PURIFICATION OF METHANOL

In view of the fact that commercial methanol is now sufficientl !ure for most
a!!lications" After the reaction !rocess cru#e Methanol normall contains a!!ro$imatel
%&' of water" This amount of water is not e$!ecte# to have a !rofoun# effect on #ilute
solutions of solutes in methanol( in view of the h#ro$lic nature of this solvent itself an#
its low molar volume( hence hi)h concentration of h#ro$l )rou!s" Purification of cru#e
methanol to the re*uire# !ro#uct *ualit is achieve# in two se!arate #istillation columns"
Proce#ure I
+te! %" ,istill the methanol with a )oo# fractionatin) column un#er the e$clusion of
moisture" The water content is re#uce# to %-- !!m" From this ste! !rocee# to either
ste! . or ste! /( accor#in) to re*uirements"
+te! . " Pass the methanol slowl throu)h a column of #r molecular sieves store the
methanol over a lum! of calcium h#ri#e" As lon) as the calcium h#ri#e retains its
lum! form( the water content is 01 !!m"
+te! / " For a re#uction of the water content to - " 2 !!m( the methanol is #istille#
twice in "an all3)lass still frc4n metallic so#ium" Freshl cut !ieces ( %3. ) !er L
methanol are use#( the first few tens of mL of #istillate are #iscar#e#( an# the rest(
5oilin) within -"-% -- of the 5oilin) !oint ( is use# inune#iatel 6ref " .78"
Proce#ure II
+te! %" Reflu$ 9"2 L methanol for .th over 2- ) ma)nesium" ,istill 9 L an# reflu$
these over silver nitrate for .9h ( un#er e$clusion of atmos!heric moisture an# car5on
#io$i#e"
+te! . " ,istill the methanol an# sha:e it with activate# alumina for .9h " Filter
throu)h a sintere# )lass filter into a vessel which contains an atmos!here of !ure
nitro)en( from which the methanol is #istille# a)ain in an all3)lass sstem" +!ecific
con#uctances of 2$%- + are rea#il o5taine# with this metho#" ;ith a con#uctivit
cell seale# 5etween the con#enser an# receiver in the last #istillation ste! ( the
mininal s!ecific con#uctance o5serve# was % " 2$%- + < cin "
Proce#ure III 6removal of 5ases an# heav metal8
+te! % " Con#ition a #r macro reticular or macro3!orous sulfonate#3 !olstrene3
t!e cation e$chan)e resin in the h#ro)en3ion form for .9h with methanol to !re3
swell it an# eliminate the remova5le water"
+te! . " Pre!are a % = . mi$ture 65 volume8 of a stron)l aci#ic cation e$chan)e
resin 6e")"( ,uolite C3.- ( !retreate# successivel with . NHC% (% " 2N NaOH ( an#
.N HC%8 an# a stron)l 5asic anion e$chan)e resin 6e")"( ,uolite A3%7.( !retreate#
successivel with %" 2N NaOH( .N HC%( an# %" 2N NaOH8( wash with water( #r
an# !reswell it in methanol for .9h"
+te! /" Pass the methanol to 5e !urifie# successivel throu)h a 7 to %- cm column of
the mi$e# e$chan)er from +te! .( then throu)h a 7 to %- cm column of the
cor#itione# resin from +te! % at a rate of / rnLlmin"
This treatment re#uces the concentration of amines( that !ro#uce an o5no$ious o#or in
the methanol( to 0-"% !!m( an# remeves this o#or "The concentration of ions( such as Na(
>( M). ( Ca.?( Cl( N-@( an# +O is re#uce# from .3%- !!m to 0-"-. !!m each Man
heav metal ions will also 5e retaine# on these columns" +!ecific removal of Fe/?( Cu.?(
Co. ?( P5. ?( etc"( on !olmers with anchore# chelatin) a)ents( such as tiron( is
#escri5e# in ref" /- an# /%"
Other im!urities are either not o5no$ious an# can 5e tolerate# at the levels at which the
are !resent in hi)h )ra#e commercial methanol( or( li:e car5on #io$i#e an# other aci#ic
im3 !urities( are remove# 5 !roce#ures I or III" For the removal of other im!urities( such
as acetone or formal#eh#e"Purifie# methanol shoul# 5e !revente# from 5ein) o$i#iAe#
to formal#eh#e 5 e$clusion of air"