivity to BPA, % 81 78
19 (o,p -isomer)
Example 10
Synthesis of Bisphenol A using a sulfated zirconia catalyst.
Phenol (47.3 g), acetone (3.0 g), and sulfated zirconia (1.0 g, F26830, calcined @ 550°C/3 hr) was charged into a stirred autoclave, and the resulting mixture was heated for 3 days at 125°C. The conversions were acetone 41 %, phenol 7%, and the selectivity to bisphenol A was greater than 95% (p,p'/o,p' = 65/35).