United States Patent [ 1 9 1

Eek
US005741 9 56A
5, 741 , 9 56
Ap r . 2 1 , 1 9 9 8
[ 1 1 ] Patent Number :
[ 45] Date o f Patent:
[ 54] PROCESS FOR THE PREPARATION OF
PENTAERYTHRITOL
[ 75] Inv ento r : Ll uis Eek. B ar c el o na. Sp ain
[ 73 ] Assig nee: Patentes y No v edades. B ar c el o na.
Sp ain
[ 2 1 ] Ap p l . No . : 756, 3 40
[ 2 2 ] Fil ed: No v . 2 6, 1 9 9 6
[ 3 0] Fo r eig n Ap p l ic atio n Pr io r ity Data
May 2 2 , 1 9 9 6 [ ES] Sp ain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 601 1 2 9
[ 51 ] Int. Cl . 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C07C 2 9 /2 0
[ 52 ] US. Cl . 568 /8 53
[ 58 ] Fiel d o f Sear c h . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 568 /8 44. 8 53 .
568 /8 54
[ 56] Ref er enc es Cited
U. S. PATENT DOCUMENTS
4/1 9 57 Mitc hel l et a] . ,
4/1 9 61 Po y nto n .
8 /1 9 76 Pal mer et al l .
4/1 9 78 Lee.
8 /1 9 78 Ec kl er .
7/1 9 8 1 Gup to n et al . .
5/1 9 8 2 Winsl o w, J r . et a1 . .
9 /1 9 8 6 Gup to n et a1 . .
2 , 79 0, 8 3 6
2 , 9 78 , 51 4
3 , 9 75, 450
4, 08 3 , 9 3 1
4, 1 05, 575
4, 2 77, 62 0
4, 3 2 8 , 3 66
4, 61 2 , 3 8 9
FOREIGN PATENT DOCUMENTS
62 68 04 1 /1 9 62
2 61 8 43 7/1 9 8 8
1 1 62 8 2 4 l /l 9 62
l 9 1 0 057 3 /1 9 68
79 9 1 8 2 1 /1 9 57 United King do m .
9 58 654 1 2 /1 9 59 United King do m .
Pr imar y Ex aminer - Gar y Geist
Assistant Ex aminer - Kar l Puttl itz
Atto r ney , Ag ent, o r Fir m- Staas & Hal sey
[ 57] AB STRACT
B el g ium .
Cz ec ho sl o v akia .
Ger many .
Ger many .
A p r o c ess f o r the p r ep ar atio n o f p entaer y thr ito l . c o mp r ising
r eac ting f o r mal dehy de, ac etal dehy de and so dium hy dr o x ide
and ac idi? c atio n with f o r mic ac id. These step s take p l ac e in
a r eac to r with sup p l ies o f f o r mal dehy de. so dium hy dr o x ide.
ac etal dehy de and f o r mic ac id and at the end the so l utio n
f o r med is ev ac uated to a buf f er tank o f l ar g er c ap ac ity than
the r eac to r . In the r eac to r new r eac tio ns and ac idi? c atio ns
ar e suc c essiv el y r einin' ated by new sup p l ies. In the ? r st p l ac e
a f o r mal dehy de so l utio n is added. f o l l o wed by simul taneo us
but sep ar ate additio ns o f so dium hy dr o x ide so l utio n and
ac etal dehy de. f o r ming a r eac tio n mix tur e in suc h a way that
the ? o wr ates o f the so l utio ns v ar y with the time and that the
temp er atur e at whic h the r eac tio ns ar e c o nduc ted al so v ar ies
with the time. The o ut? o w f r o m the buf f er tank is c o nstant
and c o ntinuo us.
1 1 Cl aims, N0 Dr awing s
5. 741 . 9 56
l
PROCESS FOR THE PREPARATION OF
PENTAERYTH RITOL
FIELD OF THE INVENTION
This inv entio n c o nc er ns a p r o c ess f o r the p r ep ar atio n o f
p entaer y thr ito l . c o mp r ising the initial step s o f : [ a] r eac ting
f o r mal dehy de with ac etal dehy de. to g iv e p entac r y thn' to se;
and subseq uent r eac tio n o f the p entaer y thr ito se with f o r m
al dehy de and so dium hy dr o x ide. to g iv e a so l utio n c o ntain
ing p entaer y thr ito l ; and [ b] ac idi? c atio n o f said
p entaer y thr ito l - c o ntaining so l utio n with f o r mic ac id; said
step s [ a] and [ b] being c o nduc ted in a r eac to r . with the
sup p l y o f f o r mal dehy de ( CHZ O) . so dium hy dr o x ide
( NaOH) . ac etal dehy de ( Ac H) and f o r mic ac id ( HCOOH)
and at the end o f said step s the f o r med p entaer y thr ito l
c o ntaining so l utio n being dr ained to a buf f er tank o f a
c ap ac ity g r eater than that o f the r eac to r . new r eac tio ns and
a new ac idi? c atio n o p er atio n being suc c essiv el y r einitiated
in said r eac to r by f r esh sup p l ies.
The manuf ac tur e o f p entaer y thr ito l has been kno wn f o r
many y ear s and. as stated in the abo v e p ar ag r ap h. is based
o n the r eac tio n o f f o r mal dehy de with ac etal dehy de in a basic
medium. The f o r mate c o r r esp o nding to the base used is
o btained in the p r o c ess. As al kal ine ag ents. basic al l y used
ar e c al c ium hy dr o x ide and so dium hy dr o x ide. the l atter
being the o ne used in the p r esent p r o c ess.
PRIOR ART REFERENCE
A number o f side r eac tio ns g iv ing r ise to many
by - p r o duc ts o c c ur in the p entaer y thr ito l manuf ac tur ing p r o
c ess. Thus. in the basic medium used. v ar io us p entaer y thr ito l
f o r r nal s ar e f o r med. mainl y the c y c l ic mo no f o r mal ( kno wn
as CMF) and the l inear mo no f o r mal ( kno wn as PMF) . the
amo unt ther eo f being l ar g er the g r eater is the ex c ess o f
f o r mal dehy de r el ativ e to the ac etal dehy de used in the r eac
tio n. Al so f o r med ar e dip entaer y thr ito l . tr ip entaer y thr ito l
and p o l ip entaer y thr ito l s in g ener al . the p r o p o r tio ns o f whic h
in the r eac tio n l iq uo r ar e inc r eased if the p r o p o r tio n o f
f o r mal dehy de added r el ativ e to the ac etal dehy de is r educ ed.
Al so . in an al kal ine medium. the f o r mal dehy de auto c o n
denses f o r ming sug ar ty p e p o l y hy dr o x y l ated c o mp o unds.
g ener ic al l y kno wn as f o r mo ses. The ac etal dehy de al so p r o
duc es al do l ty p e c o ndensatio n p r o duc ts whic h may r eac t
bo th with themsel v es and with the o ther c o mp o unds in the
r eac tio n medium.
Al l these r eac tio ns sho w the c o mp l ex ity o f the p r o c ess
and ex p l ain the amo unt o f p ubl ished p atents r ef er r ing to the
way o f av o iding the ap p ear anc e o f these imp ur ities as f ar as
p o ssibl e. bo th to ac hiev e a better y iel d f r o m the main
r eac tio n o f p r o duc ing p entaer y thr ito l . and to ac hiev e a mo r e
e? ic ient sep ar atio n and o btain a p ur er p r o duc t.
The sy nthesis o f p entaer y thr ito l inv o l v es the r eac tio n o f
f o ur mo l es o f f o r mal dehy de and o ne mo l e o f ac etal dehy de.
The r eac tio n takes p l ac e in two dif f er entiated step s. The ? r st
at a p H o f f r o m 1 0 to 1 1 is an al do l c o ndensatio n. in whic h
thr ee mo l es o f f o r mal dehy de and o ne mo l e o f ac etal dehy de
ar e c o nsumed. to g iv e p entaer y thr ito se.
Ther eaf ter . the al dehy de o btained in the al do l c o ndensa
tio n is subj ec ted to a c r o ssed Canniz z ar o r eac tio n. at a p H o f
no t l ess than 9 . wher eby o ne mo l ec ul e o f the p entr aer y th
r ito se is r educ ed to p entaer y thr ito l . and ano ther o f f o r mal
dehy de is o x idiz ed to f o r mic ac id. whic h in the so dium
hy dr o x ide al kal ine medium g iv es the so dium f o r mate.
1 0
2 0
2 5
3 0
3 5
45
50
65
2
The temp er atur es at whic h these r eac tio ns ar e c o nduc ted
ar e f undamental .
The Canniz z ar o r eac tio n is sl o w at l o w temp er atur es o f
2 03 0 C. . whil e the al do l r eac tio n is f ast at these tem_
p er atur es. Fur ther mo r e. the Canniz z ar o r eac tio n is do minant
at 4060 C. . Ther ef o r e. the r eac tio n mix tur e temp er atur e
sho ul d o nl y be r aised af ter al l the ac etal dehy de has been
c o nsumed. To ac hiev e a g r eater ex tensio n o f the al do l iz atio n
r eac tio n ( 1 ) . an ex c ess o f f o r mal dehy de is used in the
so l utio n.
This f o r mal dehy de ex c ess has sp ec ial c o nno tatio ns.
Under the in? uenc e o f the al kal i. it under g o es the Canniz
z ar o r eac tio n to g iv e methano l and so dium f o r mate. wher eby
the so l utio n p H dr o p s and p r ev ents the r emaining r eac tants
f r o m adeq uatel y r eac ting . Or . if ther e is an ex c ess o f so dium
hy dr o x ide. auto c o ndensatio ns to g iv e f o r mo ses ar e c aused
Ev en wo r se. as said abo v e. the ex c ess o r de? c ienc y o f
f o r mal dehy de af f ec ts the p r esenc e o f hig her o r l o wer deg r ee
o f f o r r nal s o f the v ar io us p entaer y thr ito l s f o r med and a
smal l er o r l ar g er p r o p o r tio n o f these same p entaer y thr ito l s
( d. i- . tr i- and p o l ip entaer y thr ito l ) .
Al l these r eac tio ns dep end o n the temp er atur e. p H and
r eac tio n time and o n the c o nc entr atio n. amo unt and
seq uenc e in whic h the r eac tants ar e added. wher eby c o m
p r o mise c o nditio ns al l o wing f o r hig h y iel ds o f p entaer y th
r ito l with the l east p o ssibl e amo unt o f imp ur ities hav e to be
f o und.
B r itish p atent GB 9 58 . 654 ex p l ains the in? uenc e o f the
temp er atur e and time o f the dif f er ent r eac tio ns. as wel l as o f
the ex c ess f o r mal dehy de used and desc r ibes a c o ntinuo us
p r o c ess in sev er al step s.
Fr enc h p atent FR 2 . 43 2 . 49 3 disc l o ses a v er tic al r eac to r
div ided into v ar io us stag es o p er ating c o ntinuo usl y wher ein
eac h stag e is at a dif f er ent temp er atur e and with dif f er ent
mo l ar p r o p o r tio ns o f so dium hy dr o x ide. f o r mal dehy de and
ac etal dehy de.
In o ther p atents the use is disc l o sed o f v ar io us r eac to r s in
ser ies. suc h as f o r ex amp l e Ger man p atent DE 1 . 9 1 0. 057
whic h uses sev en r eac to r s in c asc ade and in eac h o f whic h.
v ar iabl e amo unts o f ac etal dehy de ar e added to an initial
f o r mal dehy de and so dium hy dr o x ide so l utio n. A simil ar
sy stem is used in do c ument CS 2 61 . 8 43 .
Al l these p atents. whic h hav e imp r o v ed the p r o duc tio n
y iel ds o f p entaer y thr ito l o v er the ear l ier p atents. disc l o se
p r o c esses in whic h the r eac tio n is c o nduc ted c o ntinuo usl y .
either in sev er al r eac to r s in c asc ade o r in tubul ar r eac to r s.
Co ntinuo us o p er atio n has its adv antag es. but al so its
dr awbac ks. Amo ng the l atter ther e may be c ited the dif f ic ul ty
o f g etting the r eac tants to mix su? ic ientl y q uic kl y . and the
subseq uent c o o l ing . sinc e. o ther wise. undesir abl e c o l o ur ed
p r o duc ts ar e f o r med as a r esul t o f the r eac tio n being hig hl y
ex o ther mal .
Fur ther mo r e. if sev er al r eac to r s ar e used. the p r o c ess
bec o mes mo r e ex p ensiv e and if the tubul ar r eac to r is used.
it must be v er y l o ng . Tubes 9 5 m l o ng ar e disc l o sed in the
p atents ( GB 9 58 . 654) . This is so . bec ause a c er tain dwel l
time is r eq uir ed in the r eac to r . to g ether with a hig h l iq uid
? o wr ate ther ein. To ac hiev e the mix tur e as q uic kl y as
p o ssibl e. the r eac to r diameter mu st be smal l and. ther ef o r e.
it must hav e a substantial l eng th and this makes temp er atur e
c o ntr o l in the v ar io us r eac to r p o r tio ns di? ic ul t.
Other step s o f the kno wn p r o c esses ar e desc r ibed in
v ar io us p ubl ic atio ns. Thus. it is desc r ibed that o nc e the
r eac tio n has taken p l ac e in the c o ntinuo us r eac to r o r
r eac to r s. the r esul ting mix tur e is sl ig htl y ac idi? ed either
with ac etic ac id ( US. Pat. No . 2 . 79 0. 8 3 6. US. Pat. No .
5. 741 . 9 56
3
2 . 9 78 . 51 4) o r with f o r mic ac id ( B E 62 6. 8 04. DE 1 . 1 62 . 8 2 4) .
Ther eaf ter . the ex c ess f o r mal dehy de is r emo v ed by steam
entr ainment distil l atio n ( US. Pat. No . 2 . 79 0. 8 3 6. US. Pat.
No . 2 . 9 78 . 51 4) and the r esul ting f o r mal dehy de- f r ee so l utio n
is ev ap o r ated under v ac uum to a c o nc entr atio n suc h that the
p entaer y thr ito l p r ec ip itates in p ar t. but no t the so dium f o r
r nate. Ther eaf ter the p r ec ip itated p entaer y thr ito l is sep ar ated
f r o m the r est o f the so l utio n. either by c entr if ug atio n o r by
? l tr atio n. Af ter washing . the so l id is f o r med by
p entaer y thr ito l . p entadier y thr ito l and p o l y p entaer y thr ito l s.
l inear f o r mal ( PMF) . tr ac es o f so dium f o r mate and o ther
imp ur ities and f o r ms the so - c al l ed r aw p entaer y thr ito l . The
? l ter ed so l utio n c o ntains the so dium f o r mate. the p en
taer y thr ito l whic h is so l ubl e under the wo r king c o nditio ns.
the CMF and the r emaining imp ur ities o r f o r mo ses. This
so l utio n is sent to the so dium f o r mate r ec o v er y . either by
c r y stal l iz atio n. by c o o l ing o r by ev ap o r atio n. The r aw p en
taer y thr ito l is r edisso l v ed and subj ec ted to hig h- temp er atur e
ac id hy dr o l y sis ( US. Pat. No . 2 . 9 78 . 51 4) . GB 79 9 . 1 8 2 . GB
9 58 . 654) af ter whic h the r esul ting so l utio n is p ur i? ed by
p assing it thr o ug h an ac tiv ated c ar bo n bed. dec o l o ur ing it.
The p ur i? ed p entaer y thr ito l so l utio n is tr ansf er r ed to the
ev ap o r ato r - c r y stal l iz er s wher e the so l utio n is c o nc entr ated.
The c r y stal susp ensio n is ? l ter ed o r c entr if ug ed by kno wn
tec hniq ues.
Residual so l utio ns ar e p r o duc ed in eac h o f the abo v e
desc r ibed step s and bene? c ial use ther eo f is f undamental f o r
o btaining an ec o no mic al l y p r o ? tabl e y iel d.
On the o ther hand. the imp ur ities p r o duc ed in the r eac tio n
must be r emo v ed f r o m the sy stem thr o ug h a l iq uid f l o w
kno wn as waste l iq uo r .
Nev er thel ess. these p r o c esses hav e dr awbac ks. sinc e the
waste l iq uo r is ac c o mp anied by a c er tain amo unt o f v al uabl e
p r o duc ts whic h it is wanted to o btain ( p entaer y thr ito l and
so dium f o r mate) . wher eby the ? nished p r o duc t y iel d is
r educ ed if they ar e no t r ec o v er ed. The l iter atur e c o ntains
v ar io us p atents study ing r ec o v er y p r o c esses o f these v al u
abl e p r o duc ts f r o m the waste l iq uo r ( f o r ex amp l e US. Pat.
No . 4. 08 3 . 9 3 1 . US. Pat. No . 4. 1 05. 575. US. Pat. No .
4. 2 77. 62 0. US. Pat. No . 4. 3 2 8 . 3 66) . This r ec o v er y inv o l v es
a number o f additio nal o p er atio ns f o r whic h eq uip ment and
r eag ents making the p r o c ess mo r e ex p ensiv e ar e r eq uir ed
The ex c ess waste l iq uo r ? nal l y has to be subj ec ted to a
bio l o g ic al tr eatment to destr o y the o r g anic matter .
SUMMARY OF THE INVENTION
It is an aim o f the inv entio n to o v er c o me the abo v e
mentio ned dr awbac ks. and to r educ e to a minimum the
ex p ense o f the abo v e tr eatments. to whic h end the p r o p o r tio n
o f waste l iq uo r p r o duc ed in the p l ant is r educ ed to the
smal l est p o ssibl e amo unt. This is. as said abo v e. o ne o f the
aims o f the inv entio n and is ac hiev ed basic al l y by r educ ing
the p r o duc tio n o f by - p r o duc ts dur ing the r eac tio n.
These aims ar e ac hiev ed by means o f a p r o c ess o f the ty p e
desc r ibed in the ? r st p ar ag r ap h o f this desc r ip tio n and whic h
is c har ac ter iz ed in that. in the ? r st p l ac e. a f o r mal dehy de
so l utio n and ther eaf ter . simul taneo usl y but sep ar atel y . a
so dium hy dr o x ide so l utio n and ac etal dehy de ar e sup p l ied.
f o r ming a r eac tio n mix tur e and bec ause the ex it ? o w f r o m
the said buf f er tank is substantial l y c o nstant and c o ntinuo us.
Ac c o r ding to the inv entio n. it has sur p r ising l y been seen
that if the NaOH is added g r adual l y suc h that the p H o f the
r eac tio n mix tur e o f the aq ueo us f o r mal dehy de so l utio n and
the ac etal dehy de is hel d at al l times between 1 0 and 1 1 . the
temp er atur e v ar ies with the el ap sed time and the ac etal de
hy de ? o wr ate al so v ar ies with the time. the amo unts o f
sec o ndar y c o mp o unds o f the r eac tio n ar e r educ ed by 2 0 to
40% o v er the c o nv entio nal p r o c esses.
1 0
2 5
3 0
3 5
45
50
55
65
4
In a p r ef er r ed embo diment o f the inv entio n the ? o wr ate o f
the said so dium hy dr o x ide so l utio n sup p l y is subj ec t at l east
to a v ar iatio n and al so the ac etal dehy de sup p l y ? o wr ate is
subj ec t at l east to a v ar iatio n.
The v ar iatio n o f eac h o f said ? o wr ates may take p l ac e
either substantial l y c o ntinuo usl y o r deter mine at l east two
p er io ds o f dif f er ent ? o wr ates. the ? o wr ates being hel d
substantial l y c o nstant dur ing eac h o f said p er io ds.
The inv entio n al so c o ntemp l ates that the temp er atur e at
whic h the r eac tio ns ar e c o nduc ted be v ar iabl e and that this
v ar iatio n be substantial l y c o ntinuo us. This v ar iabil ity may
be deter mined by at l east two p er io ds at di? er ent temp er a
tur es.
Ac c o r ding to ano ther f eatur e o f the inv entio n. at the star t
o f the r eac tio ns. the temp er atur e is hel d in the r ang e o f 2 0
to 3 8 C. . whil e at the end o f the r eac tio ns the temp er atur e
is hel d in the r ang e o f 42 to 48 C.
Al so ac c o r ding to the inv entio n. the c o nc entr atio n o f the
f o r mal dehy de so l utio n is in the r ang e o f 2 0 to 3 0 wt %. the
c o nc entr atio n o f the so dium hy dr o x ide so l utio n is in the
r ang e o f 1 2 to 2 0 wt % and the ac etal dehy de is substantial l y
p ur e. The mo l ar p r o p o r tio ns CH2 O/NaOH/Ac H ar e in the
r ang e o f 5. 1 - 9 . 5/ 1 . 05- 1 . 4/ 1 . 0.
In a p r ef er r ed embo diment o f the inv entio n. the suc c es
siv e sup p l ies to the r eac to r c o mp r ise: a ? r st p er io d in whic h
substantial l y hal f o f the v o l umes is sup p l ied. the temp er atur e
being hel d within the r ang e o f 2 2 to 2 8 C. ; a sec o nd p er io d
in whic h substantial l y o ne f o ur th p ar t o f the v o l umes is
sup p l ied. the temp er atur e being hel d within the r ang e o f 3 2
to 3 8 C. . the dur atio n o f said sec o nd p er io d being substan
tial l y the same as that o f the ? r st p er io d; and a thir d p er io d
in whic h the sup p l ies to the r eac to r ar e c o mp l eted. the
temp er atur e being hel d within the r ang e o f 42 to 48 C. . the
dur atio n o f said thir d p er io d being g r eater than that o f the
sec o nd p er io d.
Onc e the r eac tio n has ended. the r esul ting so l utio n is
ac idi? ed. Ther eaf ter the v o l atil e c o mp o unds. f o r mal dehy de
and methano l . ar e r emo v ed entr ained by steam. the so l utio n
is c o nc entr ated by ev ap o r atio n under v ac uum and the ? r st
susp ensio n o btained is f il ter ed by kno wn tec hniq ues.
The so l id o btained. p entaer y thr ito l . dip entaer y thr ito l and
f o r mal s. is disso l v ed in the mo ther l iq uo r s o f the ? l tr atio n o f
the so l ids o btained in the subseq uent c r y stal l iz atio ns o f
p r ep ar atio n o f the p entaer y thr ito l . a mix tur e o f ap p r o x i
matel y 8 6- 9 0% o f mo no p entaer y thr ito l and 1 0- 1 4% o f
dip entaer y thr ito l . This so l utio n o f p entaer y thr ito l and f o r
mal s is hy dr o l y z ed in an ac id medium ac c o r ding to c o nv en
tio nal p r o c edur es and is then p ur i? ed with ac tiv ated c ar bo n
and suitabl y c o nc entr ated and c r y stal l iz ed
Dep ending o n the q ual ity desir ed. the r eac tio n is c o n
duc ted in o ne way o r ano ther to o btain either a sing l e q ual ity
o f mo no p entaer y thr ito l o f 9 49 7. 7% p ur ity o r two dif f er en
tiated q ual ities. o ne o f 9 8 % mo no p entaer y thn' to l and the
o ther kno wn as tec hnic al p enta c o ntaining f r o m 8 6- 9 0%
o f mo no p entaer y thr ito l and 1 0- 1 4% o f dip entaer y thr ito l .
The so dium f o r mate o btained simul taneo usl y with the
p entaer y thr ito l in the r eac tio n is p r o duc ed by c o nc entr atio n
and c r y stal l iz atio n o f the ? l tr ate o f the ? r st susp ensio n
ac c o r ding to c o nv entio nal p r o c edur es.
The inv entio n al so c o ntemp l ates that the hy dr o l y sis o f the
f o r mal s may be c ar r ied o ut p r io r to the c o nc entr atio n o f the
r eac tio n so l utio n.
Onc e the additio n o f r eac tants has ended. it is desir abl e to
ho l d the mix tur e at a temp er atur e o f 45+ f o r a time. to
make sur e that the r eac tio n is c o mp l ete. Ther eaf ter . it is
5. 741 . 9 56
5
ac idi? ed with f o r mic ac id at p H 5- 6 to av o id subseq uent
undesir abl e r eac tio ns and is ev ac uated to a tank f r o m whic h
the p r o c ess is c ar r ied o ut c o ntinuo usl y .
Ex amp l es 1 and 2 ar e g iv en bel o w. c o r r esp o nding to the
p r o c ess o f the inv entio n and Ex amp l e 3 r el ating to a c o n
v entio nal p r o c ess. al l o wing c o mp ar iso ns to be establ ished.
EXAMPLE 1
To a r eac to r p r o v ided with stir r ing and a c o o l ing sy stem
to ho l d the adeq uate temp er atur e. ther e was added a 2 2 %
f o r mal dehy de so l utio n and then. sep ar atel y but
simul taneo usl y . a 1 6% NaOH so l utio n and the p ur e
ac etal dehy de. suc h that the p H was hel d al way s between
1 0- 1 1 . The ? o wr ate was suc h that hal f o f the r eac tants
sup p l y was ef f ec ted in 2 5 minutes and the temp er atur e was
hel d at 2 5 C. Ther eaf ter . the sup p l y ? o wr ate was v ar ied so
that hal f o f the r emaining sup p l y was c har g ed in a f ur ther 2 5
minutes. with the temp er atur e being al l o wed to r ise to 3 5 C.
Final l y . the r emaining sup p l y was added o v er 3 5 minutes
and the temp er atur e was c o ntr o l l ed so as no t to r ise abo v e
45 C. at the end o f the r eac tio n. The p r o p o r tio ns o f to tal
CH2 O/NaOH/Ao H added had the mo l ar r atio o f 5. 4/ 1 . 1 2 /1 .
Af ter the sup p l y had ter minated. the mix tur e was hel d f o r 1 0
minutes at 45 C. Ther eaf ter . the mix tur e was ac idi? ed with
f o r mic ac id to p H 5. 5 and ev ac uated f r o m the r eac to r to a
buf f er tank. f r o m whic h the p r o c ess bec ame c o ntinuo us. and
was subj ec ted to the p r o c esses o f r emo v al o f v o l atil e
c o mp o unds. c o nc entr atio n. ? l tr atio n. hy dr o l y sis. p ur i? c a
tio n and c r y stal l iz atio n. ac c o r ding to kno wn p r o c esses. as
desc r ibed her einbef o r e.
Tabl e 1 g iv es the initial c o nc entr atio ns o f the f o r mal de
hy de and so dium hy dr o x ide so l utio ns. as wel l as the c o n
c entr atio ns o f mo no p entaer y thr ito l . dip entaer y thr ito l and
imp ur ities p r esent in the r eac tio n l iq uo r at the end o f the
r eac tio n. The two p r o duc t q ual ities mentio ned abo v e. i. e.
o ne 9 8 % mo no p enta and the o ther 8 6- 9 0% mo no p enta and
1 01 4% dip entaer y thr ito l . wer e p r o duc ed f r o m that so l u
tio n.
The amo unt o f o r g anic imp ur ities f r o m whic h it was no t
p o ssibl e to r ec o v er p entaer y thr ito l was 3 . 1 % r el ativ e to the
p entaer y thr ito l o btained. whic h r ep r esents a 3 5% r educ tio n
o v er the c o nv entio nal p r o c ess.
EXAMPLE 2
To a r eac to r p r o v ided with stir r ing and a c o o l ing sy stem
to ho l d the adeq uate temp er atur e. ther e was added a 2 2 %
f o r mal dehy de so l utio n and then. sep ar atel y but
simul taneo usl y . a 1 6% NaOH so l utio n and the p ur e
ac etal dehy de. suc h that the p H was hel d al way s between
1 0- 1 1 . The ? o wr ate is suc h that hal f o f the r eac tants sup p l y
was ef f ec ted in 2 5 minutes and the temp er atur e was hel d at
2 5 C. Ther eaf ter . the sup p l y ? o wr ate was v ar ied so that hal f
o f the r emaining sup p l y was c har g ed in a f ur ther 2 5 minutes.
with the temp er atur e being al l o wed to r ise to 3 5 C. Final l y .
the r emaining sup p l y was added o v er 3 5 minutes and the
temp er atur e was c o ntr o l l ed so as no t to r ise abo v e 45 C. at
the end o f the r eac tio n. The p r o p o r tio ns o f to tal CH
2 O/NaOIr l /Ac H added had the mo l ar r atio o f 9 . 2 /1 . 1 /1 . Af ter
the sup p l y had ter minated. the mix tur e was hel d f o r 1 0
minutes at 45 C. Ther eaf ter . the mix tur e was ac idi? ed with
f o r mic ac id to p H 5. 5 and ev ac uated f r o m the r eac to r to a
buf f er tank. f r o m whic h the p r o c ess bec ame c o ntinuo us. and
was subj ec ted to the p r o c esses o f r emo v al o f v o l atil e
c o mp o unds. c o nc entr atio n. ? l tr atio n. hy dr o l y sis. p ur i? c a
tio n and c r y stal l iz atio n. ac c o r ding to kno wn p r o c esses. as
desc r ibed her einbef o r e.
2 5
3 0
3 5
45
50
55
65
6
Tabl e 1 g iv es the initial c o nc entr atio ns o f the f o r mal de
hy de and so dium hy dr o x ide so l utio ns. as wel l as the c o n
c entr atio ns o f mo no p entaer y thr ito l . dip entaer y thr ito l and
imp ur ities p r esent in the r eac tio n l iq uo r at the end o f the
r eac tio n. A sing l e q ual ity o f p entaer y thr ito l with a max imum
o f 2 . 3 % o f dip entaer y thr ito l . was p r o duc ed f r o m this so l u
tio n.
The amo unt o f o r g anic imp ur ities f r o m whic h it was no t
p o ssibl e to r ec o v er p entaer y thr ito l was 3 . 8 % r el ativ e to the
p entaer y thr ito l o btained. whic h r ep r esents a 2 1 % r educ tio n
o v er the c o nv entio nal p r o c ess.
EXAMPLE 3
To a r eac to r p r o v ided with stir r ing and a c o o l ing sy stem
to ho l d the adeq uate temp er atur e. ther e was added o n the o ne
hand a mix tur e o f a 2 2 % f o r mal dehy de ( CH2 O) so l utio n and
a 1 6% so dium hy dr o x ide ( NaOH) so l utio n and o n the o ther
the p ur e ac etal dehy de ( Ac H) . in amo unts suc h that the mo l ar
r atio CH2 O/NaOI- l /Ac H was 5. 4/1 . 1 5/1 . The ac etal dehy de
additio n o p er atio n l asted 50 minutes and the heating /c o o l ing
was c o ntr o l l ed suc h as to ho l d a max imum temp er atur e o f
46 C. Af ter ho l ding the mix tur e at this temp er atur e f o r a
f ur ther 1 0 minutes. it was ac idi? ed with f o r mic ac id to p H
5. 5. The r eac to r mix tur e was sent to a buf f er tank. f r o m
whic h the p r o c ess bec ame c o ntinuo us. and was subj ec ted to
the p r o c esses o f r emo v al o f v o l atil e c o mp o unds.
c o nc entr atio n. ? l tr atio n. hy dr o l y sis. p ur i? c atio n and
c r y stal l iz atio n. ac c o r ding to kno wn p r o c esses.
Tabl e 1 g iv es the initial c o nc entr atio ns o f the f o r mal de
hy de and so dium hy dr o x ide so l utio ns. as wel l as the c o n
c entr atio ns o f mo no p entaer y thr ito l . dip entaer y thr ito l and
imp ur ities p r esent in the r eac tio n l iq uo r at the end o f the
r eac tio n. B o th p r o duc t q ual ities i. e. o ne 9 8 % mo no p enta and
the o ther 8 69 0% mo no p enta and 1 0- 1 4% dip entaer y thn' to l .
wer e p r o duc ed f r o m that so l utio n.
The amo unt o f o r g anic imp ur ities f r o m whic h it was no t
p o ssibl e to r ec o v er p entaer y thr ito l was 4. 8 % r el ativ e to the
p entaer y thr ito l o btained.
TAB LE 1
PATENT YIELDS EX. 1 EX. 2 Ex . 3
Initial f o r mal dehy de 2 2 2 2 2 2
c o nc entr atio n
Initial so dium hy dr o x ide % 1 6 1 6 1 6
c o nc entr atio n
Fo nnal dehy de/ac etal dehy de 5. 4 9 . 2 5. 4
mo l ar r atio
So dium hy dr o x ide/ac etal dehy de 1 . 1 2 1 . 1 0 1 . 1 5
mo l e: r atio
Mo no p entaer y thr ito l % 9 . 56 6. 73 9 . 6
Dip entaer y thr ito l % 0. 69 0. 1 5 0. 41
DPFJ MPE + DPE 6. 7 2 . 2 4. 1
Imp ur ities % 3 . 1 3 . 8 4. 8
Dif f er enc e 1 . 7 1 0
Yiel d r el ativ e to ac etal dehy de % 8 0. 3 79 . 7 78 . 8
What I c l aim is:
1 . A p r o c ess f o r the p r ep ar atio n o f p entaer y thr ito l . c o m
p r ising the initial step s o f : l a] r eac ting f o r mal dehy de with
ac etal dehy de. to g iv e p entaer y thr ito se: and subseq uent r eac
tio n o f said p entaer y thr ito se with f o r mal dehy de and so dium
hy dr o x ide. to g iv e a so l utio n c o ntaining p entaer y thr ito l ' . and
[ bl ac idi? c atio n o f said p entaer y tl u' ito l - c o ntaining so l utio n
with f o r mic ac id; said step s [ a] and [ bl being c o nduc ted in
a r eac to r . with the sup p l y o f f o r mal dehy de ( CHZ O) . so dium
hy dr o x ide ( NaOH) . ac etal dehy de ( Ac H) and f o r mic ac id
( HCOOH) and at the end o f said step s the f o r med
5. 741 . 9 56
7
p entaer y thr ito l - c o ntaining so l utio n being dr ained to a buf f er
tank o f a c ap ac ity g r eater than that o f the r eac to r . new
r eac tio ns and a new ac idi? c atio n o p er atio n being suc c es
siv el y r einitiated in said r eac to r by f r esh sup p l ies. wher ein.
in the ? r st p l ac e. a f o r mal dehy de so l utio n and ther eaf ter .
simul taneo usl y but sep ar atel y . so dium hy dr o x ide so l utio n
and ao etal dehy de ar e sup p l ied. f o r ming a r eac tio n mix tur e
and bec ause the ex it ? o w f r o m the said butf er tank is
substantial l y c o nstant and c o ntinuo us.
2 . The p r o c ess o f c l aim 1 . wher ein the so dium hy dr o x ide
is added g r adual l y suc h that the p H o f said r eac tio n mix tur e
is hel d between 1 0 and 1 1 . and thr o ug ho ut the additio n the
temp er atur e and the ac etal dehy de ? o wr ate v ar y .
3 . The p r o c ess o f c l aim 1 . wher ein at l east o ne o f the
so dium hy dr o x ide sup p l y and ac etal dehy de sup p l y ? o wr ates
under g o es at l east o ne v ar iatio n.
4. The p r o c ess o f c l aim 3 . wher ein the v ar iatio n o f eac h
o f said ? o wr ates takes p l ac e substantial l y c o ntinuo usl y .
5. The p r o c ess o f c l aim 3 . wher ein the v ar iatio n o f eac h
o f said ? o wr ates deter mines at l east two p er io ds o f dif f er ent
? o wr ates. the ? o wr ates being hel d substantial l y c o nstant
dur ing eac h o f said p er io ds.
6. The p r o c ess o f c l aim 1 . wher ein said r eac tio ns ar e
c o nduc ted at a v ar iabl e temp er atur e.
7. The p r o c ess o f c l aim 6. wher ein said v ar iabil ity is
substantial l y c o ntinuo us.
1 0
2 5
8
8 . The p r o c ess o f c l aim 6. wher ein said v ar iabil ity deter
mines at l east two p er io ds o f dif f er ent temp er atur es.
9 . The p r o c ess o f c l aim 7. wher ein at the star t o f said
r eac tio ns the temp er atur e is hel d within the r ang e o f 2 0 to
3 8 C. . whil e at the end o f said r eac tio ns the temp er atur e is
hel d within the r ang e o f 42 to 48 C.
1 0. The p r o c ess o f c l aim 1 . wher ein the c o nc entr atio n o f
said f o r mal dehy de so l utio n is in the r ang e o f 2 0 to 3 0 wt %.
the c o nc entr atio n o f said so dium hy dr o x ide so l utio n is in the
r ang e o f 1 2 to 2 0 wt % and said ac etal dehy de is substantial l y
p ur e and the mo l ar p r o p o r tio ns CHZ OINIOH/ACH ar e in the
r ang e o f 5. l 9 . 5/1 . 051 . 4/ 1 . 0.
1 1 . The p r o c ess o f c l aim 1 . wher ein the suc c essiv e sup
p l ies to said r eac to r c o mp r ise: a ? r st p er io d in whic h
substantial l y hal f o f the v o l umes is sup p l ied. the temp er atur e
being hel d within the r ang e o f 2 2 to 2 8 C. ; a sec o nd p er io d
in whic h substantial l y o ne f o ur th p ar t o f the v o l umes is
sup p l ied. the temp er atur e being hel d within the r ang e o f 3 2
to 3 8 C. . the dur atio n o f said sec o nd p er io d being substan
tial l y the same as that o f the ? r st p er io d; and a thir d p er io d
in whic h the sup p l ies to the r eac to r ar e c o mp l eted. the
temp er atur e being hel d within the r ang e o f 42 to 48 . the
dur atio n o f said thir d p er io d being g r eater than that o f the
sec o nd p er io d