Production of phenol

Details Production of phenol Production of phenol

1999-08-03

2001-10-02

Padmanabhan, Sreeni (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Oxygen containing

C568S385000, C568S768000, C568S754000, C568S741000

Reexamination Certificate

active

06297406

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to the production of phenol and more particularly to a process for producing phenol and acetone from cumene hydroperoxide.
2. Description of the Prior Art
Phenol is an important organic chemical with a wide variety of industrial uses. It is used, for example, in the production of phenolic resins, bisphenol-A and caprolactam. A number of processes are currently in use for the production of phenol but the single process providing the largest proportion of the total production capacity is the cumene process which now accounts for over three quarters of the total U.S. production. The basic reaction involved in this process is the cleavage of cumene hydroperoxide into phenol and acetone:
C
6
H
5
C(CH
3
)
2
OOH=C
6
H
5
OH+(CH
3
)
2
CO
On the industrial scale, the cumene hydroperoxide is usually treated with dilute sulphuric acid (5 to 25 percent concentration) at a temperature of about 50° C. to 70° C. After the cleavage is complete, the reaction mixture is separated and the oil layer distilled to obtain the phenol and acetone together with cumene, alpha-methylstyrene, acetophenone and tars. The cumene may be recycled for conversion to the hydroperoxide and subsequent cleavage. The phenol produced in this way is suitable for use in resins although further purification is required for a pharmaceutical grade product.
Although the process described above is capable of producing both phenol and acetone in good yields, it would be desirable to find a process which would reduce the need for the product separation and purification steps which are inherent in a homogeneous process and would avoid the need for environmentally hazardous liquid acids.
The heterogeneous cleavage of cumene hydroperoxide (CHP) over various solid acid catalysts has already been reported. For example, U.S. Pat. No. 4,490,565 discloses the use of zeolite beta in the cleavage of cumene hydroperoxide, whereas U.S. Pat. No. 4,490,566 discloses the use of a Constraint Index 1-12 zeolite, such as ZSM-5, in the same process.
U.S. Pat. No. 4,898,995 discloses a process for the coproduction of phenol and acetone by reacting cumene hydroperoxide over a heterogeneous catalyst consisting essentially of a heteropoly acid, such as 12-tungstophosphoric acid, on an inert support, such as silica, alumina, titania and zirconia. Such heteropoly acid catalysts are inherently unstable at temperatures in excess of 350° C.
U.S. Pat. No. 5,908,800 discloses a process for producing a mixed zirconium and cerium oxide useful as a catalyst for reducing nitrogen oxides in automotive exhaust by contacting a liquid mixture of cerium and zirconium compounds with carbonate and bicarbonate under neutral or alkaline conditions to form a precipitate comprising cerium carbonate and zirconium oxyhydroxide, and then calcining the precipitate.
According to the invention, it has now been found that a solid acid catalyst comprising mixed oxides of cerium and a Group IVB metal can exhibit activity and selectivity for cumene hydroperoxide cleavage.
SUMMARY OF THE INVENTION
The present invention resides in a process for producing phenol and acetone from cumene hydroperoxide, wherein the process comprises the step of contacting cumene hydroperoxide with a solid-acid catalyst comprising a mixed oxide of cerium and a Group IVB metal.
Preferably, Group IVB metal is zirconium.
Preferably, said solid acid catalyst also contains a further metal selected from Group IB, VIIB and VII metals, and preferably selected from iron, manganese and copper.
Preferably, the solid acid catalyst is produced by calcining a catalyst precursor comprising a source of a Group IVB metal oxide with a source of cerium oxide at a temperature of at least 400° C.
Preferably, said temperature is at least 500° C. and more preferably is 600-700° C.
Preferably, said catalyst precursor is precipitated from a liquid mixture containing ions of cerium and said Group IVB metal at a pH less than 9, and more preferably, 3 to 8.
Preferably, said contacting step is conducted at a temperature of 20 to 150° C. and a pressure of atmospheric to 1000 psig and more preferably at a temperature of 40 to 120° C. and a pressure of atmospheric to 400 psig.
The process of the invention can achieve significant conversion of cumene hydroperoxide to phenol and acetone with low coproduction of impurities such as mesityl oxide and diacetone alcohol.
DESCRIPTION OF SPECIFIC EMBODIMENTS
The process of the invention uses a mixed oxide of a Group IVB metal and cerium as a solid acid catalyst for the cleavage of cumene hydroperoxide into phenol and acetone.
The present catalyst may have a calculated mole ratio, expressed in the form of XO
2
/CeO
n
where X is at least one Group IVB metal (i.e., Ti, Zr, and Hf), of up to 1000, e.g., up to 300, e.g., from 2 to 100, e.g., from 4 to 80, although it is to be appreciated that these forms of oxides, i.e., XO
2
and CeO
n
, may not actually be present in the catalyst of the invention.
The Group IVB metal oxide is preferably selected from titania, zirconia and hafnia, with zirconia being most preferred. The Group IVB and cerium metal species present in the final catalyst are not limited to any particular valence state and may be present in any positive oxidation value possible for the respective species.
Suitable sources of the Group IVB metal oxide include compounds capable of generating such oxides during calcination with ceria, such as oxychlorides, chlorides, and nitrates. Alkoxides may also be used as the sources of the Group IVB metal oxide, for example zirconium n-propoxide and titanium i-propoxide. A preferred source of the Group IVB metal oxide is hydrated zirconia. The expression, hydrated zirconia, is intended to connote a material comprising zirconium atoms covalently linked to other zirconium atoms via bridging oxygen atoms and further comprising available surface hydroxyl groups. These available surface hydroxyl groups are believed to react with the ceria species to form the present acidic catalyst component. Hydrated zirconia can be formed by precalcination of Zr(OH)
4
at a temperature of about 100° C. to about 400° C.
While not being bound by this chemistry, it is speculated that interactions between the zirconia and ceria may be similar to those between zirconia and tungstate oxides, and therefore hydrothermal treatment of the hydrated Group IVB metal oxide, such as hydrated zirconia, could promote the interaction with the ceria species. The hydrothermal treatment conditions may include a temperature of at least 80° C., e.g., at least 100° C. The hydrothermal treatment may take place in a sealed vessel at greater than atmospheric pressure. However, a preferred mode of treatment involves the use of an open vessel under reflux conditions. Agitation of hydrated Group IVB metal oxide in the liquid medium, e.g., by the action of refluxing liquid and/or stirring, promotes the effective interaction of the hydrated oxide with the liquid medium. The duration of the contact of the hydrated oxide with the liquid medium may be at least 1 hour, e.g., at least 8 hours. The liquid medium for this treatment may have a pH of about 7 or greater, e.g., 9 or greater. Suitable liquid media include water, hydroxide soglutions (including hydroxides of NH
4
+
, Na
+
, K
+
, Mg
2+
, and Ca
2+
), carbonate and bicarbonate solutions (including carbonates and bicarbonates of NH
4
+
, Na
+
, K
+
, Mg
2+
, and Ca
2+
), pyridine and its derivatives, and alkyl/hydroxyl amines.
Suitable sources of cerium oxide include, but are not limited to, oxygen-containing salts, for example cerium sulfate.
In one embodiment of the invention, the catalyst is prepared by impregnating a hydrothermally treated hydrated oxide of the Group IVB metal with an aqueous solution containing cerium ions, followed by drying. The resulting catalyst precursor is then calcined in the manner described below.
In another embodiment of the invention, the catalyst is prepared by co-precipitation

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