Patent GB-485485-A (GB)
Title: A process for the dehydration of secondary and tertiary alcohols and their carboxylic acid esters
IPC: C07C29/86
Filed: 1936-12-16
Abstract: An aqueous mixture or solution of one or more of the following compounds, secondary and tertiary alcohols or their carboxylic acid esters, is dehydrated by treatment with a solvent for the compound, substantially immiscible with water and comprising essentially at least one aliphatic mixed or symmetrical ether boiling at at least 50 DEG  C., the organic compound being recovered in an anhydrous or substantially anhydrous state by direct azeotropic distillation. Suitable ethers are the di-normal propyl, di-isopropyl, di-normal, iso-, secondary and tertiary butyl, symmetrical normal, iso-, secondary and tertiary amyl, hexyl, heptyl and octyl, diallyl, dicrotyl, diisobutenyl, pentenyl, hexenyl, methyl butyl, ethyl propyl, ethyl butyl, propyl butyl, propyl isopropyl, ethyl isobutenyl, butyl isobutenyl, and propyl isopentenyl ethers.  Other components of the solvents may be paraffin hydrocarbons, olefines, olefine polymers, light naphthas, halogenated hydrocarbons and/or organic oxy-compounds different from those treated.  Secondary or tertiary monohydric and/or polyhydric alcohols such as the substituted glycols, polyglycols, glycerols and those containing more than three carbinol groups may be extracted.  The invention is described with particular reference to the extraction of the alcohol solutions. When the solution is not very dilute, the solvent is added and distilled off carrying with it the water.  The non-aqueous layer of the distillate is returned to the distillation vessel or column. When all the water is removed, the ether is distilled off.  The ether used with respect to any particular alcohol must be such that a two phase distillate results.  Thus, ethers boiling from 50-110 DEG  C., e.g. di-isopropyl and ethyl tertiary amyl ethers, and from 50-150 DEG C., are suitable for the dehydration of isopropyl alcohol, and secondary butyl alcohol respectively.  When the ether is difficult to separate from or has a boiling point higher than that of the alcohol, the ether is added in amount smaller than that needed to remove all the water. The distillate is stratified, the non-aqueous layer returned to the distillation system until most of the water has been removed, then the ether and water are taken off together.  In some cases, the addition of the solvent to the alcohol containing small quantities of water may cause stratification, and the layers may be separated and distilled separately.  Examples disclose the dehydration of (1) a constant boiling mixture of isopropyl alcohol and water employing ethyl tertiary butyl ether; (2) an isopropyl alcohol-water constant boiling mixture employing methyl tertiary amyl ether; (3) a tertiary butyl alcohol-water constant boiling mixture employing ethyl tertiary butyl ether; (4) aqueous secondary butyl alcohol employing dinormal butyl ether and, alternatively, di-secondary butyl ether or di-isobutyl ether. Specification 424,135, [Group IV], is referred to.  The Specification as open to inspection under Sect. 19 comprises also the use of methyl propyl ether, and the dehydration of organic non-acid-acting oxy-compounds, alcohols and carboxylic acid esters generally, aldehydes and ketones being referred to. This subject-matter does not appear in the Specification as accepted.ALSO:An aqueous mixture or solution of one or more of the following compounds viz., secondary and tertiary alcohols or their carboxylic acid esters, is dehydrated by treatment with a solvent for the compound, substantially immiscible with water and comprising essentially at least one aliphatic mixed or symmetrical ether boiling at at least 50 DEG  C., the organic compound being recovered in an anhydrous or substantially anhydrous state by direct azeotropic distillation, or by fractionally distilling the extract phase containing the organic compound.  Suitable ethers are the di-normal propyl, di-isopropyl, di-normal, iso-, secondary and tertiary butyl, symmetrical normal, iso-, secondary and tertiary amyl, hexyl, heptyl and octyl, diallyl, dicrotyl, diisobutenyl, pentenyl, hexenyl, methyl butyl, ethyl propyl, ethyl butyl, propyl butyl, propyl isopropyl, ethyl isobutenyl, butyl isobutenyl, and propyl isopentenyl ethers. Other components of the solvents may be paraffin hydrocarbons, olefines, olefine polymers, light naphthas, halogenated hydrocarbons and/or organic oxy-compounds different from those treated.  Secondary or tertiary monohydric and/or polyhydric alcohols such as the substituted glycols, polyglycols, glycerols and those containing more than three carbinol groups may be extracted.  The invention is described with particular reference to the extraction of the alcohol solutions.  When dilute solutions are to be extracted, the solvent may be injected into a vertical contact vessel under pressure, passing upwardly in counter-current to the alcohol solution.  The solvent may however be the continuous phase.  Dispersion may be effected by stirring. Extraction may be effected at about 15-30 DEG C. and at atmospheric pressure.  The extract phase is fractionally distilled.  When the alcohol solution is not very dilute, the solvent is added and distilled off carrying with it the water.  The non-aqueous layer of the distillate is returned to the distillation vessel or column.  When all the water is removed, the ether is distilled off.  The ether used with respect to any particular alcohol must be such that a two phase distillate results.  Thus, ethers boiling from 50-110 DEG  C., e.g. di-isopropyl and ethyl tertiary amyl ethers, and from 50-150 DEG  C., are suitable for the dehydration of isopropyl alcohol, and secondary butyl alcohol respectively.  When the ether is difficult to separate from or has a boiling point higher than that of the alcohol, the ether is added in amount smaller than that needed to remove all the water.  The distillate is stratified, the non-aqueous layer returned to the distillation system until most of the water has been removed, then the ether and water are taken off together.  In some cases, the addition of the solvent to the alcohol containing small quantities of water may cause stratification, and the layers may be separated and distilled separately.  Examples disclose the dehydration of (1) a constant boiling mixture of isopropyl alcohol and water employing ethyl tertiary butyl ether; (2) an isopropyl alcohol-water constant boiling mixture employing methyl tertiary amyl ether; (3) a tertiary butyl alcohol-water constant boiling mixture employing ethyl tertiary butyl ether; (4) aqueous secondary butyl alcohol employing dinormal butyl ether and, alternatively, di-secondary butyl ether or di-isobutyl ether.  Specification 424,135 is referred to.  The Specification as open to inspection under Sect. 91 comprises also the use of methyl propyl ether, and the dehydration of organic non-acid-acting oxy-compounds, alcohols and carboxylic acid esters generally, aldehydes and ketones being referred to. This subject-matter does not appear in the Specification as accepted.