Field of the Invention

The present invention relates to improvements in a process for the preparation of p-aminophenol from nitrobenzene. Description of the Background Art

The compound p-aminophenol (PAP) is an important chemical intermediate used in the preparation of the analgesic acetaminophen. A number of other derivatives having a wide variety of industrial applications may also be prepared from PAP. One method for preparing PAP involves the catalytic hydrogenation of nitrobenzene in an acid medium. In this process, phenylhydroxylamine is first formed, and this intermediate promptly rearranges in the acid reaction medium to form PAP.

Henke, et al. (U.S. Patent No. 2,198,249) reportedly were the first to disclose a process for the preparation of PAP by the catalytic hydrogenation of nitrobenzene in an acid medium. A number of process variations have since been disclosed. For example, Spiegler (U.S. Patent No. 2,765,342) studied the reaction extensively. Among the factors explored by Spiegler was the effect on reduction rate and p-aminophenol yield of including a surfactant selected from among quaternary ammonium compounds and several non-quaternary compounds. Among the quaternary ammonium compounds used was dodecyl

trimethylammonium chloride. The non-quaternary compounds investigated include two simple tertiary amine salts! triethylamine sulfate and tributylamine βulfate, as well as dioσtadeσyl prσpyleneamine dioleate. From a plot of rate and yield data, Spiegler concluded that- the rate/yield performance of all of the quaternary ammonium compounds examined was superior to that of the non-quaternary compounds.

Later, Brown et al. (U.S. Patent No. 3,535,382) reported that certain nonioniσ polyether polyol surfactants could be substituted for Spiegler's quaternary ammonium compounds.

R.G. Benner (U.S. Patent No. 3,383,416) used the Henke et al. approach of charging all the nitrobenzene at once, but used a carbon-supported platinum σataiyst and quaternary ammonium surfactant, preferably dodeσyl trimethylammonium chloride, as disclosed by Spiegler. Benner purposely interrupted the hydrogenation well before all the nitrobenzene had been consumed. In the presence of two liquid phases, aqueous and nitrobenzene, a carbon-supported platinum catalyst is preferentially wetted by the nitrobenzene, so most of the catalyst is suspended in the nitrobenzene layer, permitting the removal of the upper aqueous solution of PΛP and aniline by decantation. The PAP is then recovered from the aqueous layer and purified.

While Benner proposed quaternary ammonium salts as the surfactant, other surfactants have been utilized, including amine oxide (Sathe, U.S. Patent No. 4,176,138) and amine salts (Derrenbaσher, U.S. Patent No. 4,307,249). Use of these surfactants tends to result in formation of stable emulsions, which makes separation of the desired PΛP product difficult.

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There remains a need in the art for improvements in the process for preparing p-aminophenol by catalytic hydrogenation of nitrobenzene.

SUMMARY OF THE INVENTION In accordance with the present invention, a process for preparing p-aminophenol comprises catalytically hydrogenating nitrobenzene in an acidic reaction medium containing an alkσxylated fatty amine of the formula (I) ι

wherein R represents alkyl having from about 6 to about 20 carbon atoms; Rj and R ₂ are the same or different, and are represented by the formula -[ (CH ₂ ) _a 0] _n H, wherein m is an integer of from 1 to about 5, and n is an integer from 1 to about 10.

Detailed Description of the Preferred Embodiments The improved process of the present invention involves catalytic hydrogenation of nitrobenzene in an acid reaction medium containing an alkoxylated fatty amine surfactant of the formula (I) as set forth above, wherein R, i and R ₂ are as previously defined. In preferred embodiments, the acidifying agent is sulfuriσ acid, although other acids can be used.

In preferred embodiments of the present invention, the alkyl group R has from about 8 to about 16 carbon atoms, more preferably from about 10 to about 14 carbon atoms, and most preferably 12 carbon atoms. The alkyl group R can be branched, but in preferred embodiments is straight chain.

, As noted above, | and R ₂ can be the same or different, and are represented by the formula -[ (CH ₂ ) _β 0] _n H, wherein m is an integer of from 1 to about

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5, and n is an integer from 1 to about 10. In preferred embodiments, m is 2 or 3, most preferrably 2.

In accordance with one aspect of the embodiment wherein Rj and R ₂ are the same and m is 2, n is preferrably 1. In a particularly preferred embodiment wherein n is 1 for both Rj and R ₂ , R is a straight chain alkyl group having about 12 carbon atoms.

In another embodiment, Rj and R ₂ are different. In accordance with one aspect of this embodiment, m is 2 and n is 2 or 3. In a preferred aspect of this embodiment wherein m is 2 and R _t and R ₂ are different, R is a straight chain alkyl group of about 12 carbon atoms. In accordance with a particularly preferred aspect of this embodiment, the n of R _t is 2 and the n of R ₂ is 3.

In yet another embodiment wherein R _x and R ₂ are different, m preferably is 2, and the n of Ri is 8 while the n of R ₂ is 7.

During catalytic hydrogenation of nitrobenzene in the acid reaction medium, the amine surfactant of the present invention can be present in the reaction medium at a concentration within the range of from about 0.1- 50 g/1, preferably about 0.5-25 g/1, and more preferably about 1-15 g/1. The invention is illustrated by the following examples, which are not intended to be limiting. Example I

The following reagents were charged into a six liter glass hydrogenator equipped with Teflon coated mechanical agitator and Teflon coated baffles: 4000 ml deionized water, 1200 g nitrobenzene, 2 g 1.5% platinum on carbon catalyst, 4 g Ethomeen™ C/12 (Akzo Inc.) surfactant, and 665 g sulfuric acid. The mixture was heated to 80 degrees C under a nitrogen atmosphere.

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The reactor then was purged with hydrogen, pressurized to 10 psig, and the agitation increased to 1000 rpm. After 2.5-3.0 hours the agitation was stopped and the reactor purged with nitrogen. After cooling to room temperature the two phases were separated and the aqueous phase analyzed by HPLC. The results were compared in th£ following Examples to a standard experiment with docecyldimethyl amine (ADMA™ 2, Ethyl Corp.) as the surfactant. Example II

Emulsions were prepared by adding an acidic solution of p-aminophenol and surfactant (50 g PAP/1, 15% sulfuric acid, and 2 g surfactant/1) to a rapidly stirred mixture of nitrobenzene and carbon. The resulting emulsions were transferred to graduated cylinders and placed in a water bath at 75 degrees C. The time required for the phases to separate was recorded and taken as a measure of emulsion stability. The results are shown in Table 1 below: Table 1

Emulsion Volume, ml Time ADMA™ 2 Ethomeen™ C/12 Ethomeen™ C/15

20 40

35 15

30

12 20

Specifications for Table 1: 50 mg/ml PAP, 2.0 mg/ml Surfactant, 14.5 w/v Sulfuric Acid, 5.0 mg/ml carbon, 0.25 O/A (organic to aqueous ratio by volume).

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Example III

Emulsions were prepared and tested as in Example

II, except with the specifications set forth below.

The results are shown in Table 2 below:

Table 2

Emulsion Volume, ml

Ethomeen™ C/12 Ethomeen™ C/15

7 50

10 50 10 50

10 50 10 50

Specifications for Table 2: 50 mg/ml PAP, 12.0 mg/ml

Surfactant, 14.5 w/v Sulfuric Acid, 5.0 mg/ml carbon, 0.25 0/A.

Example IV

Emulsions were prepared and tested as in Example

II, except with the specifications set forth below.

The results are shown in Table 3. Table 3

Emulsion Volume, ml

Ethomeen™ C/12 Ethomeen™ C/15

15 50

13 40 11 25

11 25 11 25 11 20

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Specifications for Table 3» 50 mg/ml PAP, 1.0 mg/ml Surfactant, 14.5 w/v Sulfuric Acid 5.0 mg/ml carbon, 0.25 O/A. Example V Surfactants Ethomeen™ C/12 and Ethomeen™ C/15 were tested in a six liter hydrogenator and compared to ADMA™ 2. Both equivalent weight and moles of the two Ethomeen™ products were used. The results are summarized in Table 4 below. Table 4

On an equivalent mole basis, both of the Ethomeen™ products settled faster than ADMA™. Both of the Ethomeen™ products exhibited higher yield and selectivity, although the Ethomeen™ C/12 product was better yet. For equivalent weight charges, the rates for both Ethomeen™ products were about the same, but slightly lower than the equivalent mole basis experiments. The yie. ^' :d and selectivity were also lower, but Ethomeen™ C/12 was still better than ADMA™.

In all cases, the Ethomeen™ C/12 product exhibited the greatest emulsion instability. The emulsions were considerably less stable than with ADMA™, and also less stable than Ethomeen™ C/15. A reduction in emulsion stability is very beneficial for commercial production

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of PAP, since a considerable amount of down time associated with commercial production of PAP is due to emulsion related problems.

Furthermore, in a recycle experiment, use of Ethomeen™ C/12 was found to result in much greater catalyst recycle activity than use of ADMA, which may allow reduced catalyst use. Additionally, solid PAP which was isolated from the recycle experiment with Ethomeen™ C/12, was compared to PAP isolated from a typical experiment with ADMA. No unusual impurities were found in the HPLC assay of the PAP from the Ethomeen ¹ C/12 recycle experiment.

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