METHOD OF HYDROGENATION

Abstract

Provided is a method of hydrogenation comprising forming a reaction mixture comprising (a) one or more reactant selected from the group consisting of phenol, one or more derivatives of phenol, and mixtures thereof; (b) hydrogen; and (c) catalyst, wherein the catalyst comprises beads that comprise one or more acid-functional organic resin and one or more metal selected from the group consisting of palladium, platinum, silver, gold, rhodium, ruthenium, copper, iridium, and mixtures thereof.

Claims

1. A method of hydrogenation comprising forming a reaction mixture comprising (a) one or more reactant selected from the group consisting of phenol, one or more derivatives of phenol, and mixtures thereof; (b) hydrogen; and (c) catalyst, wherein the catalyst comprises beads that comprise one or more acid-functional organic resin and one or more metal selected from the group consisting of palladium, platinum, silver, gold, rhodium, ruthenium, copper, iridium, and mixtures thereof.

2. The method of claim 1, wherein the acid-functional organic resin comprises carboxylic acid groups.

3. The method of claim 1, wherein the acid-functional organic resin comprises acrylic polymer.

4. The method of claim 1, wherein the metal comprises palladium.

5. The method of claim 1, wherein the reactant is phenol.

6. The method of claim 1, wherein the hydrogenation produces one or more products that comprise cyclohexanone or a derivative thereof.

7. The method of claim 1, wherein the method is conducted at temperature less than 200 C.

Description

COMPARATIVE EXAMPLE 1C

[0052] To a 15 mL glass-lined, steel, pressure reactor (Endeavor Reactor available from Argonaut Technologies) equipped with mechanical stirring and gas inlet was added strong acid cation exchange resin (0.9 g). This resin was conditioned by rinsing the resin three times with 5 mL aliquots of acetone. After the resin had been conditioned, the reactor was charged with phenol (2.0 g) and isooctane solvent (3.5 g). Once all the ingredients were added, the reactor was closed, stirring commenced (350 rpm) and inertion process commenced by pressurizing to 21 bar (300 psi) with N.sub.2 (inert gas) followed by depressurization. This pressurization/depressurization cycle was done a further two times. Upon completion of reactor inertion, the reactor contents were pressurized to 21 bar (300 psi) with H.sub.2(g). The reactor was then heated to 110 C. for four hours. After the four hours, the contents of the reactor were allowed to cool, and the liquid contents were subjected to gas chromatography/mass spectrometry (GC/MS) to determine phenol conversion and cyclohexanone selectivity. Results are listed in Table 1.

EXAMPLES 2-7

[0053] To a 15 mL glass-lined, steel, pressure reactor (Endeavor Reactor available from Argonaut Technologies) equipped with mechanical stirring and gas inlet was added metal doped polymer catalyst (prepared as described in Example 2 of U.S. Pat. No. 8,552,223B2) (varying amounts, as shown in Table 1). This catalyst was conditioned by rinsing the catalyst three times with 5 mL aliquots of acetone. After the resin had been conditioned, the reactor was charged with phenol (2.0 g) and isooctane solvent (3.5 g). Once all the ingredients were added, the reactor was closed, stirring commenced (350 rpm), and inertion process commenced by pressurizing to 21 bar (300 psi) with N.sub.2 (inert gas) followed by depressurization. This pressurization/depressurization cycle was done a further two times. Upon completion of reactor inertion, the reactor contents were pressurized to 21 bar (300 psi) with H.sub.2(g). The reactor was then heated to 110 C. for four hours. After the four hours, the contents of the reactor were allowed to cool, and the liquid contents were subjected to GC/MS to determine phenol conversion and cyclohexanone selectivity. Results are listed in Table 1.

[0054] Results:

TABLE-US-00002 TABLE 1 All of Examples 2-7 used 2.8 grams of metal per liter of resin. amount of Conversion Selectivity Example Metal Resin catalyst (%) (%) 1C none Resin A15 0.9 g 0 0 2 Pd Resin A15 0.9 g 69 86.7 3 Pd Resin A36 0.9 g 81 93.6 4 Ru Resin A36 0.9 g 20 0 5 Pd Resin A35 0.09 g 78 63.3 6 Pd Resin A35 0.009 g 63 55.0 7 Pd Resin HP333 0.9 g 90 95.7

[0055] The inventive Examples 2-7 showed some conversion of reactant, while the comparative example 1C showed no conversion. Palladium performed better than ruthenium. Example 7, which used a weak-acid resin, showed the best conversion and the best selectivity.