United S ta tes Pa tent [ 1 9 1

Kuros a ka et a l .
[ 1 1 1 4 , 4 3 4 , 3 0 5
[ 4 5 ] F eb . 2 8 , 1 9 8 4
[ 5 4 ] PROCES S F OR PRODUCTION OF
HYDROQUINONE
[ 7 5 ] Inv entors : Nob no Kuros a ka , Ya m a g uc h i;
M a koto Ya s uda , Iw a kuni; Ta da teru
M ura ka m i, Ota ke, a l l of J a p a n
[ 7 3 ] A s s ig nee: M its ui Petroc h em ic a l s Indus try , L td. ,
Toky o, J a p a n
[ 2 1 ] A p p l . N0 . : 3 2 6 , 2 7 7
[ 5 6 ] Ref erenc es Cited
U. S . PA TENT DOCUM ENTS
4 , 1 1 2 , 2 4 4 9 /1 9 7 8 Now a k et a l . . . . . . . . . . . . . . . . . . . . . . . 5 6 8 /7 6 8
4 , 1 7 3 , 6 2 3 l / 1 9 8 1 Ha s h ioto et a ] . 5 6 8 /7 6 8
4 , 3 4 6 , 2 0 3 1 /1 9 8 1 Wirth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 6 8 /7 6 8
Prim a ry Exa m iner-Werren B . L one
[ 5 7 ] A B S TRA CT
Hig h q ua l ity h y droq uinone is p roduc ed f rom p -diis o
p rop y l b enz ene dih y drop eroxide a t a h ig h y iel d a c c ord
ing to th e dis c l os ed p roc es s . Th e p -diis op rop y l b enz ene
[ 2 2 ] F il ed= De ~ 1 1 9 8 1 dih y drop eroxide is dec om p os ed in th e p res enc e of a n
_ _ _ I _ _ a c id c a ta l y s t a nd th e c onc entra tion of th e h y drop erox
[ 3 0 ] F oreig n A l l p l l c a tl on Priority Da m ide is m a inta ined in th e ra ng e of 0 . 1 to 1 % b y w eig h t;
Dec . 5 , 1 9 8 0 [ J P] J a p a n . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . s s -1 7 os 1 s th e rem a ining h y drop oroxido in th e dec om p os ition S top
is f urth er s ub j ec ted to a n a c id dec om p os ition p rior to
[ 5 1 ] Int. Cl . 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C0 7 C 3 7 /0 8 th e rec ov ery of th e f orm ed h y droq uinone p roduc t
[ 5 2 ] US . Cl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 6 8 /7 6 8 ; 5 6 8 /3 8 5 '
[ 5 8 ] F iel d of S ea rc h . . . . . . . . . . . . . . . . 5 6 8 /7 6 8 , 7 9 8 , 7 4 1 , 3 8 5 1 3 Cl a im s , 1 Dra w ing F ig ure
A l ta m a y } p ee-ra m s
1 1 /: 5 9 4 .
l l m ia rv ? g kg a ?
/ -. 0 1 Pe_ . ' a ,
a um ? a v m NA T/m il v * + "A f r/4 .
? nz -- ' [ V4 7 2 2
M IB K "M ew s
-' -' --_ P
8 2 5 % ? !
A L B A /"( g 0 y r
2 . 3 5 . . . . ? /s rm . r1 5 7 7 .
2 M 7 A ? m a y ! g a g
F M M /
"4 7
4 , 4 3 4 , 3 0 5
%\ \
F eb . 2 8 , 1 9 8 4
US . Pa tent
4 , 4 3 4 , 3 0 5
1
PROCES S F OR PRODUCTION OF
HYDROQUINONE
B A CKGROUND OF THE INVENTION
1 . F iel d of th e Inv ention , p
Th e p res ent inv ention rel a tes to a p roc es s f or p roduc
ing h y droq uinone h a v ing a g ood c ol or f rom p -diis op ' ro
p y l b enz ene dih y drop eroxide ( us ua l l y ref erred to h ere
ina f ter a s p -DHP) a t a h ig h y iel d.
2 . Des c rip tion of th e Prior A rt I
It h a s b een p rev ious l y know n in th e a rt th a t h y dro
q uinone is p roduc ed b y oxidiz ing , in a l iq uid p h a s e,
p -diis op rop y l b enz ene ( us ua l l y ref erred to h ereina f ter a s
p -DIPH) a nd/or p -diis op rop y l b enz ene m onoh y drox
y p eroxide ( us ua l l y ref erred to h ereina f ter a s p -M HP)
w ith m ol ec ul a roxy g en f rom p -DHP, f ol l ow ed b y de
c om p os ition of p -DHP in th e p res enc eof a n a c id c a ta
l y s t. How ev er, in s uc h a n oxida tion rea c tion, it is dif f i
c ul t to s el ec tiv el y p roduc e onl y p -DHP. F urth erm ore,
V th e s ep a ra tion of h ig h p urity p -DHP f rom th e oxida tion
rea c tion m ixture is a dif f ic ul t op era tion a nd is c om p l i
c a ted, h enc e exp ens iv e, to op era te. F or th es e rea s ons ,
m a teria l s oth er th a n p -DI-IP-inc l uding v a rious kinds
of b y -p roduc ts , unrea c ted s ta rting m a teria l s , interm edi
a te p roduc ts a nd th e l ike-a re g enera l l y us ed a s s ta rting
m a teria l s f or th e a c id dec om p os ition. How ev er, w h en
th es e s ta rting m a teria l s a re dec om p os ed in th e p res enc e
of a n a c id, it is not ea s y to is ol a te h y droq uinone h a v ing
a h ig h p urity a t a c om m erc ia l l y a c c ep ta b l e rec ov ery
y iel d. Th is is b ec a us e th e rea c tion m ixture c onta ins
v a rious c om p onents oth er th a n p -DHP inc l uding b y
p roduc ts deriv ed f rom th es e c om p onents a s w el l a s
b y -p roduc ts deriv ed b y p -DHP.
F or c onv enienc e th e f ol l ow ing a b b rev ia tions a re us ed
in th e f ol l ow ing des c rip tion:
p -DHP = p -diis op rop y l b enz ene dih y drop eroxide
p -DIPB = p -diis op rop y l b enz ene
p -M HP = p -diis op rop y l b enz ene m onoh y drop eroxide
p -HHP= p -2 -h y droxy -2 -p rop y l -a , a -dim eth y l b enz y l h y
drop eroxide
Va rious a ttem p ts h a v e b een m a de to rec ov er h y dro
q uinone h a v ing a h ig h p urity a t a g ood rec ov ery y iel d.
How ev er, th ere h a v e b een f ew m eth ods p rop os ed th a t
a re c onv enient to op era te a nd a c h iev e th e des ired q ua l
ity of th e p uri? ed h y droq uinone a s w el l a s th e y iel d of
th e p uri? ed h y droq uinone b a s ed on p -DHP. Th us , p rior
to th e p res ent inv ention th ere a re no m eth ods f or rec ov
ering h y droq uinone w h ic h s a tis f y a l l th e a b ov e-m en
tioned req uirem ents .
B RIEF DES CRIPTION OF THE DRA WINGS
F IG. 1 is a f l ow c h a rt il l us tra ting s c h em a tic a l l y th e
op era tiona l s tep s a nd p roc edures , inc l uding rea c ta nts
a nd p roduc ts , of Exa m p l e 1 .
S UM M A RY OF THE INVENTION
A n ob j ec t of th e p res ent inv ention is to ob v ia te th e
a b ov e-m entioned p rob l em s in th e a rt a nd to p rov ide a
p roc es s f or p roduc ing a nd rec ov ering h ig h q ua l ity h y
droq uinone a t a g ood y iel d us ing a p -DHP a s a s ta rting
m a teria l in a n a c id dec om p os ition rea c tion in a s im p l e
a nd c onv enient op era tion.
Oth er ob j ec ts a nd a dv a nta g es of th e p res ent inv ention
w il l b e a p p a rent f rom th e des c rip tion s et f orth b el ow .
5
2 0
2 5
3 0
3 5
5 0
5 5
6 5
2
In a c c orda nc e w ith th e p res ent inv ention, a p roc es s is
p rov ided f or p roduc ing h y droq uinone c om p ris ing th e
s tep s of : ( l ) dec om p os ing p -diis op rop y l b enz ene dih y
drop eroxide in th e p res enc e of a n a c id c a ta l y s t; ( 2 ) dis
til l ing th e rea c tion m ixture, a f ter rem ov ing th e a c id
c a ta l y s t th eref rom , s o th a t l ow b oil ing p oint c om p o
nents s uc h a s a c etone, w a ter a nd th e l ike c onta ined in
th e rea c tion m ixture a re rem ov ed f rom th e rea c tion
m ixture; a nd, ( 3 ) rec ov ering th e th us f orm ed h y droq ui
none f rom th e dis til l a tion res idue, c h a ra c teriz ed in th a t
th e dec om p os ition is ef f ec ted under c onditions s uc h
th a t th e c onc entra tion of th e h y drop eroxide is m a in
ta ined w ith in th e ra ng e of a b out 0 . 1 th roug h a b out 1 %
b y w eig h t a nd in w h ic h th e rem a ining h y drop eroxide in
th e dec om p os ition s tep is f urth er s ub j ec ted to a n a c id
dec om p os ition in a dis til l a tion c ol um n during th e re
m ov a l of th e l ow b oil ing p oint c om p onents or in a
dow ns trea m p ortion of th e dis til l a tion c ol um n b ef ore
th e rec ov ery of th e f orm ed h y droq uinone, th us dec rea s
ing th e h y drop eroxide c onc entra tion.
DETA IL ED DES CRIPTION OF THE
INVENTION
A s is w el l -know n in th e a rt, p -DHP is c om m erc ia l l y
a dv a nta g eous l y p roduc ed b y a ir oxidiz ing , in a l iq uid
p h a s e, p -DHP a nd/or' p -M HP. Th es e oxida tion rea c tion
m ixtures us ua l l y c onta in, in a ddition to p -DHP, p -DIPB
a nd p -M I-IP, p -2 -h y droxy -2 -p rop y l -a , a -dim eth y l b en
z y l h y drop eroxide ( us ua l l y ref erred to h ereina f ter a s
p -HHP), oth er a l c oh ol s , ol e? ns , ta r m a teria l s a nd th e
l ike. In th e p ra c tic e of th e p res ent inv ention th es e oxida
tion rea c tion m ixtures c a n th em s el v es b e us ed a s a s ta rt
ing m a teria l f or th e a c id dec om p os ition. A l terna tiv el y ,
in order to c onv ert p -HHP c onta ined in th es e m ixtures
to p -DHP, th e a b ov e-m entioned oxida tion rea c tion
m ixtures c a n b e us ed a f ter th ey a re f urth er oxidiz ed b y
a n oxida tion a g ent s uc h a s h y drog en p eroxide. F urth er
m ore, th es e ty p es of oxida tion rea c tion m ixtures m a y b e
us ed a f ter a p ortion or a l l of th e unrea c ted s ta rting
m a teria l s or b y -p roduc ts a re s ep a ra ted a nd rem ov ed
th eref rom .
In th e a c tua l a c id dec om p os ition, a n org a nic s ol v ent
c a p a b l e of dis s ol v ing h y droq uinone a nd p -DHP c a n b e
a dv a nta g eous l y us ed. In v iew of th e p os t-trea tm ent
op era tion, des ira b l e org a nic s ol v ents inc l ude ( 1 ) s ol
v ents w h ic h h a v e a b oil ing p oint h ig h er th a n th a t of
w a ter a nd w h ic h a re ( 2 ) ins ol ub l e or onl y s l ig h tl y s ol u
b l e in w a ter, a nd p ref era b l y ( 3 ) a re th os e s ol v ents w h ic h
a re c om p a tib l e w ith a n a rom a tic h y droc a rb on. Exa m
p l es of s uita b l e org a nic s ol v ents w h ic h s a tis f y th es e
th ree req uirem ents a re ketones h a v ing a p p roxim a tel y 6
th roug h 1 0 c a rb on a tom s , s uc h a s , f or exa m p l e, m eth y l
is ob uty l ketone, diis op rop y l ketones , diis ob uty l ketone
a nd th e l ike or, m ixtures of th es e ketones . In a ddition,
oth er org a nic s ol v ents s uc h a s a rom a tic h y droc a rb ons
c a n b e us ed tog eth er w ith th e a b ov e-m entioned org a nic
s ol v ents , a s l ong a s th e des ired rea c tion is not a dv ers el y
a f f ec ted.
Th e c a ta l y s ts ' us ed in th e a c id dec om p os ition of th e
p res ent inv ention inc l ude a w a ter-s ol ub l e a c id s uc h a s
s ul f uric a c id, p h os p h oric a c id, p erc h l oric a c id a nd th e
l ike, or a s ol id a c id s uc h a s s il ic a -a l um ina , s il ic a
m a g nes ia , c a tion exc h a ng e res ins a nd th e l ike. Th e de
s ira b l e c a ta l y s t is s ul f uric a c id, . f rom th e p oint of v iew of
its l ow c os t a nd th e g ood s el ec tiv ity a c h iev ed.
Th e c ontent of th e h y drop eroxide c onta ined in th e
s ta rting m a teria l ( inc l uding th e s ol v ent w h en a s ol v ent
is us ed) f ed to th e a c id dec om p os ition s tep is des ira b l y
4 , 4 3 4 , 3 0 5
3
w ith in th e ra ng e of a p p roxim a tel y 4 0 th roug h 8 0 %, in
order to m a inta in ea s y c ontrol of th e rea c tion a nd f or
ec onom y . A s us ed in th is des c rip tion, s p ec i? c a tion a nd
c l a im s th e c ontent ( or p erc enta g e) of th e h y drop eroxide
is exp res s ed in term s of p erc ent b y w eig h t, b a s ed on th e
a s s um p tion th a t, ev en if th e h y drop eroxide is us ed a s a
m ixture of v a rious h y drop eroxides , a l l th e h y drop erox
ides v a re p -M HP w h en th e c ontent of th e h y drop erox-
ides a re titra ted w ith p ota s s ium iodide ( th e is ol a ted
iodine is b a c k titra ted w ith s odium th ios ul f a te).
Th e a m ount of th e c a ta l y s t us ed in th e a c id dec om p o
s ition l a rg el y dep ends up on th e ty p e of c a ta l y s t us ed
a nd th e a m ount of w a ter p res ent in th e rea c tion m ixture.
A s a n exa m p l e, w h en th e w a ter c ontent in th e rea c tion
m ixture is in th e ra ng e of 1 th roug h 4 % b y w eig h t a nd
w h en s ul f uric a c id is us ed a s a c a ta l y s t, th e c onc entra
tion-of th e c a ta l y s t in th e rea c tion m ixture is des ira b l y
a b out 0 . 1 th roug h a b out 2 % b y w eig h t. In th e c a s e
w h ere a c om p ound s uc h a p -HHP, w h ic h c a n b e c ov -
erted to p -DHP b y th e a c tion of a p eroxide, is c onta ined
in th e s ta rting m a teria l of th e a c id dec om p os ition, a
p eroxide s uc h a s h y drog en p eroxide m a y b e a dded to
th e rea c tion m ixture to a c h iev e th e des ired c onv ers ion.
Th e rea c tion tem p era ture a nd th e p eriod of tim e
req uired f or th e a c id dec om p os ition rea c tion a re not
s p ec i? c a l l y l im ited, h ow ev er th e a c id dec om p os ition is
a dv a nta g eous l y c a rried out a t a tem p era ture of a b out
2 0 C. th roug h a b out 9 0 C. , m ore p ref era b l y a b out 5 0
C. th roug h a b out 8 0 C. , f or a p eriod of tim e of a b out 5
to a b out 6 0 m inutes , m ore p ref era b l y a b out 1 5 . to a b out
3 0 m inutes . _ .
In th e p ra c tic e of th e p res ent inv ention, it is im p orta nt
to a dj us t th e c onc entra tion of th e h y drop eroxide in th e
rea c tion m ixture of th e a c id dec om p os ition to a b out 0 . 1
. th roug h a b out 1 % b y w eig h t, m ore p ref era b l y a b out 0 . 2 - '
th roug h a b out 0 . 5 % b y w eig h t, b y a p p rop ria te s el ec tion
of th e a b ov e-m entioned rea c tion c onditions . Wh en th e
a c id dec om p os ition rea c tion is c a rried out until th e
c onc entra tion of th e h y drop eroxide in th e rea c tion m ix
ture f a l l s b el ow th e l ow er l im it of th e a b ov e-m entioned
ra ng e, not onl y th e tota l y iel d of th e h y droq uinone is
dec rea s ed, b ut a l s o th e q ua l ity of th e h y droq uinone is
a dv ers el y a f f ec ted. On th e oth er h a nd, w h en op era ting
under c onditions w h ere inc om p l ete a c id dec om p os ition
oc c urs , th e a m ount of th e rem a ining h y drop eroxide is
g rea ter th a n th e up p er l im it of th e a b ov e-m entioned
ra ng e w h ic h c a us es p rob l em s in th a t a da ng erous a b nor
m a l rea c tion is l ikel y to oc c ur in th e p os t-trea tm ent
op era tion s uc h a s dis til l a tion a nd a l s o th a t th e tota l y iel d
of th e h y droq uinone is dec rea s ed. Th us , it is v irtua l l y
nec es s a ry to op era te th e a c id dec om p os ition rea c tion a t
a h y droq uinone c onc entra tion w ith in th e a b ov e-m en
tioned ra ng e. '
1 Th e a c id dec om p os ition rea c tion c a n b e term ina ted
b y rem ov a l of th e a c id c a ta l y s t. In th e c a s e w h ere a
w a ter-s ol ub l e a c id s uc h a s s ul f uric a c id is us ed, th e a c id
c a ta l y s t c a n b e c onv enientl y rem ov ed f rom th e rea c tion
m ixture b y c onta c ting th e rea c tion m ixture w ith a n
a q ueous s ol ution of a neutra l s a l t s uc h a s , f or exa m p l e,
a n a q ueous s ol ution of s odium s ul f a te, p ota s s ium s ul f a te,
s odium c h l oride, s odium p h os p h a te, or a m m onium s ul
f a te; p ref era b l y a n a q ueous s ol ution of a s ul f a te is us ed.
Th us , th e w a ter-s ol ub l e a c id is extra c ted f rom th e rea c
tion m ixture to th e a q ueous s ol ution l a y er. In order to
reus e th e a q ueous s ol ution of th e neutra l s a l t, a s m a l l
a m ount of a b a s ic c om p ound s uc h a s s odium h y droxide
c a n b e a dv a nta g eous l y a dded to th e a q ueous s ol ution of
th e neutra l s a l t. How ev er, it s h oul d b e noted th a t th e
2 5
4
us e of a n exc es s a m ount of th e b a s ic c om p ound is not
des ira b l ein order to, p rev ent a c h a ng e in th e p rop erties
of th e h y droq uinone. F or th is rea s on, th e b a s ic c om
p ound is p ref era b l y us ed in a m a nner s uc h th a t, a f ter
c onta c ting w ith th e a q ueous neutra l s a l t s ol ution, th e oil
l a y er c onta ining th e h y droq uinone is on th e a c id s ide,
f or exa m p l e, w ith in th e p H ra ng e of a p p roxim a tel y 2
th roug h 5 . Th e term p H of th e oil l a y er a s us ed h erein
m ea ns a p H v a l ue of a w a ter l a y er determ ined a f ter th e
oil l a y er is th oroug h l y s h a ken w ith a n eq ua l v ol um e of
w a ter.
In th e p ra c tic e of th e a b ov e-m entioned extra c tion, in
order to dec rea s e th e s ol ub il ity of th e h y droq uinone in
th e w a ter l a y er a nd to im p rov e th e s ep a ra tion of th e
w a ter l a y er f rom th e oil l a y er , th e us e of a h ig h l y c on
c entra ted a q ueous s ol ution of a neutra l s a l t s uc h a s , f or
- exa m p l e, a c onc entra tion of a p p roxim a tel y 5 ' th roug h
3 0 %, b y w eig h t, is des ira b l e. F urth erm ore, in th e c a s e
Wh er h y drdc a rb ons s uc h a s a rom a tic h y droc a rb ons
a re c onta ined in th e oil ' l a y erf in a n a m ount of a p p roxi
m a tel y 3 th roug h 2 0 %, b y w eig h t, th e s ep a ra tion is ev en
"f urth er im p rov ed. Exa m p l es of th e a rom a tic h y droc a r
b ons us edi' f or th is s ep a ra tion inc l ude tol uene, xy l ene,
eth y l b enz ene} c um ene, c y m ene, m es ity l ene, p s eudoc u
m ene, diis op rop y l b enz ene' a nd th e l ike. A m ong th es e
h y droc a rb ons , in th e c a s e w h ere a ketone is us ed a s a n
' a c id dec om p os ition rea c tion s ol v ent, a h y droc a rb on
h a v ing -a b oil ing p oint h ig h er th a n th a t of th e ketone is
des ira b l y ' -' us ed, ta king into a c c ount th e s ep a ra tion op er
" a tion' in v th e l a tterv s tep .
Th e rea c tion m ixture f rom w h ic h th e a c id c a ta l y s t
h a s b een rem ov ed s til l c onta ins th e rea c tion s ol v ent,
b y -p roduc ts , w a ter a nd th e l ike, in a ddition to a c etone
a nd h y droq uinone, a nd- th eref ore, th es e c om p onents
4 0
4 5
5 0
5 5
6 0
6 5
s h oul d b e rem ov ed f rom th e rea c tion m ixture. In order
to rem ov e th es e c om p onents f rom th e rea c tion m ixture,
a dis til l a tion op era tion c a n b e c a rried out ? rs t. In th e
p ra c tic e of th e dis til l a tion, a s ol v ent, w h ic h h a s a b oil ing
p oint h ig h er th a n th a t of w a ter a nd w h ic h is ins ol ub l e or
onl y s l ig h tl y s ol ub l e in w a ter b ut v is c a p a b l e of dis
s ol v ing h y droq uinone c a n a dv a nta g eous l y is a l s o p res
ent, s inc e th e h y droq uinone c a n b e ob ta ined in th e f orm
of a s ol ution a f ter th e rem ov a l of a c etone a nd w a ter.
Wh en a s ol v ent is us ed during th e a c id dec om p os ition
rea c tion, th is s ol v ent is inev ita b l y p res ent in th e res ul
ta nt rea c tion m ixture a nd, th eref ore, f urth er a ddition of
s ol v ent is - not nec es s a ry . F urth erm ore, th e s ol v ent
s h oul d b e dis til l ed of f a f ter th e rem ov a l of a c etone,
w a ter a nd th e l ike. In th e dis til l a tion, in order to p rev ent
dec rea s ing th e q ua l ity of th e h y droq uinone a nd m a in
ta ining ta r or oth er h ig h b oil ing p oint c om p onents in a
dis s ol v ed f orm , a n a rom a tic h y droc a rb on h a v ing a b oil
ing p oint h ig h er th a n th a t of th e s ol v ent p ref era b l y is
a l s o p res ent during th e dis til l a tion. If s uc h a n a rom a tic
h y droc a rb on is us ed in th e a c id dec om p os ition rea c tion
or in th e a c id rem ov a l op era tion, f urth er a ddition of th e
a rom a tic h y droc a rb on is not nec es s a ry .
In order to rem ov e a c etone a nd w a ter f rom th e rea c
tion m ixture f rom w h ic h th e a c id c a ta l y s t h a s b een
rem ov ed, dis til l a tion c a n b e c a rried out b y us ing one
dis til l a tion c ol um n, or b y us ing tw o or m ore dis til l a tion
c ol um ns a c etone is ? rs t dis til l ed of f a nd th en w a ter is
rem ov ed. , . . . ~ ,
In th e c ol um n b ottom l iq uid f rom w h ic h w a ter h a s
b een rem ov ed, th ere is p res ent th e rem a ining h y drop er
oxide w h ic h h a s not b een c om p l etel y dec om p os ed dur
. ing th e a c id, dec om p os ition s tep . Th e rem a ining h y dro
p eroxide is f urth er dec om p os ed in th e p res enc e of a n
4 , 4 3 4 , 3 0 5
5
a c id ins ide th e dis til l a tion c ol um n f rom w h ic h w a ter h a s
b een rem ov ed, or in a dow ns trea m p ortion of th e dis til
l a tion c ol um n, b ef ore th e rec ov ery of th e res ul ta nt h y
droq uinone. Th is a dv a nta g eous l y p rev ents th e c on
s um p tion of th e h y droq uinone during th e s ub s eq uent
dis til l a tion s tep a nd a l s o p rev ents dec rea s ing th e q ua l ity
of th e h y droq uinone. -' . = -r Th e a c id dec om p os ition of th e rem a ining h y drop er
oxide m entioned a b ov e c a n b e ef f ec ted in th e p res enc e
of a n a c id c a ta l y s t s im il a r to th e a c id c a ta l y s t us ed in th e
a c id dec om p os ition rea c tion. In th e, m os t p ref erred
em b odim ent of th e p res ent inv ention, a s m a l l a m ount of
a non-v ol a til e w a ter~ s ol ub l e a c id, s uc h a s s ul f uric a c id
or p h os p h oric ra c id, is a dded to th e f eed m a teria l enter
ing th e w a ter rem ov a l dis til l a tion c ol um n. ' A s a res ul t,
th e a c id c a ta l y s t' c a n' b e unif orm l y m ixed w ith th e f eed
m a teria l s o th a t th e s ide-rea c tions c a n b e p rev ented,
a nd, "s inc e th e w a ter c onta ined in th e b ottom of th e
w a ter rem ov a l dis til l a tion c ol um n is dec rea s ed a nd th e
a c id s treng th is inc rea s ed, th edes ired a iddec om p os i
tion a t th e tem p era ture of th e dis til l a tion ' p roc eeds
s m ooth l y . = 1 ' = 1 . '
A l th oug h th e a m ount of s ul f uric . a c id; p h os p h oric
a c id or th e l ike a dded, ; is . not s p ec i? c a l l y c ritic a l , th e
a ddition of a p p roxim a tel y 0 . 0 0 1 th roug h 0 . 1 p a rts b y
w eig h t of th e a c id, b a s ed on 1 0 0 p a rts b y w eig h t of th e
f eed m a teria l s to th e dis til l a tion c ol um n, is g enera l l y
s uf f ic ient. S a tis f a c tory res ul ts a re ob ta ined w h en th e
c onc entra tion of th e h y drop eroxide in th e c ol um n b ot
tom l iq uid is dec rea s ed _ to one-h a l f or l es s of th a t of th e
f eed m a teria l , ol - a b out' 0 . 0 7 % or l es s b y w eig h t b y th is
trea tm ent. a ' v ' '
Th e" c ol um n b ottom l iq uid th us trea ted is th en s ub
j ec ted to a dis til l a tion op era tion in order to rem ov e th e
a b ov e-m entioned s ol v ent w h ic h is ins ol ub l e or onl y
s l ig h tl y s ol ub l e in w a ter. In th e c a s e w h ere th e b ottom
tem p era ture of th e dis til l a tion c ol um n is too h ig h during
th e s ol v ent rem ov a l dis til l a tion, l os s of th e res ul ta nt
h y droq uinone oc c urs b ec a us e a c ondens a tion rea c tion
a p p a rentl y oc c urs . On th e oth er, h a nd, if th e b ottom
tem p era ture of th e dis til l a tion c ol um n is too l ow , th e
h y droq uinone is c ry s ta l l iz ed, s o th a t v a rious p rob l em s
inc l uding c l og g ing of th e dis til l a tion c ol um n a re c a us ed.
' In order, to s im ul ta neous l y s ol v e th es e p rob l em s , th e
s ol v ent m a y b e rem ov ed b y a n a z eotrop ic dis til l a tion
tog eth er w ith w a ter a nd th e h y droq uinone m a y b e
w ith dra w n in th e f orm of a n a q ueous s ol ii' tion f rom th e
b ottom of th e dis til l a tion c ol um n; Oil -s ol ub l e h ig h b oil
ing p oint b y -p roduc ts a re a l s o w ith dra w n, tog eth er
w ith a rom a tic h y droc a rb ons f rom th e b ottom of th e
dis til l a tion c ol um n. F or th is rea s on, th e a q ueous h y dro
q uinone s ol ution tends to b e em ul s i? ed a nd s ep a ra tion
b ec om es dif f ic ul t. How ev er, , a dil uted a q ueous s ol ution
of a neutra l s a l t s uc h a s s odium s ul f a te a t a c onc entra
tion, f or exa m p l eof 1 -5 %' b y w eig h t, c a n b e ef f ec tiv el y
us ed to ob v ia te th e a b ov e-m entioned p rob l em s .
S inc e th e c ol um n b ottom l iq uid is a l l ow ed to s ta nd to
s ep a ra te th e oil l a y er a nd, th e w a ter l a y er, b oth l a y ers
c a n b e s ep a ra ted in a c onv entiona l m a nner. In order to
rec ov er th e h y droq uinone f rom th e w a ter l a y er, th e
w a ter l a y er c a n b e c onc entra ted to c ry s ta l l iz e th e h y
droq uinone. If des ired, in order to inc rea s e th e p urity
a nd th e' q ua l ity of th e h y droq uinone, v a rious know n
op era tions s uc h a s a n a c tiv a ted c a rb on trea tm ent, a
reduc ing a g ent trea tm ent, a rec ry s ta l l iz a tion m eth od
a nd th e l ike c a n b e us ed in a ny c om b ina tion th ereof .
Th us , des ired h y droq uinoneh ig h in q ua l ity c a n b e ob
ta ined a nd a t a h ig h y iel d. ' -
6
Th e p res ent inv ention w il l b e f urth er il l us tra ted b y ,
b ut is b y no m ea ns l im ited to, th e f ol l ow ing Exa m p l es
a ndCom p a ra tiv e Exa m p l es in w h ic h a l l p a rts a nd p er
c enta ' g es a re exp res s ed on a w eig h t b a s is unl es s oth er
w is e noted, '
_ " , EXA M PL E 1
Th e p roc edures of th is exa m p l e a re il l us tra ted s c h e
m a tic a l l y in th e f l ow c h a rt of F IG. 1 . M eth y l is ob uty l
ketone, w a s a dded to th e oxida tion p roduc ts ob ta ined
f rom th e a ir oxida tion of p -diis op rop y l b enz ene. Th us , a
l iq uid c onta ining 2 3 % of p -diis op rop y l b enz ene dih y
drop eroxide ( DHP), 1 0 % of p -2 -h y droxy -2 -p rop y l -a , a
2 0
2 5
dim eth y l b enz y l h y droip eroxide ( HHP), 5 % of p -diis o
p rop y l b en' z ene m onoh y drop eroxide ( M HP), 5 2 % of
m eth y l is ob uty l { ketone, 1 % of w a ter a nd 9 % of th e
oth er p roduc ts w a s ' ob ta ined. Th e h y drop eroxide c on
c entra tion of th is l iq uid w a s 6 4 %.
I "Th e h y drop eroxide c onc entra tion a s us ed h erein is
b a s ed on th e a s s um p tion th a t a l l th e h y drop eroxides a re
p -diis op rop y l b enz ene m onoh y drop eroxides . Th e c on
tent of th e h y drop eroxides is a na l y z ed b y a dding a s a tu- _
ra ted p ota s s ium iodide s ol ution to th e l iq uid under a n
a c etic a c id a c idity a nd, tl ien titra ting th e is ol a ted iodine
w ith s odium th ios ul f a te to determ ine th e c onc entra tion
of th e h y drop eroxide' g roup . _
' , To th e oxida tion p roduc t w h ic h inc l uded m eth y l
is ob uty l ketone, 2 . 6 p a rts of 6 0 % a q ueous p eroxide,
3 0
b a s ed on 1 0 0 p a rts of th e oxida tion p roduc t, w a s a dded.
Th en, a n a c id dec om p os ition rea c tion w a s c a rried out in
v th e p res enc e of 0 . 5 % of s ul f uric a c id a nd 3 . 0 % of w a ter
a t a tem p era ture of 7 2 C. , w h ereb y c rude h y droq ui
w a s l iq uid inc l uding 0 . 3 5 % of th e unrea c ted h y drop er
" oxide w a s ob ta ined. Th e y iel d of th e h y droq uinone w a s
4 0
4 5
9 8 1 1 1 0 1 % b a s ed- on th e' tota l a m ounts of p -DHP a nd
p -HHP. Th e c ol or, th a t is h ue, of th e res ul ta nt c rude
h y droq uinone l iq uid w a s 0 . 1 0 , w h ic h w a s v ery g ood,
w h en th e a b s orb a nc e w a s determ ined a t a w a v el eng th
of 4 2 0 nm ( c el l 1 0 m m ) b y us ing dis til l ed w a ter a s a
ref erenc e l iq uid. _ , ~ .
_ To th e res ul ta nt a c id dec om p os ition rea c tion m ixture,
s uf f ic ient c um ene w a s a dded to a c h iev e a 1 0 % c onc en
tra tig n. Th erea f ter, th e res ul ta nt rea c tion m ixture w a s
c onta c ted w ith a _ v 2 0 % a q ueous s odium s ul f a te s ol ution
w h ic h c onta ined a s m a l l a m ount of s odium h y droxide,
th en, th e s ul f uric ' a c id w a s extra c ted a nd neutra l iz ed,
"w h ereb y th e p H of th e oil l a y er of th e neutra l iz ed m ix
ture b ec a m e 3 . 5 . '
5 5
6 0
6 5
A f ter th e neutra l iz a tion, th e oil l a y er w a s dis til l ed a t
a tm os p h eric p res s ure, during w h ic h a c etone w a s dis
til l ed f rom th e top of th e c ol um n a nd a l iq uid c onta ining
4 8 % of m eth y l is ob uty l ketone, 1 5 % of h y droq uinone,
1 4 % of c um ene, 1 4 . 3 % of h ig h b oil ing p oint im p urities ,
8 % of w a ter, 0 . 4 % of a c etone a nd 0 . 3 % of th e h y dro
p eroxide w a s ob ta ined a s a s til l -b ottom p roduc t. To th e
s til l -b ottom l iq uid, 0 . 0 0 2 p a rts , b a s ed on 1 0 0 p a rts of th e
s til l -b ottom l iq uid, of s ul f uric a c id w a s a dded, a nd
c h a rg ed to a b a tc h dis til l a tion c ol um n, w h ere th e l iq uid
w a s dis til l ed under a tm os p h eric p res s ure to rem ov e th e
w a ter f rom th e top of th e c ol um n until th e w a ter c on
tent in th e b ottom l iq uid of th e dis til l a tion c ol um n w a s
0 . 7 %. Th e h y drop eroxide c ontent of th e b ottom l iq uid
of th e c ol um n w a s 0 . 0 7 %. >
Th en, 5 0 p a rts of a 2 % a q ueous s odium s ul f a te s ol u
_ . _ tion h a v ing a n a dj us ted p H of 3 w a s a dded to 5 0 p a rts of
th e res ul ta nt b ottom l iq uid of th e b a tc h dis til l a tion c ol
um n a nd th e m ixture w a s c h a rg ed to a s ec ond b a tc h
_ ' . dis til l a tion_ c ol um n, _ w h ere th e m eth y l is ob uty l ketone
4 , 4 3 4 , 3 0 5
7
w a s dis til l ed of f , tog eth er w ith w a ter, in th e f orm of a n
a z eotrop ic c om p os ition f rom th e top of th e c ol um n. A l l
th e w a ter dis til l ed of f , tog eth er w ith th e m eth y l is ob uty l
ketone, in th e f orm of a n a z eotrop ic c om p os ition w a s
rec y c l ed to th e dis til l a tion c ol um n. Th e c ol um n b ottom
l iq uid of th e m eth y l is ob uty l ketone s trip p ing c ol um n
th us ob ta ined w a s a l l ow ed to s ta nd. Th us , th e oil l a y er
a nd th e w a ter l a y er w ere s ep a ra ted f rom ea c h oth er.
Th e c ol orv or h ue of th e w a ter l a y er c onta ining h y dro
q uinone w a s 0 . 8 0 , w h en th e a b s orb a nc e w a s determ ined
under a w a v el eng th of 4 2 0 nm ( c el l 1 0 m m ) b y us ing
dis til l ed w a ter a s a ref erenc e l iq uid. Th e p erc ent h y dro
q uinone rec ov ered w a s 1 0 0 % th roug h th e dew a tering
c ol um n a nd th e m eth y l is ob uty l ketone s trip p ing c ol
um n. Th e h y droq uinone c onta ined in th e w a ter l a y er
th us ob ta ined w a s extra c ted w ith m eth y l is ob uty l ke
tone, c ry s ta l l iz ed, a nd rec ry s ta l l iz ed. Wh en 5 p a rts of
th e rec ry s ta l l iz ed p roduc t w a s dis s ol v ed in 1 0 0 p a rts of
5 % b y v ol um e a q ueous a c etic a c id, th e Ha z en v a l ue
w a s 5 , a v ery a c c ep ta b l e v a l ue.
EXA M PL E 2 '
Th e a c id dec om p os ition rea c tion, neutra l iz a tion a nd
a c etone s trip p ing w ere c a rried out in th e s a m e m a nner
a s des c rib ed in Exa m p l e 1 . Th us , a s til l -b ottom l iq uid
c onta ining 4 8 % of m eth y l is ob uty l ketone, 1 5 % of h y
droq uinone, 1 4 % of c um ene, 1 4 . 3 % of h ig h b oil ing
, p oint im p urities , 8 % of w a ter, 0 . 4 % of a c etone a nd
0 . 3 % of th e h y drop eroxide w a s ob ta ined. To th is l iq uid
0 . 0 1 p a rt, b a s ed on 1 0 0 p a rts of th e s til l -b ottom l iq uid, of
s ul f uric a c id w a s a dded a nd dew a tered a s des c rib ed in
Exa m p l e 1 until th e w a ter c ontent of th e c ol um n b ottom ;
l iq uid w a s 0 . 7 %. Th e h y drop eroxide c ontent of ' th e
c ol um n b ottom l iq uid w a s 0 . 0 3 %.
Th erea f ter, th e m eth y l is ob uty l ketone w a s dis til l ed
of f , tog eth er w ith w a ter a s a n a z eotrop ic c om p os ition,
in th e m a nner des c rib ed in Exa m p l e 1 . Th e c ol or or h ue
of th e res ul ta nt w a ter l a y er inc l uding th e h y droq uinone
w a s 0 . 7 5 , w h en th e a b s orb a nc e w a s determ ined a s de
, s c rib ed in Exa m p l e 1 . Th e rec ov ery y iel d of th e h y dro
q uinone th roug h a dew a tering c ol um n a nd a m eth y l
is ob uty l ketone s trip p ing c ol um n w a s 1 0 0 %. F urth er
m ore, th e s til l -b ottom w a ter l a y er of th e m eth y l is ob uty l
ketone s trip p ing c ol um n w a s trea ted a s des c rib ed in
Exa m p l e 1 . Th e Ha z en v a l ue of th e-res ul ta nt p roduc t
w a s 5 , w h ic h is v ery g ood.
COM PA RA TIVE EXA M PL E A
Th e a c id dec om p os ition rea c tion, neutra l iz a tion a nd
a c etone s trip p ing w ere c a rried out a s des c rib ed in Ex
a m p l e l . Th us , a s til l -b ottom l iq uid c onta ining 4 8 % of
m eth y l is ob uty l ketone, 1 5 % of h y droq uinone, 1 4 % of
c um ene, 1 4 . 3 % of h ig h b oil ing p oint im p urities , 8 % of
w a ter, 0 . 4 % of a c etone a nd 0 . 3 % of th e h y drop eroxide
w a s ob ta ined. Th e s til l -b ottom l iq uid w a s dis til l ed in th e
. m a nner a s des c rib ed in Exa m p l e 1 , exc ep t th a t th e s ul f u
- ric a c id w a s not a dded until th e w a ter c ontent th ereof
b ec a m e 0 . 3 %; th e h y drop eroxide c ontent in th e c ol um n
b ottom l iq uid w a s 0 . 2 3 %.
Th erea f ter, th e m eth y l is ob uty l ketone w a s dis til l ed
of f , tog eth er w ith w a ter a s a n a z eotrop ic c om p os ition,
a s des c rib ed in Exa m p l e 1 . Th e c ol or or h ue of th e
res ul ta nt w a ter l a y er c onta ining th e h y droq uinone w a s
2 0
2 5
3 0
4 0
4 5
5 0
5 5
6 0
6 5
8
determ ined a s des c rib ed in Exa m p l e 1 . Th e res ul t w a s
2 . 5 , w h ic h is v ery p oor. Th e rec ov ery y iel d of th e h y
droq uinone th roug h a dew a tering c ol um n a nd m eth y l
is ob uty l ketone s trip p ing c ol um n w a s 9 7 . 5 %. Th e
Ha z en v a l ue of th e p roduc t ob ta ined f rom th e w a ter
l a y er c onta ining h y droq uinone a s des c rib ed in Exa m p l e
1 w a s 3 0 , w h ic h is a l s o v ery p oor.
COM PA RA TIVE EXA M PL E B
To th e oxida tion p roduc t of Exa m p l e 1 to w h ic h
m eth y l is ob uty l ketone w a s a dded, 2 . 6 p a rts of a 6 0 %
a q ueous h y drog en p eroxide, b a s ed on 1 0 0 p a rts of th e
oxida tion p roduc t, w a s a dded, a nd a f urth er a c id de
c om p os ition rea c tion w a s c a rried out under th e c ondi
tions of 2 . 5 % of s ul f uric a c id c ontent a nd 1 . 5 % of w a ter
c ontent a t a tem p era ture of 7 5 C. , until th e c ontent of
th e unrea c ted h y drop eroxide w a s 0 . 0 3 %. Th e y iel d of
th e h y droq uinone, b a s ed on th e tota l a m ounts of p -DHP
a nd p -HHP, w a s 8 8 m ol %, w h ic h w a s v ery l ow , a s
c om p a red w ith th a t of Exa m p l e 1 . Th e c ol or or h ue of
th e res ul ta nt a c id dec om p os ition p roduc t w a s deter
m ined, in term s of th e a b s orb a nc e, a s des c rib ed in Ex
a m p l e 1 . Th e a b s orb a nc e w a s 0 . 4 1 , w h ic h is v ery p oor.
Th is dem ons tra tes th a t c om p l ete dec om p os ition l ea ds
to l ow y iel ds .
EXA M PL E 3
To th e oxida tion p roduc t ob ta ined a s des c rib ed in
Exa m p l e 1 a nd to w h ic h m eth y l is ob uty l ketone w a s
a dded, 2 . 6 p a rts , b a s ed on 1 0 0 p a rts of th e oxida tion
p roduc t, of 6 0 % a q ueous h y drog en p eroxide w a s
a dded. Th en th e a c id dec om p os ition rea c tion w a s c a r
ried out under c onditions of 0 . 3 5 % s ul f uric a c id c ontent
a nd 3 . 0 % w a ter c ontent a t a tem p era ture of 7 5 %. Th e
unrea c ted h y drop eroxide c ontent in th e c rude h y dro
q uinone l iq uid w a s 0 . 7 8 % a nd th e y iel d of h y droq ui
none, b a s ed on th e tota l a m ounts of p -DI-IP a nd p -HHP,
w a s 9 7 m ol %. Th e c ol or or h ue of th e c rude h y droq ui
none l iq uid determ ined a s des c rib ed in Exa m p l e 1 w a s
0 . 1 1 . Th e a c id dec om p os ition rea c tion m ixture w a s
neutra l iz ed a nd a c etone s trip p ed a s des c rib ed in Exa m
p l e 1 , p roduc ing s til l -b ottom l iq uid c onta ining 0 . 5 5 % of
th e h y drop eroxide. To 1 0 0 p a rts of th is l iq uid, 0 . 0 2 p a rts
of s ul f uric a c id w a s a dded, a nd dew a tering w a s c a rried
out b y dis til l a tion a s des c rib ed in Exa m p l e 1 , until th e
w a ter c ontent of th e c ol um n b ottom l iq uid b ec a m e
0 . 4 %. Th e h y drop eroxide c ontent in th e c ol um n b ottom
l iq uid w a s 0 . 0 5 %.
Th erea f ter, th e m eth y l is ob uty l ketone w a s dis til l ed
of f tog eth er w ith w a ter, a s a n a z eotrop ic c om p os ition,
a s des c rib ed in Exa m p l e 1 . Th e c ol or or h ue of th e
res ul ta nt w a ter l a y er c onta ining h y droq uinone a l s o w a s
determ ined in a m a nner a s des c rib ed in Exa m p l e 1 . Th e
res ul t w a s 0 . 7 8 w h ic h is extrem el y g ood. Th e y iel d or
h y droq uinone th roug h th e dew a tering c ol um n a nd th e
m eth y l is ob uty l ketone s trip p ing c ol um n w a s 1 0 0 %.
Th e Ha z en v a l ue of th e res ul ta nt p roduc t ob ta ined f rom
th e w a ter l a y er of th e s til l -b ottom l iq uid of th e m eth y l
is ob uty l ketone s trip p ing c ol um n a s des c rib ed in Exa m
p l e 1 w a s 5 , w h ic h is v ery g ood.
Th e res ul ts of th e a b ov e Exa m p l es of th e inv ention
a nd Com p a ra tiv e Exa m p l es a re s h ow n in th e f ol l ow ing
Ta b l e I.
4 , 4 3 4 , 3 0 5
1 . A p roc es s f or p roduc ing h y droq uinone c om p ris ing
th e s eq uentia l s tep s of : v
( l ) dec om p os ing p -diis op rop y l b enz ene dih y
drop e roxide in th e p res enc e of a w a ter-s ol ub l e a c id
c a ta l y s t s el ec ted f rom s ul f uric a c id, p h os p h oric
a c id, a nd p erc h l oric a c id a t a tem p era ture of a b out
2 0 C. to a b out 9 0 C. w h il e m a inta ining th e h y dro
p eroxide c onc entra tion w ith in th e ra ng e of a b out
0 . 1 to a b out 1 % b y -w eig h t;
( 2 ) dis til l ing th e rea c tion m ixture, a f ter rem ov ing th e
a c id c a ta l y s t th eref rom , w h ereb y l ow b oil ing p oint
c om p onents c onta ined in th e rea c tion m ixture a re
rem ov ed f rom th e rea c tion m ixture;
( 3 ) f urth er s ub j ec ting th e rem a ining h y drop eroxide
f rom dec om p os ition s tep ( 1 ) to a n a c id dec om p os i
tion ins ide th e dis til l a tion c ol um n, or in a dow n
s trea m p ortion of , th e dis til l a tion c ol um n, a nd re
m ov ing th e l ow b oil ing p oint c om p onents , inc l ud
ing w a ter, w h ereb y th e c ontent of th e h y drop erox
ide is dec rea s ed; a nd '
( 4 ) rem ov ing th e th us f orm ed h y droq uinone f rom th e
dis til l a tion res idue. '
2 . A p roc es s a s c l a im ed in c l a im 1 , w h erein th e dis til
l a tion f or rem ov ing th e l ow b oil ing p oint c om p onents is
c a rried out in th e p res enc e of a s ol v ent
w h ic h h a s a b oil ing p oint h ig h er th a n th a t of w a ter,
w h ic h is ins ol ub l e or onl y s l ig h tl y s ol ub l e in w a ter,
_ a nd is c a p a b l e of dis s ol v ing h y droq uinone
w h ereb y th e h y droq uinone s ol ution is rec ov ered a s a
c ol um n b ottom l iq uid a nd th erea f ter th e h y droq uinone
s ol ution is dis til l ed in th e p res enc e of w a ter in a dis til l a
tion c ol um n, th e s ol v ent is rec ov ered f rom th e top of
th e c ol um n a s a n a z eotrop e w ith w a ter a nd th e h y dro
q uinone is rec ov ered f rom th e b ottom of th e c ol um n in
th e f orm of a n a q ueous s ol ution. '
3 . A p roc es s a s c l a im ed in c l a im 1 or 2 , w h erein th e
p -diis op rop y l b enz ene. dih y drop eroxide is deriv ed f rom
th e a ir oxida tion of p -diis op rop y l b enz ene, p -diis op ro
p y l b enz ene m onoh y drop eroxide or a m ixture th ereof .
4 . A p roc es s a s c l a im ed in c l a im 1 or 2 , w h erein a n
org a nic s ol v ent, w h ic h h a s a b oil ing p oint h ig h er th a n
th a t of w a ter, w h ic h is ins ol ub l e or onl y s l ig h tl y s ol ub l e
in w a ter, a nd is c a p a b l e of dis s ol v ing h y droq uinone,
c oexis ts in th e h y drop eroxide dec om p os ition s tep in th e
p res enc e of th e a c id c a ta l y s t.
5 . A p roc es s a s c l a im ed in c l a im 4 , w h erein s a id or
g a nic s ol v ent is a ketone or m ixture of ketones h a v ing
f rom 6 to 1 0 c a rb on a tom s .
6 . A p roc es s a s c l a im ed in c l a im 5 , w h erein s a id ke
tones a re m eth y l is ob uty l ketone, diis op rop y l ketone
a nd diis ob uty l ketone.
7 . A p roc es s a s c l a im ed in c l a im 1 or 2 , w h erein th e
c ontent of th e h y drop eroxide c onta ined in th e s ta rting
2 0
2 5
3 0
3 5
4 0
4 5
5 0
5 5
6 5
9 1 0
TA B L E I
Crude Hy drg g uinone A c etone Dew a tering Wa ter
h y dro- B ottom B ottom S ol u.
c ol or p eroxide h y dro- h y dro: c ol or Produc t HQ
( a b s or- c onc . p eroxide p eroxide H2 0 ( a b s or- rec ov ery
7 No. b a nc e) ( w t %) y iel d ( w t %) H1 8 0 4 " ( w t %) ( w t %) b a nc e) Ha z en ( %)
l 0 . 1 0 . 3 5 9 8 0 . 3 0 . 0 0 2 0 . 0 7 7 0 . 7 0 . 8 5 1 0 0
2 0 . 1 - v 0 . 3 5 9 8 0 . 3 0 . 0 1 0 . 0 3 0 . 7 0 . 7 5 5 1 0 0
A 0 . 1 0 . 3 5 9 8 0 . 3 0 . 0 0 . 2 3 0 . 3 2 . 5 3 0 9 7 . 5
B 0 . 4 1 0 . 0 3 8 8 _ - 7 - _ _ - _ -
3 0 . 1 l 0 . 7 8 9 7 0 . 5 5 0 . 0 2 0 . 0 5 0 . 4 0 . 7 8 5 1 0 0
in m ol e p erc ent c a l c ul a ted on th e tota l a m ounts of p -DHP a nd p -HHP.
"a q ueous , in p a rts b a s ed up on 1 0 0 p a rts of th e b ottom l iq uid.
Wh a t is c l a im ed is : - 1 5 m a teria l to b e dec om p os ed in th e p res enc e of th e a c id
c a ta l y s t is 4 0 th roug h 8 0 % b y w eig h t.
8 . A p roc es s a s c l a im ed in c l a im 1 or 2 , w h erein th e
dec om p os ition rea c tion of th e h y drop eroxide in th e
p res enc e of th e a c id c a ta l y s t is c a rried out a t a tem p era
ture of a b out 5 0 to a b out 8 0 C. f or a b out 5 to a b out 6 0
m inutes .
9 . A p roc es s a s c l a im ed in c l a im 1 or 2 , w h erein th e D
c onc entra tion of th e h y drop eroxide is m a inta ined in th e
ra g e of a b out 0 . 2 to a b out 0 . 5 % b y w eig h t during th e
dec om p os ition s tep .
1 0 . A p roc es s a s c l a im ed in c l a im 1 , w h erein th e
a m ount of s a id a c id is a b out 0 . 0 0 1 to a b out 0 . 1 p a rt b y
w eig h t, b a s ed on 1 0 0 p a rts b y w eig h t of th e f eed m a te
ria l to b e f ed to th e dis til l a tion c ol um n.
1 1 . A p roc es s f or p roduc ing h y droq uinone c om p ris
ing th e s eq uentia l s tep s of :
( l ) dec om p os ing p -diis op rop y l b enz ene dih y
drop eroxide in th e p res enc e of a w a ter-s ol ub l e a c id
c a ta l y s t s el ec ted f rom s ul f uric a c id, p h os p h oric
a c id, a nd p erc h l oric a c id a t a tem p era ture of a b out
2 0 C. to a b out 9 0 C. a nd m a inta ining th e c onc en
tra tion of th e h y drop eroxide in th e ra ng e of a b out
0 . 1 to a b out 1 % b y w eig h t;
( 2 ) dis til l ing th e rea c tion m ixture, a f ter rem ov ing th e
a c id c a ta l y s t th eref rom , w h ereb y l ow b oil ing p oint
c om p onents c onta ined in th e rea c tion m ixture a re
rem ov ed f rom th e rea c tion m ixture in th e p res enc e
of a s ol v ent w h ic h h a s a b oil ing p oint h ig h er th a n
th a t of w a ter a nd w h ic h is ins ol ub l e or onl y s l ig h tl y
s ol ub l e in w a ter b ut is c a p a b l e of dis s ol v ing h y dro
q uinone; _
( 3 ) f urth er s ub j ec ting th e rem a ining h y drop eroxide
f rom th e dec om p os ition s tep to a n a c id dec om p os i
tion in th e p l ura l dis til l a tion c ol um ns during th e
rem ov a l of th e l ow b oil ing p oint c om p onents a nd
/or s a id s ol v ent w h ereb y th e c ontent of th e h y dro
p eroxide is dec rea s ed, a nd s ol v ent is rec ov ered a s
a n a z eotrop e; a nd
( 4 ) rec ov ering th e th us f orm ed h y droq uinone f rom
th e dis til l a tion res idue.
1 2 . A p roc es s f or p roduc ing h y droq uinone c om p ris
ing th e s eq uentia l s tep s of :
( l ) dec om p os ing p -diis op rop y l b enz ene dih y
drop eroxide in th e p res enc e of s ul f uric a c id or
p h os p h oric a c id, a nd m a inta ining th e c onc entra ~
tion of th e h y drop eroxide in th e ra ng e of a b out 0 . 1
to a b out 1 % b y w eig h t;
( 2 ) dis til l ing th e rea c tion m ixture a t a tem p era ture of
a b out 2 0 C. to a b out 9 0 . C. , a f ter rem ov ing s a id
s ul f uric a c id or p h os p h oric a c id th eref rom ,
w h ereb y l ow b oil ing p oint c om p onents c onta ined
in th e rea c tion m ixture a re rem ov ed f rom th e rea c
tion m ixture;
4 , 4 3 4 , 3 0 5
1 1 1 2
( 3 ) f urth er s ub j ec ting th e rem a ining h y drop eroxide ( 4 ) rec ov ering th e th us f orm ed h y dm q uinone f rom
f rom th e dec om os ition s te to a n a c id dec om os i- ' th e dis til l a tion res idue . . . .
t. . th d. I: t. 1 p d . v th p 1 . 1 3 . A p roc es s a s c l a im ed 1 n c l a im 1 1 or 1 2 m w h ic h
1 m e 1 s _ a 1 0 1 % c o um n unng e rem ov ? th e dec om p os ition rea c tion is c onduc ted a t a tem p era
of th e l ow b oil m g p om t c om p onents w h ere b y th e 5 m m of a b out 5 0 C_ to a b out 3 0 C_
c ontent of th e h y drop eroxide is dec rea s ed; a nd - * * * *
1 5
: 3 0 '
3 5
4 5
, 5 5
6 5