PRODUCTION OF HYDROQUINONE

Abstract: A process for making hydroquinone from phenol where­ in phenol is oxidised in the presence of a copper catalyst to p-benzoquinone and the p-benzoquinone is directly hyd­ rogenated without additional catalyst to hydroquinone.

Description: PRODUCTION OF HYDROQUINONE This invention relates to the production of hydroquinone. It is known that phenol can be oxidised to pbenzoquinone in the presence of copper catalysts; see for example US-PS 3,987,068. Improvements to these copper-catalyzed oxidations of phenol to p-benzoquinone have been disclosed and claimed in EP-A 0070665 and European Patent Application No. 83300210.8. Heretofore, p-benzoquinone has been converted to hydroquinone by the use of various catalysts. Thus, for example, Sabatier passed quinone vapours mixed with hydrogen over a reduced copper catalyst (e.g., a heterogeneous vapour-phase system) to obtain hydroquinone (Comptes rendus Ac. Sc. vol. 146, p. 457, 1908 and vol. 172 p. 733, 1921), but in this process the catalyst has a very limited life. R. Cornubert and J. Phelisse, Compt. Rend. 229, 460 (1949) disclose use of Raney nickel to convert quinone to hydroquinone. US PS 2,495,521 discloses nickel, cobalt, or coppercatalyzed heterogeneous vapour phase hydrogenation of benzoquinone in the presence of steam. Popova et al., Chem. Abs. 53,?75 (19595 disclose hydrogenation of benzoquinone with nickel, platinum and palladium - calcium carbonSte-. N. Calvin, J. Am. Chem Soc. 61'2230 (1939) discloses use of a copper-quinoline complex derived from cuprous acetate to promote hydrogenation of purified quinone, but this process is limited in that, almost, only one-half mole of hydrogen is taken up per mole of the Copper I - quinoline complex and thus the hydrogenation is very inefficient and perhaps not catalytic. Also of interest is the disclosure of Yananaka et al., Bull. Inst. Phys. Chem. Research (Tokyo) 14, 31 1935 which reduces quinones to oxy compounds with copper and Al203-promoted nickel. We have now found that a good yield of hydroquinone is readily obtained when the p-benzoquinone in a reaction mass obtained by oxidation of phenol with a copper catalyst is hydrogenated directly, i.e., without isolation, and without any additional catalyst. It is quite obvious that such a "one-pot process provides a highly efficient means to obtain hydroquinone which is a commercial chemical much used in the photographic industry and as an inhibitor used in the stabilization of rubber compounds. Thus, the present invention provides a process for making hydroquinone from phenol by oxidation of phenol to p-benzoquinone and conversion of p-benzoquinone to hydroquinone, characterised in that phenol is oxidised in the presence of a copper catalyst to p-benzoquinone and the p-benzoquinone is directly hydrogenated without additional catalyst to hydroquinone. The oxidation of phenol to p-benzoquinone with a copper catl--st. us, as ind1cated, well known in the art and any of such processes nay be used. Preferably, a process such as that disclosed in US-PS 3,987,068 will be used. Most preferably, the hydrogenation step of this invention wil] be used with the processes disclosed in (a) EP-A 0070665 where a diva lent copper catalyst promoted with an alkali metal is used (molar ratio of base to copper being no greater than about 2.0) and may also be further enhanced with water in an amount less than about 10% by volume of the reaction solution, and (b) European Patent ApplicationtNo. 83300210.8 where. a monovalent copper catalyst promoted with water is used (preferably 1 to 4 moles of water per mole of phenol). The hydrogenation step in the process will be carried out in a homogeneous, liquid phase simply by first removing oxygen from the system and then pressuring in hydrogen to a pressure of 34 to 345 bar gauge, preferably 69 to 207 bar gauge (about 500 to about 5000 psig, preferably about 1000 to about 3000 psig) and effecting the hydrogenation at a temperature from about 1000 to about 2Q00C, preferably from about 125C to about 1750C. In order to further exemplify the process, the following Examples are given: Example 1 500 mmole of phenol are oxidised in 350 ml of acetonitrile containing 35 mmole of CuCl2. An oxygen-containing gas (39% 02, 61% N! is continuously sparged through the mixture at t5"( > -nd 52 bar (750 psi) at 500 m'zhr. After four hour the. reaction mixture contains four mmole of phenol, 263 mmole of benzoquinone and six mmole of p-chlorophenol (99% conv., 53% selectivity). The oxygen is flushed from the system and hydrogen gas is admitted to a pressure of 207 bar (3,000 psi). The mixture is heated for fifteen hours at 1750C to give 135 mmoles of hydroquinone, 2 mmoles of unreacted p-benzoquinone, 17 mmoles of catechol, 6 mmoles of p-chlorophenol, 17 mmoles of phenol and a large amount of quinhydrone (a 1:1 complex of hydroquinone and p-benzoquinone). Yield calculations are difficult because of the low accuracy of the quinhydrone analysis, but a yield of up to about 71% is believed to be achieved. Example 2 In an experiment similar to Example 1, except that the CuCl2 catalyst is promoted with LiOH (one mole per mole of Curl2), selectivity to p-benzoquinone is about 70% at 99% conversion. The reaction mixture is hydrogenated by pressurizing 138 bar (2000 psi) of hydrogen on it at 1750C to give a yield of hydroquinone about the same as in Example 1. Example 3 Similar results are obtained when the process of Example 1 is carried out with a CuCl catalyst promoted with 500 mmcle of water.

Claims: CLAIMS 1. A process for making hydroquinone from phenol by oxidation of phenol to p-benzoquinone and conversion of p-benzoquinone to hydroquinone, characterised in that phenol is oxidised in the presence of a copper catalyst to p-benzoquinone and the p-benzoquinone is directly hydrogenated without additional catalyst to hydroquinone. 2. A process as claimed in claim 1, wherein the copper catalyst used in the oxidation of phenol is divalent and is promoted with an alkali metal. 3. A process as claimed in claim 1, wherein the copper catalyst used in the oxidation of phenol is a monovalent copper catalyst promoted with water. 4. A process as claimed in any of claims 1 to 3, wherein the hydrogenation is carried out under a hydrogen pressure of from 34 to 345 bar gauge and at a temperature of from 100 to 2000C.

Inventors: CHAO-YANG, HSU, LYONS, JAMES E.
Applicants: SUN REFINING AND MARKETING COMPANY
Application year: 1983
Main classification: C07C37
IPC codes: C07C39, C07C27, C07C67, C07C37, C07C46, B01J23, C07B61