United States Patent [ .

1 9 ]
[ 1 1 ] 3,9 9 6,29 8
Izumi et al . [ 4 5 ] D ec . 7 , 1 9 7 6
[ 5 4 ] PROCESS FOR THE HYD RATION OF 2,87 6,266 3/ 1 9 5 9 Wegner . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260 / 64 1
()LEFINS 3,7 5 8,61 5 9 / 1 9 7 3 Izumi et al . . . . . . . . . . . . . . . . . . . . . . . . . 260 / 64 1
[ 7 5 ] . Inv ento rs: Yusuke Izumi, Sh innany o ; Sumio FOREIGN PATENTS OR APPLICATIONS
Akiy ama, To kuy ama; Kiny a . . 4
Yamazaki, Yo no ; Masato To do ; 4 86,7 83 6/ 1 9 38 United Kingdo m . . . . . . . . . . . . . . . 260 / 6 1
Takao To mita, b o th o f To kuy ama, OTHER PUBLICATIONS
3" o f Japan Kaiser et al . , I. & E. C. Pro duc t R & P , v o l . 1 , D ec .
[ 7 3] Assignee: To kuy ama So da Kab ush iki Kaish a, 1 9 62, Reprint, pp. 29 64 30 1 . '
Japan
[ 22] Fil ed; No v _ 1 , 1 9 7 4 Primary Examiner-Jo seph E. Ev ans
Atto rney , Agent, o r F irm-Sh erman & Sh al l o w ay
[ 21 ] Appl . No . : 5 20 ,0 9 4 ,
Rel ated US. Appl ic atio n D ata [ 5 7 ] ABSTRACT
63 C _ _ ' A pro c ess f o r th e preparatio n o f mo no h y dric al c o h o l s
[ 1 21 5 3; 21 2: 25 0 o f 86f N0 238 1 29 Marc h 27 1 9 7 2 b y c o ntac ting a mo no o l ef in o f 2-4 c arb o n ato ms w ith
' an aqueo us so l utio n c o ntaining a h etero po 1 y ac id io n,
[ 30 ] Fo reign Appl ic atio n Prio rity D ata th ereb y sub j ec ting th e o l ef in to a h y dratio n reac tio n,
May 31 1 9 7 1 Japan _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 4 64 87 20 c h arac terized in th at said aqueo us so l utio n c o ntains th e
h etero po l y -ac id io n in a c o nc entratio n o f at l east
[ 5 2] US. Cl ; . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260 / 64 1 ; 25 2/ 4 1 1 R IMO OOO mo l per l iter and h as a PH ranging f ro m 2' 0 to
[ 5 1 ] Int. Cl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C0 7 C 29 / 0 4 4 5 and th e aqueo us So l utio n is h eated to a tempera_
[ 5 8] Fl el d o f Searc h . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260 / 64 1 ture suf f ic ientl y h igh f o r initiating th e h y dratio n reac _
[ 5 6] Ref erenc es Cited tio n, w h il e th e f ree iro n io n c o nc entratio n th erein is
maintained at no t h igh er th an 1 0 ppm sub stantial l y
. UNITED STATES PATENTS th ro ugh o ut th e w h o l e h y dratio n reac tio n perio d.
2,1 62,9 1 3 6/ 1 9 39 Ev erso l e et al . . . . . . . . . . . . . . . . . . . . 260 / 64 1
2,1 7 3,1 87 9 / 1 9 39 Tanner . . . . . . . . . . . . . . . . . 1 . . . . . 260 / 64 1
2,5 7 9 ,60 1 1 2/ 1 9 5 1 Nel so n et al . . . . . . . . . . . . . . . . . . . . . . 260 / 64 1 4 Cl aims, 2 D raw ing Figures
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1 .
PROCESS FORTHE HYD RAT ION OF OLEFINS
Th is is a c o ntinuatio n o f appl ic atio n Ser. No .
238,1 29 , ? l ed Mar. 27 , 1 9 7 2 no w ab ando ned.
Th is inv entio n rel ates to a pro c ess f o r th e h y dratio n
o f o l e? ns, w h ic h c o mprises h y drating an o l e? n b y c o n
tac ting it w ith an aqueo us so l utio n c o ntaining a
h etero po l y -ac id io n as th e c atal y st, rec o v ering al c o h o l
f ro m th e resul ting aqueo us so l utio n o f th e c o rrespo nd
ing al c o h o l , and rec y c l ing th e aqueo us so l utio n c o n
taining th e h etero po l y ac id io n remaining af ter th e re
mo v al o f al c o h o l to th e h y dratio n step to use it again
f o r th e h y dratio n o f o l e? n. '
A numb er o f c atal y sts h av e b een kno w n as ef f ec tiv e
f o r direc t h y dratio n o f o l e? ns. Partic ul arl y , th e util ity
o f h etero po l y -ac id and w ater-so l ub l e sal ts th ereo f f o r
th e h y dratio n o f o l e? n to pro duc e al c o h o l andeth er is
kno w n f ro m British Pat. No . 4 87 ,384 . Mo re spec i?
c al l y , th e h etero po l y -ac id inc l udes b o ro tungstic ac id,
ph o sph o tungstic ac id, sil ic o tungstic ac id, sil ic o mo l y b
dic ac id, and ph o sph o mo l y b dic ac id. It is kno w n th at
th o se h etero po l y -ac ids general l y exh ib it o l ef in-h y drat
ing ac tiv ity al so in th e f o rm o f w ater-so l ub l e sal ts
th ereo f . To w it, h etero po l y -ac id in w ater is sub stan
tial l y disso c iated into a h y dro gen io n and a h etero po l y
ac id io n, simil arl y to o rdinary mineral ac id, and sh o w s
th e c atal y tic ac tiv ity f o r h y dratio n o f o l ef ins as th e
resul t o f th e c o nc urrent presenc e o f th e tw o ty pes o f
io ns. .
Th us, in th e h y dratio n reac tio n o f o l e? n, th e
h etero po l y -ac id io n ac ts as th e main c atal y st, w h il e th e
h y dro gen io n ef f ec tiv el y ac ts as an ac tiv ato r o f th e
f o rmer. Fo r th is reaso n, w h en a h etero po l y -ac id is used
as th e c atal y st f o r h y dratio n o f o l e? n in th e f o rm o f sal t,
a neutral sal t exh ib its o nl y v ery mino r c atal y tic ac tiv ity ,
and th eref o re an ac idic sal t is adv antageo usl y em
pl o y ed. In o th er w o rds, th e c o nc urrent presenc e o f
h etero po l y -ac id io ns and h y dro gen io ns in th e aqueo us
so l utio n pro v ides th e adv antageo us c atal y st sy stem. As
th e ty pic al metal s f o r f o rming w ater-so l ub l e, ac idic
sal ts o f th e h etero po l y -ac ids, al kal i metal s suc h as so
dium and po tassium; and c al c ium, magnesium, c ad
mium and al uminum may b e named. ,
Ac c o rding to th e inv entio n, th e o ptimum resul ts are
5
2
ac id io ns. Th us w e c o n? rmed th e nec essity to av o id th e
sub stantial presenc e o f f ree iro n io ns.
Ac c o rding to th e inv entio n, th e c atal y st sy stem is
c o mpo sed o f h etero po l y -ac id io ns and h y dro gen io ns as
al ready mentio ned. Fo r th is reaso n th e h etero po l y -ac id
io n-c o ntaining aqueo us so l utio n is c o ntac ted w ith o l e
? n at a pH ranging f ro m 2. 0 to 4 . 5 . Suc h an ac idic
so l utio n al w ay s disso l v es iro n o r iro n c o mpo unds as it
c o ntac ts w ith th e reac to r, distil l atio n sy stem o f th e
f o rmed al c o h o l , transf erring pipes, etc . , and c o nse~
quentl y unav o idab l y c o ntains f ree iro n io ns at gradual l y
inc reasing c o nc entratio n. Furth ermo re, sinc e th e sub
j ec t pro c ess c o nc erns h y dratio n, w ater must b e added
,. to th e reac tio n sy stem and, b ec ause th e w ater itsel f
20
25
30
35
4 0
4 5
o b tained f ro m' th e h y dratio n o f o l e? n using th e ;
h etero po l y -ac id, w h en th e mo l ar c o nc entratio n o f c ata
l y tic c o mpo nent range is l / 4 0 ,0 0 0 H30 0 , and th e pH
range is 2. 0 - 4 . 5 . Th e reac tio n is perf o rmed at 1 0 0 ~
5 0 0 kgl c mz, and at 1 5 0 37 0 C. Th e h igh er th e mo l ec
ul ar w eigh t o f th e o l e? n, th e l o w er may b e th e reac tio n
temperature, w ith in th e ab o v e-spec i? ed range. Fo r
exampl e, th e temperature range o f 20 0 - 35 0 C. is
rec o mmended f o r h y dratio n o f eth l ene, w h il e it is 20 0
- 30 0 C. f o r pro py l ene, and 1 7 0 - 25 0 ? C. f o r b utene.
Th e c atal y tic ac tiv ity o f th o se h etero po l y -ac id io ns in
th e h y drating reac tio n o f o l e? ns th us b eing extremel y
h igh , w e f o und th at th e durab il ity o f th e ac tiv ity is
rel ativ el y sh o rt. Fo r exampl e, o ur experiments c o n
? rmed th at in an iro n reac to r, 1 0 % o f th e c atal y st de
c o mpo sed, under th e ,reac tio n c o nditio ns o f 30 0 C.
and 1 5 0 kg/ c m , w ith in appro ximatel y 6 day s.
5 0
5 5
60
We searc h ed f o r th e c ause o f suc h dec rease o f ac tiv
ity o c c urring w ith dec o mpo sitio n o f th e c atal y st, etc . ,
and disc o v ered th at th e dec rease in c atal y tic ac tiv ity
c o ntains' iro n io ns al th o ugh in mino r quantities, f ro m
th is so urc e al so iro n io ns gradual l y ac c umul ate in th e
reac tio n sy stem.
It is no w f o und, ac c o rding to th e inv entio n, th at b y
sub stantial l y av o iding th e c o nc urrent presenc e o f f ree
iro n w ith th e c atal y st io ns c o mpo sed c h ie? y o f
h etero po l y -ac id io ns, th e c atal y st sy stem c an b e used
repetitiv el y , w ith o ut sub stantial reduc tio n in th e c ata
l y tic ac tiv ity o v er pro l o nged perio ds o f time.
It h as prev io usl y b een repo rted th at iro n sil ic o tung
state, iro n sil ic o ph o sph ate' , f erric sul f ate, f erric mo l y b
date, etc . are used as c atal y sts f o r th e h y dratio n reac
tio n o f o l e? ns (f o r exampl e, Brennsto f f -Ch em. 38, 321
(1 9 5 7 ), U. S. Patent 2. 87 6,266). In v iew o f th is kno w n
inf o rmatio n, it is quite unexpec ted th at ev en a v ery
smal l amo unt o f iro n io ns ab ruptl y reduc es th e c atal y tic
ac tiv ity o f h etero po l y -ac id io ns as desc rib ed ab o v e.
Th us, ac c o rding to th e sub j ec t pro c ess f o r th e prepa
ratio n o f mo no h y dric al c o h o l w h ic h c o mprises c o ntac t
ing a mo no o l e? n o f 2 to 4 c arb o n ato ms w ith an aque
o us so l utio n c o ntaining h etero po l y -ac id and th ereb y
h y drating th e o l e? n, th e c h arac teristic f eatures residing
in th at th e aqueo us so l utio n c o ntains th e h etero po l y
ac id io n at a c o nc entratio n o f at l east 1 / 4 0 ,0 0 0 mo l per
l iter and h as a pH ranging f ro m 2. 0 to 4 . 5 . Mo reo v er,
w h en th e so l utio n is h eated to th e temperature suf ?
c ientl y h igh f o r initiating th e h y dratio n reac tio n, w h il e
th e f ree iro n io n c o nc entratio n in th e so l utio n is main
tained at no t h igh er th an 1 0 ppm sub stantial l y th ro ugh
o ut th e w h o l e perio d o f said reac tio n, mo no h y dric
al c o h o l c o rrespo nding to th e starting o l e? n c an b e
prepared w ith h igh c o nv ersio n and h igh sel ec tiv ity ,
w ith o ut any sub stantial reduc tio n in th e c atal y st s ac tiv
ity f o r a pro l o nged perio d.
Th e prec ise mec h anism w ith w h ic h th e f ree iro n io n
c auses th e dec rease in c atal y tic ac tiv ity is no t y et c l ear.
Our o pinio n is th at eith er th e c atal y st io n and iro n io n
reac t to f o rm prac tic al l y inert, inso l ub l e matter, o r th e
iro n io n ac ts c atal y tic al l y to pro mo te dec o mpo sitio n o f
th e h etero po l y -ac id. Co nc erning th e dec rease in th e
c atal y tic ac tiv ity w h ic h h as b een regarded as b eing
' c aused b y th e c atal y st s dec o mpo sitio n, it is c o n? rmed
th at suc h dec rease is no t v ery apprec iab l e af ter th e f irst
c irc ul atio n o f th e c atal y st so l utio n in th e f l o w reac tio n
sy stem, b ut upo n repetitiv e rec irc ul atio n o f th e so l u
tio n, iro n io ns gradual l y ac c umul ate in th e so l utio n to
c ause a marked reduc tio n in th e c atal y tic ac tiv ity .
- Th is c an b e c l earl y demo nstrated b y o ur experi
ments. Fo r exampl e, th e c o rrel atio n o f th e c atal y st s
' dec o mpo sitio n ratio n (w h ic h is th e reduc tio n ratio and
takes pl ac e w h en iro n io ns are sub stantial l y . present in .
th e reac tio n sy stem f o r prac tic ing th e present' iny en
tio n, i. e. , th e aqueo us so l utio n c o ntaining h etero po l y
h as sub stantial l y equiv al ent signi? c anc e to th e l o w ering
ratio in th e c atal y tic ac tiv ity ) w ith th e c o nc entratio n o f
" c o nc urrentl y existing iro n io ns is il l ustrated in FIG. 1 ,
- ,as to an aqueo us so l utio n o f sil ic o tungstic ac id at 1 . 0 3
3,9 9 6,29 8
3
mo l / l iter c o nc entratio n, used at 29 0 C. and 1 5 0
kgl c mzG o f pro py l ene f o r 24 0 h o urs. As c an b e under
sto o d f ro m FIG. 1 , up to 5 ppm o f iro n io n c o nc entra
tio n h ardl y interf eres w ith th e c atal y st s ac tiv ity , i. e. ,
th e c atal y st s dec o mpo sitio n ratio is no mo re th an 2%
w h ereas th e detrimental ef f ec t o f th e iro n io n c o nc en
tratio n b ec o mes inc reasingl y no tab l e as it inc reases
f ro m 1 0 to 1 5 ppm. At 1 5 ppm, nearl y 1 0 % o f th e
c atal y st is dec o mpo sed and, b ey o nd 1 5 ppm, th e c ata
l y tic ac tiv ity is dec reased atsuc h a rate as no t to b e
industrial l y ac c eptab l e. Sub stantial l y th e same ten
denc y is rec o gnized in th e c atal y tic ac tiv ities o f o th er
h etero po l y -ac id io ns, e. g. , b o ro tungstic ac id io ns, ph o s
ph o tungstic ac id io ns, sil ic o mpo l y b dic ac id io ns, and
ph o sph o mo l y b dic ac id io ns. Al so th e dec o mpo sitio n
rate is sub stantial l y unaf f ec ted b y pH v ariatio ns in th e
so l utio n w ith in th e ac idic range. Ac c o rding to th e pre
sent inv entio n, th eref o re, th e c o nc entratio n o f f ree iro n
io ns in th e c atal y tic aqueo us so l utio n to b e suppl ied to ,
o r c aused to b e present in, th e h y dratio n reac tio n sy s
tem, th ro ugh rec irc ul atio n o r o th er kno w n means, is
c o ntro l l ed to b e no t h igh er th an 1 0 ppm and pref erab l y
b el o w 5 ppm.
As so urc es o f f ree iro n io ns w h ic h ac c umul ate in th e
reac tio n sy stem during th e preparatio n o f al c o h o l
th ro ugh th e direc t h y dratio n o f o l e? n, th e f o l l o w ing
c an b e enumerated: '
a. El utio n f ro m c o nstruc tio n material s o f th e equip;
ment empl o y ed, suc h as th e reac to r, distil l atio n c o l
umn, c o nnec ting pipes; etc . , and
b . Intro duc tio n f ro m th e w ater' suppl y to th e h y dra
tio n reac tio n sy stem, th e f o rmer b eing th e mo re signi?
c ant.
Ac c o rdingl y , in th is inv entio n th e f ree iro n io n c o n
c entratio n in th e reac tio n sy stem is c o ntro l l ed so as
nev er to exc eed 1 0 ppm, pref erab l y 5 ppm, b y prev ent
ing th e entranc e and ac c umul atio n o f f ree iro n io n in
th e reac tio n sy stem th ro ugh th e ro utes (a) and (b ) as
muc h as po ssib l e, and if nec essary (as in th e maj o rity o f
c ases), b y remo v ing th e iro n io ns unav o idab l y b ro ugh t
into th e sy stem and/ o r inac tiv ating th e same w ith , f o r
exampl e, a c h el ating agent.
As th e means to adv antageo usl y prac tic e th e sub j ec t
inv entio n, f o r exampl e, th e f o l l o w ing sev eral emb o di
ments c an b e empl o y ed,
i. c o ntro l l ing th e f ree iro n io n c o nc entratio n in th e
aqueo us so l utio n to keep it b el o w 1 0 ppm, pref erab l y
b el o w 5 ppm, b y prac tic ing th e h y dratio n reac tio n in a
reac to r o f w h ic h at l east th e internal surf ac es are c o n
struc ted o f no n-f erro us metal w h ic h is no n-c o rro siv e to
th e aqueo us so l utio n.
As th e no n-f erro us metal s usef ul f o r th e ab o v e pur
po se, f o r exampl e, nic kel , c h ro mium, titanium, zirc o
nium, tantal um, sil v er, go l d, and pl atinum may b e
named. It sh o ul d b e apparent th at, w h il e th o se no n-f er
ro us metal s may b e used as th e c o nstruc tio n material o f
th e reac to r, l ining o r pl ating o f th e internal surf ac es o f
th e reac to r w ith th o se metal s is al so ef f ec tiv e. Th us,
c o nv entio nal f erro us reac to rs c an b e impro v ed to b e
suited f o r use in th e sub j ec t pro c ess, b y l ining o r pl ating
th em w ith th o se no n-f erro us metal s. Al so iro n-c o ntain
ing al l o y s w h ic h h ardl y al l o w el utio n o f iro n io ns c an b e
used under c ertain c irc umstanc es.
Ob v io usl y , it is mo re desirab l e to c o nstruc t no t o nl y
th e reac to r, b ut al so th e distil l atio n c o l umn f o r separat
ing th e f o rmed al c o h o l and c o nnec ting pipes, f ro m
th o se no n-f erro us metal s. Ho w ev er, suc h w il l make th e
reac tio n apparatus extremel y expensiv e. Fo r th is rea
25
30
35
4 5
5 0
5 5
60
65
4
so n, in prac tic e it is v irtual l y impo ssib l e to c o mpl etel y
prev ent th e entranc e o f f ree iro n io ns into th e reac tio n
sy stem and, th eref o re, it is no rmal l y desirab l e, (pro b a
b l y exc epting th e c ase w h erein v ery c aref ul l y re? ned,
iro n-f ree w ater is used), to c o nc urrentl y prac tic e th e
remo v al o f f ree iro n io ns f ro m th e aqueo us so l utio n
c o ntaining h etero po l y -ac id io ns b y th e means l ater
desc rib ed, o r b y inac tiv atio n o f th e io n b y c h el atio n,
etc .
ii. Co ntro l l ing o f th e f ree iro n io n c o nc entratio n in
th e aqueo us so l utio n to b e b el o w 1 0 ppm, pref erab l y
b el o w 5 ppm, sub stantial l y th ro ugh o ut th e w h o l e pe
rio d o f th e spec i? ed h y dratio n pro c ess, b y c o ntac ting
th e h etero po l y -ac id io n-c o ntaining aqueo us so l utio n,
w h ic h is o b tained b y separating th e f o rmed mo no h y
dric al c o h o l f ro m th e reac tio n mixture af ter c o mpl etio n
o f th e h y dratio n, w ith a c atio n exc h anger, th ereb y ad
so rb ing o r remo v ing-b y reac tio n th e f ree iro n io ns c o n
tained in said so l utio n, and rec y c l ing th e aqueo us so l u
tio n to th e h y dratio n reac tio n sy stem.
Exc h angers suited f o r th e remo v al o f f ree iro n io ns in
th e aqueo us so l utio n, are c atio n exc h ange resins and
ino rganic c atio n exc h angers. Mo re spec i? c al l y , c atio n
exc h ange resins suc h as Amb erl ite (trademark, pro duc t
o f Ro h m & Haas Co . , U. S. A. ), D iaio n (trademark,
pro duc t o f MCI, Japan) and c h el ating c atio n exc h ang
ers w h ic h f o rm c h el ate c o mpo unds w ith iro n io ns; and
ino rganic c atio n exc h angers c o mpo sed o f ph o sph ates
o f th e metal s o f Gro up IVa o f th e perio dic tab l e; f o r
exampl e, are usef ul f o r th is purpo se. ' ,
Th e treatment o f th e aqueo us so l utio n w ith suc h
c atio n exc h angers c an b e ef f ec ted b y c o nv entio nal l y
prac tic ed io n-exc h anging means, suc h as passing th e
ab o v e-spec i? ed h etero po l y -ac id io n-c o ntaining aque
o us so l utio n th ro ugh a to w er pac ked w ith th e io n ex
c h anger. v
A ty pic al emb o diment o f th is meth o d is sh o w n as a
f l o w c h art in FIG. 2. Ref erring to said ? gure, th e start
ing o l ef in is intro duc ed into th e reac to r (3) th ro ugh
pipe (1 ), and th e c atal y tic so l utio n is suppl ied into th e
same reac to r th ro ugh pipe (4 ). Th e w ater repl enish
ment to make up th e w ater reduc tio n due to its c o n
sumptio n during th e h y dratio n and f ro m o th er mino r
c auses, is ef f ec ted f ro m pipe (2). Th e reac ted so l utio n,
i. e. , a mixed aqueo us so l utio n o f th e reac tio n pro duc t
and c atal y st, is transf erred th ro ugh pipe (5 ), and ex
c h anges h eat w ith th e rec irc ul ating c atal y tic so l utio n at
th e h eat exc h anger (1 2). Th en th e so l utio n is sent to
th e distil l atio n c o l umn (6), to b e separated into th e
desired pro duc t, i. e. , al c o h o l , and th e c atal y tic so l u
tio n. Th e al c o h o l is f urth er sent into th e ref ining c o l
umn (8) th ro ugh pipe (7 ). Th e re? ned al c o h o l is w ith
draw n f ro m pipe (9 ). Th e c atal y tic so l utio n separated
at th e distil l atio n c o l umn (6) is sent to th e iro n-remo v
ing c o l umn (1 1 ) pac ked w ith th e io n exc h anger,
th ro ugh pipe (1 0 ), to b e remo v ed o f th e f ree iro n io n,
and th en rec y c l ed to th e reac to r (3) th ro ugh pipe (4 ).
iii. Co ntro l l ing o f th e f ree iro n io n c o nc entratio n in
th e aqueo us so l utio n to b e no t h igh er th an 1 0 ppm,
pref erab l y b el o w 5 ppm, sub stantial l y th ro ugh o ut th e
h y dratio n reac tio n, b y adding to th e aqueo us so l utio n a
stab il izer w h ic h c an f o rm a c h el ate c o mpo und w ith th e
f ree iro n io n in situ. '
Usef ul stab il izers are, f o r exampl e,o rth o -ph o sph o ric
ac id, meta-ph o sph o ric ac id, py ro ph o sph o ric ac id, and
po l y ph o sph o ric ac id w h ic h c an b e expressed b y ,th e
general f o rmul a, P2O5 ' nI-I2O (n stands f o r an integer);
al kal i metal sal ts th ereo f ; eth y l enediaminetetraac etic
3,9 9 6,29 8
5
ac id, nitril o triac etic ac id; and th eir w ater-so l ub l e sal ts;
etc . Th e stab il izers to b e used in ac c o rdanc e w ith th is
emb o diment are c h el ating agents w h ic h exh ib it h igh
reac tiv ity w ith f ree iro n io ns, b ut sh o w no detrimental
ef f ec t o n th e o l e? nh y drating ac tiv ity o f th e c atal y st
sy stem c o mpo sed c h ie? y o f h etero po l y -ac id. Partic u
l arl y pref erred stab il izers are po l y ph o sph o ric ac id in
w h ic h th e P20 5 c o ntent is no l ess th an 7 2. 4 w t. %, and
w ater-so l ub l e sal ts th ereo f w ith , f o r exampl e, so dium
6
purged f ro m th e auto c l av e, and th e remaining c atal y tic
so l utio n c o ntaining th e f o rmed al c o h o l w as l et stand f o r
1 0 0 h o urs at 30 0 C. and 1 0 0 kg/ c m2 G, in th e same
c o ntainer in th e auto c l av e. Th ereaf ter th e reduc tio n in
sil ic o -tungstic ac id io n c o nc entratio n in th e so l utio n
w as measured, w ith th e resul ts as sh o w n in th e l ast
c o l umn o f Tab l e 1 . Th e iro n io n c o nc entratio n in th e
so l utio n af ter th e reac tio n w as 1 4 ppm w h en th e stain
l ess steel reac to r w as used, and in al l o th er c ases no
and po tassium. No rmal l y th e use o f th o se stab il izers at 1 0 mo re th an 1 ppm.
Tab l e 1
Catal y tic
So l utio n Resul t
SW Co n- Al c o h o l SW
Co n- c entra- Reac tio n c o nditio ns c o nc en- Sel ec - Reduc tio n
struc tio n tio n Temp. Pres. Time Main tratio n tiv ity Ratio
Run No . Metal (g/ l ) pH ( C. ) (kg/ c m G) (h r. ) Ol e? n Pro duc t (w t. %) (%) (%/ 1 0 0 h rs. )
1 Stainl ess 3. 0 3. 0 230 20 0 1 Pro py l ene 1 5 0 - 8. 6 9 9 4 . 8
(Co ntro l ) steel pro pano l
SUS27
2 Ni 3. 0 3. 0 230 20 0 l " " 8. 7 9 9 1 . 2
3 Ni 1 . 0 2. 8 230 20 0 l " " 1 0 . 7 9 8 0 . 3
4 Cr 3. 0 3. 0 230 20 0 1 " 9 " 8. 8 9 9 0 . 8
5 Ag 3. 0 3. 0 230 20 0 l " " ' 8. 6 9 9 1 . 0
6 Ti 3. 0 3. 0 . 230 20 0 1 " " 8. 7 9 9 0 . 8
7 Zr 3. 0 3. 0 230 20 0 l " " 8. 8 9 9 1 . 2
8 Ta 3. 0 3. 0 230 20 0 1 " " 8. 8 9 9 0 . 8
9 Au 3. 0 3. 0 230 20 0 l " " 8. 9 9 9 0 . 3
1 0 Pt 3. 0 3. 0 230 20 0 1 " " 9 . 0 9 9 0 . 2
1 1 Cr 0 . 5 3. 3 25 0 20 0 1 " " 1 0 . 2 9 9 0 . 2
1 2 Ti 1 . 0 3 . 3 25 0 20 0 l Eth y l ene Eth ano l 6. 8 9 9 0 . 7
1 3 Ti 1 0 3. 3 25 0 20 0 1 Mixed Mixed 9 . 6 9 9 0 . 8
b uty l ene b utano l
th e ratio o f a ro ximatel 0 . 0 1 ram er l iter o f th e
pp y g p EXAMPLE 2
so l utio n is suf ? c ient to ac h iev e th e desired ef f ec t. No
c o rrespo ndingl y impro v ed resul t c an b e expec ted f ro m
th e additio n o f mo re th an 1 gram o f suc h a stab il izer
per l iter o f th e so l utio n.
Onl y a f ew exempl ary emb o diments h av ing b een
expl ained in th e f o rego ing items(i) th ro ugh (iii) as th e
spec i? c means f o r reduc ing f ree iro n io ns in th e c ata
l y tic so l utio n, and it sh o ul d b e apparent th at th e sc o pe
o f th is inv entio n is b y no means l imited th ereto . Oth er
means w h ic h are easil y c o nc eiv ab l e b y th o se skil l ed in
th e art may , o f c o urse b e empl o y ed. It is al so pref erab l e
to prac tic e tw o o r mo re o f th o se means c o nc urrentl y ,
to maintain th e f ree iro n io n c o nc entratio n in th e c ata
l y tic so l utio n at a stil l l o w ered l ev el .
EXAMPLE
A c o ntainer w h ic h w as c o nstruc ted o f th e metal spec
i? ed in Tab l e 1 , sec o nd c o l umn, w as c h arged w ith 1 5 0
ml o f th e c atal y tic so l utio n c o ntaining sil ic o tungstic
ac id io n (SW) at th e c o nc entratio n al so spec i? ed in
Tab l e 1 , and w as inserted into a SOO-ml c apac ity stain
l ess steel auto c l av e. Th e spec i? ed o l e? n w as intro
duc ed into th e c o ntainer under h eating, until th e tem
-35
4 0
4 5
5 0
Catal y tic so l utio ns eac h c o ntaining sil ic o tungstic
ac id (SWA), b o ro tungstic ac id (BWA), ph o sph o tung
stic ac id (PWA), Sil ic o mo l y b dic ac id (SMA), o r ph o s
ph o mal y b dic ac id (PMA) at c o nc entratio n o f 3 g/ l iter
w ere prepared, and th eir pH w as adj usted to 2. 8 3. 0
w ith NaOl -l . In eac h run th e c atal y tic so l utio n w as in
tro duc ed into a sil v er-l ined h igh pressure reac to r f ro m
th e upper part th ereo f , at a rate o f 3 kg/ h r. per 1 l iter
o f th e reac to r s c apac ity . Simul taneo usl y pro py l ene
w as intro duc ed into th e same reac to r f ro m th e b o tto m,
at a rate o f 0 . 26 kg/ h r. , to b e c o ntinuo usl y h y drated
under th e reac tio n c o nditio ns o f 260 C. and 1 5 0
kg/ c m2G. Th e reac tio n pro duc t w as w ith draw n f ro m
th e b o tto m o f th e reac to r to geth er w ith th e c atal y tic
so l utio n, w h ic h w assub sequentl y separated b y distil l a
tio n. Th e separated c atal y tic so l utio n w as rec irc ul ated
into th e reac to r. Th e reac to r w as c o ntinuo usl y o per
ated f o r 5 0 0 h o urs, b ut th e iro n io n c o nc entratio n in
th e rec irc ul ated aqueo us so l utio n at no time exc eeded
1 ppm. Th e av erage o ne-pass c o nv ersio n, iso pro pano l
c o nc entratio n, spac e time y iel d (S. T. Y. ) and iso pro pa
no l sel ec tiv ity o f th e initial 24 h o urs, and o f th e l ast 24
perature and pressure in th e c o ntainer reac h ed th e 5 5 h o urs, are sh o w n in Tab l e 2 b el o w .
Tab l e 2
Initial 24 Ho urs Last 24 Ho urs
SWA BWA PWA SMA PMA SWA BWA PWA SMA PMA
Co nv ersio n (7 c ) 67 64 66 68 67 67 64 65 67 5 6
Co nc entratio n (w t. %) 6. 2 5 . 9 6. 1 6. 3 5 . 3 6. 2 5 . 9 6. 0 6. 2 5 . 3
S. T. Y. (kg/ kg. c at. h r. ) 21 . 2 20 . 3 20 . 9 21 . 5 1 8. 0 21 . 2 20 . 3 20 . 7 21 . 4 21 . 3
Sel ec tiv ity (9 2) 9 8 9 9 9 8 9 8 9 9 9 8 9 9 9 8 9 8 9 9
predetermined v al ues, and h y drated f o r an h o ur. Th e
resul ts w ere as sh o w n in th e same tab l e.
In o rder to determine th e dec o mpo sitio n rate o f th e
c atal y st, af ter th e reac tio n th e unreac ted o l e? n w as
65 Th e ab o v e resul ts demo nstrate th at th e av erage per
f o rmanc e o f th e l ast 24 h o ur s o peratio n is sub stantial l y
th e same as th at o f th e initial 24 h o urs, as to al l o f th e
measurements.
3,9 9 6,29 8
7
Simil ar experiments w ere perf o rmed w ith titanium
and zirc o nium reac to rs, and th e resul ts o f 5 0 0 h o urs
8
in FIG. 2 w as no t used), are al so giv en as Runs 6
th ro ugh 1 0 .
Tab l e 3
Fe Co nc en
Co nc entratio n tratio n in
o f Catal y tic Catal y tic Al c o h o l
Run Co mpo nent So l utio n Yiel d
No . Catal y st (mo l / l iter) (ppm) (kg/ h r)
Exampl e 1 sil ic o tungstic ac id 2. 0 X 1 0 ' 2 20 . 1
2 Bo ro tungstic ac id 2. 0 X 1 0 2 20 . 1
3 Ph o sph o tungstic ac id 1 . 8 X 1 0 ' 3 1 9 . 7
4 Sil ic o mo l y b dic ac id 1 . 3 X 1 0 " 2 1 7 . 6
5 Ph o sph o mo l y b dic ac id 1 1 X 1 0 " 6 " 4 1 6. 0
Co ntro l 6 sil ic o tungstic ac id 1 . 6 X 1 0 " 1 4 1 6. 6
7 Bo ro tungstic ac id 1 . 4 X 1 0 -1 1 4 1 5 . 4
8 Ph o sph o tungstic ac id 1 . 2 X 1 0 1 1 6 1 4 . 2
9 Sil ic o mo l y b dic ac id 7 . 1 X 1 0 -4 1 8 1 3. 0
1 0 Ph o sph o mo l y b dic ac id 6. 5 X 1 0 1 9 1 2. 1
c o ntinuo us o eratio n w ere f o und to b e al mo st identic al
p EXAMPLE 4
w ith th o se o b tained w ith th e sil v er-l ined reac to r. Fur
th ermo re, a go l d-l ined reac to r w as used in simil ar ex
periments, w ith sub stantial l y th e same resul ts.
In c o ntrast th ereto , w h en a stainl ess steel h igh pres
sure reac to r w as empl o y ed, th e resul ts o f th e reac tio n
w ere sub stantial l y th e same as th o se o f th e f o rego ing
experiments during th e initial perio d. Ho w ev er, af ter
5 0 0 h o urs o f c o ntinuo us o peratio n, th e sil ic o tungstic
ac id io n c o nc entratio n dec reased b y appro ximatel y
1 0 %, and th e S. T. Y. dec reased b y appro ximatel y 3%.
Th e iro n io n c o nc entratio n in th e so l utio n at th e end o f
th e o peratio n reac h ed 1 8 ppm.
EXAMPLE 3
Pro py l ene w as h y drated th ro ugh th e pro c edures as
il l ustrated in th e ? o w c h art o f FIG. 2. Th e reac to r and
distil l atio n c o l umn w ere made o f stainl ess steel , w ith
eac h h av ing an inner diameter o f 2 inc h es. Th e pro py l
ene w as preh eated and suppl ied into th e reac to r (3)
th ro ugh pipe (1 ), and w ater and c atal y st w ere intro
duc ed th ro ugh , respec tiv el y , pipes (2) and (4 ), at suc h
rates th at th e pH o f th e c atal y tic so l utio n b ec ame 2. 8 -
3. 0 , and th e c o nc entratio n o f th e c atal y tic c o mpo nent
b ec ame 2. 1 X 1 0 3 mo i/ l iter. Th e reac tio n w as c o ntin
ued f o r 7 20 h o urs, at 280 C. and 20 0 kg/ c mzG. Th e
c atal y tic so l utio n f ro m w h ic h th e reac tio n pro duc t w as
separated at th e distil l atio n c o l umn (6) w as passed
th ro ugh a pac ked to w er ? l l ed w ith c atio n exc h ange
resin (trademark, D iaio n PK 21 6) to b e remo v ed o f
f ree iro n io ns, th en its pH w as adj usted to b etw een 2. 8
- 3. 0 , and it w as rec irc ul ated into th e reac to r. Th e
c o nc entratio n o f th e c atal y tic c o mpo nent in th e so l u
tio n and iso pro pano l y iel d in th e reac tio n pro duc t af ter
7 20 h o urs o f o peratio n w ere as sh o w n in Tab l e' 3.
Fo r c o mpariso n, th e resul ts o f th e runs prac tic ed
simiarl y , (exc ept th at th e io n-remo v ing c o l umn sh o w n
20
25
30
35
4 5
5 0
Th e h y dratio n in Run No . 2 o f Tab l e 3 (Exampl e 3)
w as repeated exc ept th at th e iro n-remo v ing c o l umn
w as pac ked w ith a c h el ating io n exc h ange resin (Ch e
l ate Resin CD 1 5 , pro duc t o f MCI). Th e resul ts w ere
identic al w ith th o se o f Run No . 2.
EXAMPLE 5
Th e c atal y st stab il izers spec i? ed in Tab l e 4 w ere
added to th e c atal y tic so l utio ns c o ntaining sil ic o tung
stic ac id io ns (SW) at th e spec i? ed c o nc entratio ns, and
to eac h o f th e c atal y st sy stems iso pro pano l w as added
at a ratio o f 6 w t. % to th e to tal amo unt o f th e c atal y st
so l utio n. Th e w h o l e sy stem w as po ured into a stainl ess
steel auto c l av e, and al l o w ed to stand f o r th e predeter
mined perio d at 30 0 C. and 1 0 0 kgl c mz. Th e resul ting
dec rease in sil ic o tungstic ac id io ns in eac h run is giv en
in Tab l e 4 . In th is Exampl e, it w as c o n? rmed th at th e
f ree iro n io n c o nc entratio n in th e c atal y tic so l utio n at
th e end o f reac tio n w as 1 0 ppm.
Fo r c o mpariso n, th e resul ts o f th e runs in w h ic h no
stab il izer w as used are sh o w n as No s. 1 and 2 o f Tab l e
4 . '
Separatel y , 1 5 0 ml o f th e c atal y tic so l utio n w ith th e
c atal y st stab il izer simil arl y added w as po ured into a
SOO-ml c apac ity auto c l av e equipped w ith a stirrer, and
into w h ic h o l e? n w as added w h il e th e sy stem w as
h eated, until th e predetermined temperature and pres
sure l ev el s w ere attained. Th e h y dratio n o f o l e? n w as
th en ef f ec ted f o r eac h predetermined perio d. Th e re
sul ts are sh o w n in Tab l e 5 . Inc idental l y , th e pH o f c ata
l y tic so l utio ns w as adj usted w ith NaOH. In Tab l e 5 ,
Run No . 6 is an exampl e in w h ic h th e stab il izer w as no t
added. It is seen f ro m th e resul ts o f Runs No s. 1 6 th at
th e stab il izers do no t adv ersel y af f ec t th e c atal y st used
in th e inv entio n.
Tab l e 4
Catal v tic Qnl minn
SW Stab il izer
Co nc en- ' Co nc en< D ec o mpo
tratio n tratio n sitio n
Run No . Catal y st (g/ l ) Ty pe (g/ l ) pH (VI/ h t)
l NaZHZSW 6. 0 3. 0 0 . 1 37
2 NaI-IQSW 3. 0 - 3. 0 0 . 0 7 6
3 Nail -1 25 W 6. 0 So dium & 0 . 3 3. 0 0 . 0 25
metaph o sph ate
4 " 6. 0 Orth c h ph o sph o ric 0 . 3 3. 0 0 . 0 0
' ac id
5 " 6. 0 So dium tripo l y - 0 . 5 0 . 3. 0 0 . 0 0 3
ph o sph ate I
6 " 6. 0 So dium tripo l y - 0 . 0 5 " 3. 0 0 . 0 4 0
ph o sph ate
3,9 9 6,29 8
Tab l e 4 ~ c o ntinued
( 4 1 g l y tj g So l utio n ' '
SW Smh j l izgr
Co nc en- Co nc en- D ec o mpo
tratio n tratio n sitio n
Run No . Catal y st (gl l ) Ty pe (g/ l ) pH ( VI/ h r. )
7 " 6. 0 ED TA-ZK 0 . 2 3. 0 0 . 0 5 4
8 " 6. 0 NTA 0 . 2 3. 0 0 . 0 60
No te
Run No s. 1 and 2 are Co ntro l s.
' ED TAQK stands f o r " r sal t o f c th y " ieu ' ac id.
" NTA stands f o r nitril o triac etic ac id.
Tab l e 5
Catal y tic So l utio n Resul ts
Stab il iger Al c o h o l
SW Co n- Co nc en- Reac tio n Co nditio ns Co nc en
c entratio n tratio n Temp. Pressure Time tratio n Sel ec tiv ity
Run No . (g/ l ) Ty pe (g/ l ) pH ( C. ) (kg/ c m G) (h r. ) (w t. %) (%)
l 3. 0 So dium tri- 0 . 3 3. 0 230 20 0 l 8. 0 9 9
po l y ph o sph ate
2 6. 0 " 0 . 5 3. 0 230 20 0 l 8. 0 9 9
3 6. 0 " 0 . 0 5 3. 0 230 20 0 l l 1 . 5 9 9
4 6. 0 Orth o ph o s~ 0 . 2 3. 0 230 20 0 l 9 . 2 9 9
ph o ric ac id
5 6. 0 ED TA 0 . 25 3. 0 230 20 0 l 8. 0 9 9
6 6. 0 - 3. 0 230 20 0 l 8. 0 9 9
Fo r c o m ariso n th e resul ts o f th e run in w h ic h no
EXAMPLE 6 p
c atal y st stab il izer w as added to th e c atal y tic so l utio n
Th e c atal y tic so l utio n c o ntaining sil ic o tungstic ac id 30 are c o nc urrentl y giv en in Tab l e 6 (Run No . 1 ).
io ns in a c o nc entratio n o f 6 g / l iter, and eith er so dium
tripo l y ph o sph ate o r diso dium eth y l enediaminetetra
ac etate (ED TA-ZNA) at th e c o nc entratio n spec i? ed in
Fro m th e same tab l e, it is apparent th at th e c atal y st
stab il izers ef f ec tiv el y pro mo te th e durab il ity o f th e
o l e? n-h y drating ac tiv ity o f th e c atal y st.
Tab l e 6
5 3mm ; So l utio n initial Perio d o f Reac tio n Af ter 5 0 0 Ho urs Reac tio n
Sta b il j ggr IPA IPA
Co nc en- C' s Co n- Co nc en- Sel ec - C' n Co n- Co nc en- Sel ec ~
Run tratio n v ersio n tratio n tiv ity S. T. Y. v ersio n tratio n tiv ity S. T. Y.
No . Ty pe (g/ l ) pH ( 7 %) (w t. %) ( C) (kg/ kg. c at. h r. ) (' 7 ! ) (w t. 7 1 ) (9 ? ) (kg/ kg. c at. h r. )
1 -- - 3. 0 7 | 8. 7 9 9 29 . 0 66 8. 5 9 9 27 . 2
(Co ntro l )
2 So dium ' 0 . 2 3. 0 7 0 8. 6 9 9 28. 7 69 8. 6 9 9 28. 7
tripo l y
ph o sph ate
3 " 0 . 0 5 3. 0 7 2 8. 7 9 9 29 . 2 7 1 8. 7 9 9 29 . 0
4 ED TA-ZNa 0 . 25 3. 0 7 0 8. 5 9 9 28. 6 7 0 8. 5 9 9 28. 5
and w ith th e H3. 0 ad' usted w ith NaOH w as
Tab l e 6 p J EXAMPLE 7
intro duc ed into a stainl ess ste ei, tub ul ar h igh pressure
reac to r f ro m th e upper part th ereo f , at a rate o f 3 kg/ h r.
per l iter o f th e reac to r s c apac ity . Simul taneo usl y , pro 5 0
py l ene (C' _ ,) w as into duc ed into th e reac to r f ro m th e
b o tto m part, at a rate o f 0 . 26 kg/ h r. Th us th e c o ntinu
o us h y dratio n o f pro py l ene w as perf o rmed at 280 C.
and 25 0 kg/ c m2G. Th e reac tio
f ro m th e b o tto m part o f th e reac to r as a mixture o f th e
n pro duc t w as w ith draw n
5 5
c atal y st aqueo us so l utio n w ith th e pro duc t. Sub se
quentl y , th e iso pro pano l pro duc ed w as separated f ro m
th e c atal y tic so l utio n b y distil l atio n, th e l atter b eing
rec irc ul ated into th e reac to r.
f ree iro n io ns at a c o nc entratio n no t h igh er th an 8 ppm.
Th e so l utio n c o ntained
60
Th e av erage o ne-pass c o nv ersio n o f pro py l ene, iso
pro pano l (IPA) c o nc entratio n, S. T. Y. , and sel ec tiv ity ,
o f th e initial 24 h o urs o f o pe ratio n w ere as sh o w n in
Tab l e 6. Th e h y dratio n w as c o ntinued f o r 5 0 0 h o urs,
w ith o ut f resh suppl y o f th e c at
age o ne-pass c o nv ersio n o f
c o nc entratio n, S. T. Y. , and se
o f o peratio n are al so giv en in
al y tic so l utio n. Th e av er- 65
pro py l ene, iso pro pano l
l ec tiv ity af ter 5 0 0 h o urs
Tab l e 6.
Catal y tic so l utio ns eac h c o ntaining sil ic o tungstic
ac id io ns (SW) b o ro tungstic ac id io ns (BW), ph o sph o
tungstic ac id io ns (PW) sil ic o mo l y b dic ac id io ns (SM)
o r ph o sph o mo l y b dic ac id io ns (PM) at in al l c ases a
c o nc entratio n o f 3 g/ l iter, and 0 . 0 5 g/ l iter o f o rth o
ph o sph o ric ac id eac h h ad th eir pH adj usted to 3 3. 3
w ith NaOH. Using th e reac to r empl o y ed in Exampl e 6,
th e c atal y tic so l utio n w as intro duc ed at a rate o f 3
kg/ h r. per l iter o f th e reac to r s c apac ity , and eth y l ene
w as intro duc ed f ro m th e upper part o f th e reac to r at a
rate o f 0 . 28 kg/ h r. Th e l iquid disc h arge w as separated
into th e al c o h o l f o rmed and th e aqueo us so l utio n o f
c atal y st, th e l atter b eing rec irc ul ated into th e reac to r as
it w as. Th e h y dratio n reac tio n w as c o ntinued f o r 5 0 0
h o urs, at 30 0 C. and 280 kg/ c mZG. In th is Exampl e,
o rth o -ph o sph o ric ac id in an amo unt equiv al ent to th at
initial l y used w as f resh l y added to th e so l utio n af ter 20 0
h o urs o f o peratio n. Th e f ree iro n io n c o nc entratio n in
th e so l utio n w as th us kept b el o w 1 0 ppm th ro ugh o ut
th e c o ntinuo us o peratio n. Th e av erage eth y l ene c o n
3,9 9 6,29 8
1 1
v ersio n and sel ec tiv ity f o r eth ano l f o r th e initial 8 h o urs
o f o peratio n, and th o se o f th e l ast 8 h o urs, w ere as
sh o w n in Tab l e 7 . Th e resul ts o f th e runs using no
o rth o -ph o sph o ric ac id are al so giv en c o nc urrentl y . In
th e Co ntro l runs, th e iro n io n c o nc entratio n reac h ed 1 8
20 ppm.
5
1 2
th e f o rmed mo no h y dric al c o h o l , and treating said re
c o v ered h etero po l y -ac id io n-c o ntaining aqueo us so l u
tio n w ith a c atio n exc h anger to separate and remo v e
th e f ree iro n io ns c o ntained in said so l utio n, and th ere
af ter rec y c l ing said aqueo us so l utio n f ro m w h ic h th e
f ree iro n io ns h av e b een remo v ed to th e h y dratio n
Tab l e 7
Initial 8 Ho urs Last 8 Ho urs
Co nv ersio n Sel ec tiv ity Co nv ersio n Sel ec tiv ity
tgb il ig r - Stab il izer stgb il iggr Stab il izer
Catal y st No t No t No t No t
Io n Added Added Added Added Added Added Added Added
SW 62 62 9 9 9 9 61 5 3 9 9 9 9
BW 62 62 9 9 9 9 6O 5 2 9 8 9 9
PW 5 8 5 7 9 9 9 9 S6 4 7 9 8 9 9
SM 5 9 5 9 9 8 9 8 5 6 5 0 9 7 9 8
PM 5 6 5 5 9 8 9 8 5 4 4 1 9 8 9 8
We c l aim:
1 . In a pro c ess f o r th e preparatio n o f mo no h y dric
al c o h o l s b y c o ntac ting a mo no -o l e? n o f 2-4 c arb o n
ato ms w ith an aqueo us so l utio n c o ntaining h etero po l y
ac id io ns sel ec ted f ro m th e gro up c o nsisting o f b o ro
tungstic ac id io ns, ph o sph o tungstic ac id io ns, sil ic o
tungstic ac id io ns, sil ic o mo l y b dic ac id io ns and ph o s
ph o mo l y b dic ac id io ns in a c o nc entratio n o f l / 4 0 ,0 0 0
to H30 0 mo l per l iter and at a pH ranging f ro m 2. 0 to
4 . 5 in th e l iquid ph ase at a pressure w ith in th e range o f
1 0 0 -5 0 0 Kgl c mzG and at a temperature w ith in th e
range o f l 5 0 -37 0 C, th ereb y to sub j ec t th e o l e? n to
h y dratio n reac tio n, th e impro v ement c o mprising main
taining th e f ree iro n io n c o nc entratio n o f said aqueo us
so l utio n at no t h igh er th an 1 0 ppm sub stantial l y
th ro ugh o ut th e w h o l e h y dratio n reac tio n perio d b y
perf o rming said h y dratio n reac tio n in a reac tio n v essel
o f w h ic h at l east th e internal surf ac e is c o nstruc ted o f a
metal sel ec ted f ro m th e gro up c o nsisting o f nic kel ,
c h ro mium, titanium,' zirc o nium, tantal um, sil v er, go l d
and pl atinum.
2. In a pro c ess f o r th e preparatio n o f mo no h y dric
al c o h o l s b y c o ntac ting a mo no -o l e? n o f 2-4 c arb o n
ato ms w ith an aqueo us so l utio n c o ntaining h etero po l y
ac id io ns sel ec ted f ro m th e gro up c o nsisting o f b o ro
tungstic ac id io ns, ph o sph o tungstic ac id io ns, sil ic o
tungstic ac id io ns, sil ic o mo l y b dic ac id io ns and ph o s
ph o mo l y b dic ac id io ns in a c o nc entratio n o f l / 4 0 ,0 0 0
to H30 0 mo l per l iter and at a pH ranging f ro m 2. 0 to
20
25
35
4 0
4 5
4 . 5 in th e l iquid ph ase at a pressure w ith in th e range o f -
1 0 0 -5 0 0 Kg/ c m G and at a temperature w ith in th e
range o f ISO-37 0 C, th ereb y to sub j ec t th e o l ef in to
h y dratio n reac tio n, th e impro v ement c o mprising main
taining th e f ree iro n io n c o nc entratio n o f said aqueo us
so l utio n at no t h igh er th an 1 0 ppm sub stantial l y
th ro ugh o ut th e w h o l e h y dratio n reac tio n perio d b y
rec o v ering th e h etero po l y -ac id io n-c o ntaining aqueo us
so l utio n f ro m th e reac tio n mixture c o ntaining th e
h etero po l y -ac id io n-c o ntaining aqueo us so l utio n and
5 0
5 5
60
65
reac tio n sy stem.
3. In a pro c ess f o r th e preparatio n o f mo no h y dric
al c o h o l s b y c o ntac ting a mo no -o l ef in o f 2-4 c arb o n
ato ms w ith an aqueo us so l utio n c o ntaining h etero po l y
ac id io ns sel ec ted f ro m th e gro up c o nsisting o f b o ro
tungstic ac id io ns, ph o sph o tungstic ac id io ns, sil ic o
tungstic ac id io ns, sil ic o mo l y b dic ac id io ns and ph o s
ph o mo l y b dic ac id io ns in a c o nc entratio n o f l / 4 0 ,0 0 0
to H30 0 mo l per l iter and at a pH ranging f ro m 2. 0 to
4 . 5 in th e l iquid ph ase at a pressure w ith in th e range o f
1 0 0 -5 0 0 Kgl c mzG and at a temperature w ith in th e
range o f ISO-37 0 C, th ereb y to sub j ec t th e o l e? n to
h y dratio n reac tio n, th e impro v ement c o mprising main
taining th e f ree iro n io n c o nc entratio n o f said aqueo us
so l utio n at no t h igh er th an 1 0 ppm sub stantial l y
th ro ugh o ut th e w h o l e h y dratio n reac tio n perio d b y
adding to said aqueo us so l utio n a stab il izer w h ic h c an
f o rm a c h el ate c o mpo und w ith th e f ree iro n io ns in said
aqueo us so l utio n. ,
4 . In a pro c ess f o r th e preparatio n-o f mo no h y dric
al c o h o l s b y c o ntac ting a mo no -o l ef in o f 2-4 c arb o n
ato ms w ith an aqueo us so l utio n c o ntaining h etero po l y
ac id io ns sel ec ted f ro m th e gro up c o nsisting o f b o ro
tungstic ac id io ns, ph o sph o tungstic ac id io ns, sil ic o n
tungstic ac id io ns, sil ic o mo l y b dic ac id io ns and ph o s
ph o mo l y b dic ac id io ns in a c o nc entratio n o f l / 4 0 ,0 0 0
to l / 30 0 mo l per l iter and at a pH ranging f ro m 2. 0 to
4 . 5 in th e l iquid ph ase at a pressure w ith in th e range o f
l 0 0 -5 0 0 Kgl c mzG and at a temperature w ith in th e
range o f ISO-37 0 C, th ereb y to sub j ec t th e o l ef in to
h y dratio n reac tio n, th e impro v ement c o mprising main
taining th e f ree iro n io n c o nc entratio n o f said aqueo us
so l utio n at no t h igh er th an 1 0 ppm sub stantial l y
th ro ugh o ut th e w h o l e h y dratio n reac tio n perio d b y
perf o rming th e h y dratio n reac tio n in a reac to r o f w h ic h
at l east th e internal surf ac es are c o mpo sed o f no n-f er
ro us metal w h ic h is no n-c o rro siv e to said aqueo us so l u
tio n.
* * * * *
UNITED STATES PATENT AND TRAD EMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT NO. 1 3,9 9 6,29 8
D ATED 3 D ec emb er 7 , 1 9 7 6
|NVENTOR(5 ) : IZUMI, ET AL.
It is c erti? edth at erro r appears in th e ab o v e-t-identif ied patent and th at said Letters Patent
are h ereb y c o rrec ted as sh o w n b el o w :
Item 7 3, l ine 2, b ef o re " Japan" insert - Yamaguc h i-Ken -.
Signed and Seal ed th is
Fif th D ay o f April 1 9 7 7
[ SEAL]
Arrest:
RUTH C. MASON C. MARSHALL D ANN
Arresting Of f ic er Co mmissio ner o f Parents and Trademarks