Patent GB-448690-A (GB)
Title: Improvements in the manufacture and production of non-knocking motor fuels
IPC: C07C9/00
Filed: 1934-10-08
Abstract: For the production of non-knocking motor fuels, the mixture of isobutyl and higher alcohols obtained by the catalytic treatment of carbon monoxide and hydrogen, for instance as described in Specification 238,319, [Class 2 (iii)], freed from methanol, is converted into olefines, for instance by catalytic treatment with alumina at 300 DEG  C., and the mixed olefines either as a whole or after separation into two or more fractions are at least in part polymerized, for instance di-isobutylene may be obtained by treating isobutylene with sulphuric acid of 50--60 per cent as described in Specification 322,102, [Class 2 (iii)], and tri-isobutylene by means of more concentrated acid such as 70 per cent acid, and dimers and trimers of isoamylene may be obtained similarly.  When the separate fractions are polymerized the polymers may be mixed with one another or with other fuels; other anti-knock agents such as iron carbonyl, lead tetraethyl and monomethyl-aniline, or "upper lubricating oils" may also be added; methanol, or the higher alcohols from the methanol synthesis, and also dyes and substances imparting odour may also be added.  A large number of particular fuels are mentioned, including mixtures of polymers of isobutylene with olefines or paraffins; isooctane (obtained by hydrogenating di-isobutylene) and mixtures thereof with olefines or paraffins obtained from them; dodecane (obtained by hydrogenation of tri-isobutylene) and mixtures thereof with di-isoolefines or with decane, dodecane or tetradecane obtained from them.  In an example, a mixture of carbon monoxide and hydrogen is passed at 200 atmospheres and 450--500 DEG  C. through a copper - lined apparatus containing a catalyst prepared by adding zinc oxide to fused potassium dichromate and reducing with hydrogen, and the reaction product is freed from methanol and water and converted to olefines as described above; the mixed olefines are treated with, e.g. 55 per cent sulphuric acid at 100 DEG  C. to polymerize the lower olefines, particularly the isobutylene, to dimers and trimers, or with 70 per cent acid which also polymerizes hexylene and heptylene to dimers; the products may be hydrogenated (for instance by nickel or pumice or silica gel) wholly or partially.  The Provisional Specification includes the dehydration of individual alcohols separated from the mixed alcohols.ALSO:For the production of non-knocking motor fuels, the mixture of isobutyl and higher alcohols obtained by the catalytic treatment of carbon monoxide and hydrogen for instance as described in Specification 238,319, [Class 2 (iii)], freed from methanol, is converted into olefines for instance by catalytic treatment with alumina at 300 DEG  C., and the mixed olefines, either as a whole or after separation into two or more fractions are at least in part polymerized, for instance di-isobutylene may be obtained by treating isobutylene with sulphuric acid of 50--60 per cent as described in Specification 322,102, [Class 1 (iii)], and tri-isobutylene by means of more concentrated acid such as 70 per cent acid, and dimers and trimers of isoanylene may be obtained similarly.  When the separate fractions are polymerized the polymers may be mixed with one another or with other fuels; other antiknock agents such as iron carbonyl lead tetracethyl and monomethyl-aniline, or "upper lubricating oils" may also be added; methanol, or the higher alcohols from the methanol synthesis, and also dyes and substances imparting odour may also be added.  A large number of particular fuels are mentioned, including mixtures of polymers of isobutylene with olefines, or paraffins; iso-octane (obtained by hydrogenating di-isobutylene) and mixtures thereof with olefines or paraffins obtained from them; dodecane (obtained by hydrogenation of tri-isobutylene) and mixtures thereof with di-isoolefines or with decane, dodecane, or tetredecane obtained from them.  In an example, a mixture of carbon monoxide and hydrogen is passed at 200 atmospheres and 450--500 DEG  C. through a copper-lined apparatus containing a catalyst prepared by adding zinc oxide to fused potassium di-chromate and reducing with hydrogen, and the reaction product is freed from methanol and water and converted to olefines as described above; the mixed olefines are treated with e.g. 55 per cent sulphuric acid at 100 DEG  C. to polymerize the lower olefines, particularly the isobutylene, to dimers and trimers, or with 70 per cent acid, which also polymerizes hexylene and heptylene to dimers; the products may be hydrogenated (for instance by nickel or pumice or silica gel wholly or partially.  The Provisional Specification includes the dehydration of individual alcohols separated from the mixed alcohols.