Us 3660503

‘United’ ‘States Patent ()f?ce 1 3,660,503 PREPARATION OF PRIMARY ALCOHOLS Herman S . Bloch, Skokie, and George R . Lester, Park Ridge, Ill., assignors to Universal Oil Products Com pany, Des laines, Ill. N o Drawing. Continuation-impart o f application Ser. No. 833,787, June 16, 1969, which is a continuation-in-part of application Ser. No. 579,499, Sept. 15, 1966. This application Aug. 18, 1970, Ser. No. 64,812 Int. Cl. C07c 1/02, 37/00 US. Cl. 260——617 H 11 Claims ABSTRACT OF THE DISCLOSURE Hydrocarbonaceous compounds such as n-paraf?ns, branched-chain para?ins, and certain cyclopara?ins can b e converted t o primary alcohols by treatment with h y drogen peroxide a s the sole hydroxylating agent in the presence of a catalyst containing a Group VIII metal such as nickel composited on kieselguhr. I n this way n-pentane can be converted to l-pentanol. This application i s a continuation-in-part of our co pending application, Ser. No. 833,787, ?led June 16, 1969‘ and now abandoned, which was a continuation-in-part o f our copending application, Ser. No. 579,499‘, ?led Sept. 15, 1966 and now abandoned. This invention relates t o a process for the production of alcohols and particularly t o a novel method for the production of primary alcohols utilizing hydrocarbo naceous compounds a s the starting materials. The use of alcohols in the chemical industry i s widely varied. For xample, aliphatic alcohols such as those con taining from 1 u p to about ‘ carbon atoms or more may b e used as solvents for other organic chemicals. I n addi tion, the alcohols are widely used i n synthesizing other organic derivatives. Speci?c uses for some f these alcohols include the use of l-pentanol a s a raw material for certain pharmaceutical preparations and use in other organic syn theses Another speci?c example i s the use of l-butanol i n the preparation of esters such as butyl acetate, a sol vent for resins and oatings, o r dibuty l phthalate, a plasti cizer, or esters useful as hydraulic ?uids, etc. I n addition, relatively long chain alcohols such as l-tetradacanol may b e used in organic synthesis, a s a plasticizer, as antifoam agents and s a base for the manufacture of wetting agents and detergents. IIt has now been discovered that alcohols, and particu larly primary alcohols, may be prepared i n a relatively inexpensive method utilizing hydrocarbonaceous com pounds such a s straight-chain or n-para?ins, branched chain para?‘lns, or cycloparaf?ns containing a t least one ethyl substituent a t the starting materials i n the process o f this invention. Heretofore the prior art has disclosed methods of treatment with peroxide o r a n oxygen-containing gas to effect a hydroxylation of hydrocarbonaceous compounds uch as para?ins or ole?ns. However, the results which are obtained i n these refer ences are markedly different from those which are ob tained by utilizing the compounds and conditions of the instant application. For example, one prior art reference discloses a process for treating hydrocarbonaceous com pounds such a s ole?ns i n a free radical reaction utilizing hydrogen peroxide, said reaction being effected a t a tem perature above 400° C . and referably from bout 400° t o about 650° C. This reference teaches that the energy uti lized to extract the labile hydrogen i s less than 90 kg. calories and preferably less than 8 5 kg. calories. However, in contradistinction t o this the present invention i s con cerned with the preparation o f primary alcohols in which 10 2 0 2 5 3 5 4 0 45 50 5 5 65 7 0 3,660,503 Patented May , 1972 2 the primary hydrogen atom on a compound has a bond energy o f 9 8 kg. calories which s considerably in excess o f that which is taught i n the prior art. Another prior art reference teaches the preparation of oxygenated hydrocarbons b y treating a hydrocarbon i n the liquid phase with oxygen, air, o r other oxygen-con taining gases using hydrogen peroxide a s the oxidation initiator. This reaction i s effected preferentially a t tem peratures ranging from about 93° to about 180° C . How ever, the alcohols which were obtained from this reac tion are secondary o r tertiary, and not predominantly primary i n structure a s are the products of this invention. I n addition, references disclose hydroxylation reactions for obtaining compounds such a s diols includ ing glycols, etc., but do not disclose the preparation of primary monohydric alcohols. A s hereinbefore set forth, i n contradistinction t o the prior art, it has now been discovered that alcohols, and particularly primary alcohols, may b e prepared accord ing t o the process hereinafter set forth i n greater detail using hydrogen peroxide as the sole hydroxylating agent and in the absence of any free gaseous oxygen. ‘It is therefore an object o f this invention t o provide a novel method for the production o f primary alcohols. Another object of this invention i s t o provide a novel method for obtaining primary alcohols utilizing para?inic hydrocarbons a s the starting material. In one aspect an embodiment o f this invention is found i n a process for the production of homologous predomi nantly primary alcohols which comprises treating a hydro carbonaceous compound selected from he group consist ing of n-parat?ns, branched-chain paraf?ns, and cyclo paraf?ns containing a t least ethyl with stoichiometric amounts of hydrogen peroxide as the sole hydroxylating agent i n the presence of a catalyst com prising a supported metal of Group VIII o f the Periodic Table a t reaction conditions including a temperature i n the range o f from about 150° t o about 350° C . and a pressure in the range o f from atmospheric to about 50 atmospheres, and recovering the resultant homologous primary alcohols. A speci?c embodiment o f this invention i s found in a process for the production o f alcohols which comprises treating n-pentane with hydrogen peroxide i n the presence of a catalyst comprising nickel composited on kieselguhr at a temperature in the range o f from about 150° to about 350° C. and at a pressure i n the range o f from atmos pheric to about 50 atmospheres, ‘and recovering the r e sultant l-pentanol, l-butanol, and l-propanol. Other objects and embodiments will be found in the following further detailed description of this invention. As hereinbefore set forth, the present invention is con cerned with a novel process for the production of alcohols, and particularly primary alcohols. I n this respect w e have now discovered that a hydrocarbonaceous compound which s saturated in nature and which contains only car bon and hydrogen atoms may b e treated with a h y droxylating agent, and preferably hydrogen peroxide a s the sole hydroxylating agent, at an elevated temperature to prepare the desired predominantly primary alcohols. Types of compounds which fall within the aforementioned de?nition will include n-paraf?ns, branched-chain paraf fins, and cyclopara?ins which contain at least one ethyl substituent on the saturated ring. The novelty of the pres ent invention resides in the fact that, under the reaction conditions and with the catalysts which are employed and in the absence o f any added free oxygen, methyl groups ‘are selectively hydroxylated. Thus, i f the hydrocarbo naceous compound which s utilized a s the feed stock is a normal paraffin, l-alkanols are produced exclusively. I n addition, i t i s a further feature o f our invention that

Us 3660503

Documents

Transcript of Us 3660503