(2013) US20130324758 Process For Manufacturing Acrolein-Acrylic Acid

US 20130324758A1
( 19 ) United Sta tes

( 12) Pa tent Applica tion Publica tion ( 10) Pub. N 0. 2 US 2013/0324758 A1
Deva ux et a ] . ( 43) Pub. Da te: Dec. 5, 2013
( 54) PROCESS FOR MAN UFACTURIN G Publica tion Cla s s i? ca tion
ACROLEIN /ACRYLIC ACID ( 51) Int CL
C07C 51/16 ( 2006 . 01)
C07C 319 /02 ( 2006 . 01)
( 75) Inventor s : J ea n- Fr a ncois Deva ux; Soucieu En C07C 45/28 ( 2006 . 01)
J a r r es t ( FR) ; J ea n- Luc Dubois ; Miller y C07C 253/18 ( 2006 - 01)
( FR) ( 52) US. Cl.
CPC . . . . . . . . . . . . . . . C07C 51/16 ( 2013. 01) ; C07C 253/18
( 2013. 01) ; C07C319 /02 ( 2013. 01) ; C07C
45/28 ( 2013. 01)
( 73) As s ig nee: Ar kema Fr a nce, Colombia /s ( FR) USPC . . . . . . . . . . . 558/315; 56 2/532; 56 2/534; 56 2/535;
56 2/549 ; 56 8/6 3; 56 8/449
( 21) Appl. N O. Z 13/9 81, 9 27 ( 57) ABSTRACT
_ The pr es ent invention r ela tes to the s elective elimina tion of
( 22) PCT Flledi J a n- 26 : 2012 pr opa na l in a cr olein- r ich s tr ea ms to pr oduce a cr olein a nd/or
a cr y lic a cid a nd/or a cr y lonitr ile a nd/or methy lmer ca ptopr o
( 86 ) PCT N O; PCT/IB12/0039 6 piona ldehy de conta ining loW a mount of pr opa na l a nd/or pr o
pionic a cid a nd/or pr opionitr ile. One s ubj ect of the pr es ent
371 ( c) ( 1) ; invention is a pr oces s for ma nufa ctur ing a cr olein compr is ing
( 2) ( 4) Da te. Aug 20 2013 a s tep of s elective elimina tion of pr opa na l in a n a cr olein- r ich
s tr ea m in conta ct W ith a ca ta ly s t compr is ing a t lea s t moly b
_ _ _ _ _ denum. Another s ubj ect of the pr es ent invention is a pr oces s
( 30) For elg n Apphca tlon Pnonty Da ta for ma nufa ctur ing a cr y lic a cid fr om g ly cer ol including a s tep
of s elective elimina tion of pr opa na l in a n a cr olein- r ich s tr ea m
J a n. 28; 2011 ( IB) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201 1/ 00046 8 in conta ct W ith a ca ta ly s t compr is ing a t lea s t moly bdenum.
US 2013/0324758 A1
PROCESS FOR MAN UFACTURIN G
ACROLEIN /ACRYLIC ACID
[ 0001] The W or k lea ding to this invention ha s r eceived
funding fr om the Eur opea n Community s Seventh Fr a me
wor k Pr og r a m FP7/2007- 2013 under g r a nt a g r eement no
22886 7.
TECHN ICAL FIELD
[ 0002] The pr es ent invention r ela tes to the s elective elimi
na tion of pr opa na l in a cr olein- r ich s tr ea ms to pr oduce
a cr olein a nd/or a cr y lic a cid a nd/or a cr y lonitr ile conta ining
loW a mount of pr opa na l a nd/or pr opionic a cid a nd/or pr opi
onitr ile.
[ 0003] One s ubj ect ofthe pr es ent invention is a pr oces s for
ma nufa ctur ing a cr olein compr is ing a s tep of s elective elimi
na tion of pr opa na l in a n a cr olein- r ich s tr ea m. Another s ubj ect
of the pr es ent invention is a pr oces s for ma nufa ctur ing a cr y lic
a cid fr om g ly cer ol including a s tep of s elective elimina tion of
pr opa na l in a n a cr olein- r ich s tr ea m.
BACKGROUN D ART
[ 0004] Acr olein is a key inter media te for the s y nthes is of
methy lmer ca ptopr opiona ldehy de a nd of methionine, a s y n
thetic a minoa cid us ed a s a n a nima l feed s upplement, W hich
ha s emer g ed a s a s ubs titute for ? s hmea l. Acr olein is a ls o a
non- is ola ted s y nthetic inter media te of a cr y lic a cid a nd a cr y
lonitr ile for W hich the impor ta nce of their a pplica tions a nd its
der iva tives is knoW n. Acr olein a ls o lea ds , via r ea ction W ith
methy l viny l ether then hy dr oly s is , to g luta r a ldehy de, W hich
ha s ma ny us es in lea ther ta nning , a s a biocide in oil W ell
dr illing a nd dur ing the tr ea tment of cutting oils , a nd a s a
chemica l s ter ila nt a nd dis infecta nt for hos pita l eq uipment.
Acr olein a ls o lea ds to py r idine or g luta r a ldehy de.
[ 0005] Acr y lic a cid is a compound tha t is us ed es s entia lly
a s poly mer iza tion monomer or comonomer for the ma nufa c
tur e of a ver y br oa d r a ng e of ? na l pr oducts . Thes e ? na l
pr oducts a r e ma nufa ctur ed by poly mer iZ a tion of the a cid or of
the der iva tives of this a cid, in the es ter ( poly a cr y la tes ) or
a mide ( poly a cr y la mides ) for m. A ver y impor ta nt outlet for
a cr y lic a cid is the ma nufa ctur e of s uper a bs or bents , in W hich
a pa r tia lly neutr a liZ ed ( mixtur e of a cr y lic a cid a nd s odium
a cr y la te or a cr y la tes of other ca tions ) a cr y lic a cid is poly mer
iZ ed, or els e a cr y lic a cid is poly mer ized a nd the poly a cr y lic
compound obta ined is pa r tia lly neutr a liZ ed. Thes e poly mer s
a r e us ed a s is or a s copoly mer s in ? elds a s va r ied a s hy g iene,
deter g ents , pa ints , va r nis hes , a dhes ives , pa per , textiles ,
lea ther , a nd the like.
[ 0006 ] Acr olein a nd/or a cr y lic a cid a r e pr oduced indus tr i
a lly by oxida tion of pr opy lene us ing oxy g en or a n oxy g en
compr is ing mixtur e in the pr es ence of ca ta ly s t s y s tems ba s ed
on mixed oxides . This r ea ction is g ener a lly ca r r ied out in the
g a s pha s e a nd g ener a lly in tW o s ta g es to g ive a cr y lic a cid: the
? r s t s ta g e ca r r ies out the s ubs ta ntia lly q ua ntita tive oxida tion
of the pr opy lene to g ive a n a cr olein- r ich mixtur e, in W hich
a cr y lic a cid is a minor component, a nd then the s econd s ta g e
ca r r ies out the s elective oxida tion of the a cr olein to g ive
a cr y lic a cid.
[ 0007] The r ea ction conditions of thes e tW o s ta g es , ca r r ied
out in tW o multitubula r r ea ctor s in s er ies or in a s ing le r ea ctor
compr is ing the tW o r ea ction s ta g es in s er ies , a r e differ ent a nd
r eq uir e ca ta ly s ts s uited to the r ea ction; hoW ever , it is not
neces s a r y to is ola te the a cr olein fr om the ? r s t s ta g e dur ing
this tW o- s ta g e pr oces s .
Dec. 5, 2013
[ 0008] The s ta r ting ma ter ia ls us ed for a cr olein or a cr y lic
a cid pr oduction r es ult fr om oil or na tur a l g a s a nd cons e
q uently the a cr olein or a cr y lic a cid a r e for med fr om a non
r eneW a ble fos s il ca r bon s ta r ting ma ter ia l. In the context of the
commitments of the ma j or ity of indus tr ia liZ ed countr ies to
r educe emis s ions of g r eenhous e g a s es , it a ppea r s pa r ticula r ly
impor ta nt to ma nufa ctur e novel pr oducts ba s ed on a r eneW
a ble s ta r ting ma ter ia l, contr ibuting to r educing the envir on
menta l effects a nd g loba l W a r ming potentia l.
[ 0009 ] Gly cer ol is der ived fr om pla nt oils in the pr oduction
of biodies el fuels or oleochemica ls s uch a s fa tty a cids or fa tty
a lcohol or fa tty es ter s . Gly cer ol is one of the r a W ma ter ia ls
envis a g ed a s a s ubs titute for pr opy lene, g ly cer ol being a ble to
be s ubj ected to a ca ta ly tic dehy dr a tion r ea ction in or der to
pr oduce a cr olein. Such a pr oces s ma kes it pos s ible to thus
r es pond to the concept of g r een chemis tr y W ithin a mor e
g ener a l context of pr otecting the envir onment. Ther e a r e a ls o
ma ny pos s ible W a y s to a cces s to r eneW a ble g ly cer ol, for
exa mple by fer menta tion of s ug a r s or by hy dr og enoly s is r ea c
tions .
[ 0010] This pr oces s is hig hly a na log ous to the s y nthetic
pr oces s s ta r ting fr om pr opy lene ins ofa r a s the inter media te
pr oduct, a cr olein, r es ulting fr om the ? r s t s ta g e is the s a me a nd
ins ofa r a s the s econd s ta g e is ca r r ied out under the s a me
oper a ting conditions .
[ 0011] HoW ever , the r ea ction of the ? r s t s ta g e of the pr oces s
of the invention, the dehy dr a tion r ea ction, is differ ent fr om
the r ea ction for the oxida tion of pr opy lene of the us ua l pr o
ces s . The dehy dr a tion r ea ction, per for med in the g a s pha s e, is
ca r r ied out us ing differ ent s olid ca ta ly s ts fr om thos e us ed for
the oxida tion of pr opy lene. The a cr olein- r ich e? luent r es ult
ing fr om the ? r s t dehy dr a tion s ta g e, intended to feed the
s econd s ta g e of oxida tion of a cr olein to g ive a cr y lic a cid,
compr is es a g r ea ter a mount of W a ter a nd in a ddition exhibits
s ubs ta ntia l differ ences a s r eg a r ds by - pr oducts r es ulting fr om
the r ea ction mecha nis ms involved.
[ 0012] N umer ous ca ta ly s t s y s tems ha ve a lr ea dy been the
s ubj ect of s tudies for the dehy dr a tion r ea ction of g ly cer ol to
a cr olein.
[ 0013] Us . Pa t. N o. 5, 387, 720 des cr ibes a pr oces s for pr o
ducing a cr olein by dehy dr a tion of g ly cer ol, in liq uid pha s e or
in g a s pha s e, a t a temper a tur e r a ng ing up to 3400 C. , over
a cidic s olid ca ta ly s ts tha t a r e de? ned by their Ha mmett a cid
ity . The ca ta ly s ts mus t ha ve a Ha mmett a cidity beloW + 2 a nd
pr efer a bly beloW 3. Thes e ca ta ly s ts cor r es pond, for
exa mple, to na tur a l or s y nthetic s iliceous ma ter ia ls , s uch a s
mor denite, montmor illonite a nd a cidic Z eolites ; s uppor ts ,
s uch a s oxides or s iliceous ma ter ia ls , for exa mple a lumina
( A1203) , tita nium oxide ( TiOZ ) , cover ed by monoba s ic, diba
s ic or tr iba s ic inor g a nic a cids ; oxides or mixed oxides s uch a s
g a mma - a lumina , Z nO/Al2O3 mixed oxide, or els e het
er opoly a cids . The us e of thes e ca ta ly s ts W ould ma ke it pos
s ible to s olve the pr oblem of for ma tion of s econda r y pr oducts
g ener a ted W ith the ir on phos pha te ty pe ca ta ly s ts des cr ibed in
the document FR 6 9 5, 9 31.
[ 0014] Accor ding to Applica tion W O 06 /087084, the
s tr ong ly a cidic s olid ca ta ly s ts W hos e Ha mmett a cidity H0 is
betW een 9 a nd 18 ha ve a s tr ong ca ta ly tic a ctivity for the
dehy dr a tion r ea ction of g ly cer ol to a cr olein a nd a r e dea cti
va ted les s q uickly .
[ 0015] In the document W O 09 /044, 081 it ha s been pr o
pos ed to ca r r y out the r ea ction for dehy dr a tion of g ly cer ol in
the pr es ence of a ca ta ly s t s y s tem compr is ing oxy g en, ir on,
phos phor us , a nd one or mor e elements chos en fr om a lka li
US 2013/0324758 A1
meta ls , a lka line- ea r th meta ls , Al, Si, B, Co, Cr , N i, V , Z n, Z r ,
Sn, Sb, Ag , Cu, N b, Mo, Y, Mn, Pt, Rh a nd the r a r e ea r ths La ,
Ce, Sm.
[ 0016 ] The document W O 09 /128, 555 des cr ibes a pr oces s
for pr epa r ing a cr olein by dehy dr a tion of g ly cer ol in the pr es
ence of a ca ta ly s t compr is ing ma inly a compound in W hich
pr otons in a heter opoly a cid a r e excha ng ed a t lea s t pa r tia lly
W ith a t lea s t one ca tion s elected fr om elements belong ing to
Gr oup 1 to Gr oup 16 of the Per iodic Ta ble of Elements .
[ 0017] In the document W O 10/046 , 227 the dehy dr a tion of
g ly cer ol is per for med in the pr es ence of a ca ta ly s t s y s tem
compr is ing oxy g en, phos phor us a nd a t lea s t one meta l chos en
fr om va na dium, bor on or a luminium.
[ 0018] However , the ca ta ly s ts r ecommended in the pr ior a r t
for pr oducing a cr olein fr om g ly cer ol g ener a lly lea d to the
for ma tion of by - pr oducts s uch a s hy dr oxy pr opa none, pr o
pa na ldehy de ( ca lled a ls o pr opa na l) , a ceta ldehy de, a cetone,
a ddition pr oducts of a cr olein to g ly cer ol, poly condens a tion
pr oducts of g ly cer ol, cy clic g ly cer ol ether s , a nd a ls o phenol
a nd poly a r oma tic compounds W hich a r e the s our ce of the
for ma tion of coke on the ca ta ly s t a nd ther efor e of its dea cti
va tion.
[ 0019 ] The pr es ence of the by - pr oducts in a cr olein, es pe
cia lly pr opa na l, pos es numer ous pr oblems for the s epa r a tion
of a cr olein a nd r eq uir es s epa r a tion a nd pur i? ca tion s teps
W hich lea d to hig h cos ts for the r ecover y of the pur i? ed
a cr olein. Fur ther mor e, W hen a cr olein is us ed for pr oducing
a cr y lic a cid, the pr opa na l pr es ent ma y be oxidized to pr opi
onic a cid, W hich is dif? cult to s epa r a te fr om a cr y lic a cid,
es pecia lly by dis tilla tion. Indeed, pr opa na l a nd pr opionic a cid
ha ve their boiling points of r es pectively 49 0 C. a nd 141 C.
W hich a r e ver y clos e to boiling points of 53 C. a nd 141 C.
r es pectively of the obj ective compounds of a cr olein a nd
a cr y lic a cid. The s a me pr oblem occur s W hen a cr olein is us ed
to ma ke methionine, or a ceta ls or a cr y lonitr ile, s ince the
boiling points of a cr y lonitr ile a nd pr opionitr ile a r e r es pec
tively 77 C. a nd 9 7 C. Thes e pr oblems exis t for the tW o
mea ns of pr oduction of a cr olein/a cr y lic a cid or a cr y loni
tr ileifr om pr opy lene or fr om g ly cer olis ince pr opa na l
r es ults a s a by - pr oduct in the g ly cer ol dehy dr a tion a nd in the
pr opy lene oxida tion, but pr opa na l is in a g r ea ter a mount in the
ca s e of g ly cer ol, pr oba bly oW ing to a loW er s electivity of the
r ea ction of dehy dr a tion of g ly cer ol.
[ 0020] Thes e impur ities tha t a r e pr es ent g r ea tly r educe the
? eld of a pplica tion of the a cr olein a nd a cr y lic a cid pr oduced
by dehy dr a tion of g ly cer ol. In pa r ticula r , impur ities s uch a s
non- poly mer iZ a ble s a tur a ted compounds ca n be pa r ticula r ly
tr oubles ome in the ? na l a pplica tion by modify ing the pr op
er ties of the ? nis hed pr oduct, by confer r ing toxic or cor r os ive
pr oper ties on the ? nis hed pr oduct or by incr ea s ing polluting
or g a nic dis cha r g es dur ing the s ta g es of ma nufa ctur e of the
a cr y lic poly mer a nd/ or of the ? nis hed pr oduct.
[ 0021] Cons eq uently , ther e is a need for a n a cr y lic a cid
W hich meets a ll the a bove- mentioned cons tr a ints , both
ups tr ea m, tha t is to s a y a n a cr y lic a cid es s entia lly ba s ed on a
non- fos s il na tur a l ca r bon s our ce, a nd doW ns tr ea m, tha t is to
s a y a n a cr y lic a cid W hich meets q ua lity s ta nda r ds a lloW ing it
to be us ed in the ma nufa ctur e of a br oa d r a ng e of technica l
poly mer s , W ithout, hoW ever , r eq uir ing a s ophis tica ted a nd
ther efor e expens ive pur i? ca tion.
[ 0022] To meet this need, it ha s a lr ea dy been pr opos ed, for
exa mple in W O 09 /044, 081, to pla ce tW o a ctive ca ta ly s t beds
in s er ies : the g a s eous r ea ction mixtur e conta ining g ly cer ol is
s ent to a ? r s t ca ta ly s t in conta ct W ith W hich the dehy dr a tion
Dec. 5, 2013
r ea ction of g ly cer ol is a t lea s t pa r tia lly ca r r ied out g ener a lly
r es ulting in s econda r y compounds s uch a s pr opa na l. The
r ea ction mixtur e thus obta ined is pa s s ed over a s econd ca ta
ly s t bed s uch a s a doped ca ta ly s t s y s tem ba s ed on ir on phos
pha te, on W hich the dehy dr a tion r ea ction of unr ea cted g ly c
er ol ma y continue a t the s a me time a s the conver s ion of
pr opa na l to a cr olein. The a cr olein obta ined a ccor ding to this
embodiment conta ins a minimiZ ed a mount of pr opa na l,
W hich W idens its ? eld of a pplica tion a nd fa cilita tes obta ining
hig h pur ity a cr y lic a cid. HoW ever , it W a s obs er ved tha t s uch
ca ta ly s ts lea d to a r a pid plug g ing of the fa cility due to the
for ma tion of pr oducts like ta r .
[ 0023] The con? g ur a tion of tW o a ctive ca ta ly s t beds in
s er ies to limit the pr es ence of pr opa na l in a cr olein ha s a ls o
been des cr ibed in the pr oces s of W O 10/046 , 227 us ing a
ca ta ly s t s y s tem ba s ed on a mixed oxide of phos phor us a nd
va na dium. HoW ever , thes e ca ta ly s ts a r e les s a ctive a t moder
a te temper a tur e.
[ 0024] The document W O 10/074, 177 r ela tes to a method
for pr epa r ing a cr y lic a cid fr om a compos ition conta ining
a cr olein a nd pr opa na l by g a s pha s e r ea ction us ing a s olid
ca ta ly s t compr is ing a t lea s t Mo a nd V a s es s entia l compo
nents . In this g a s pha s e r ea ction, a cr olein is conver ted to
a cr y lic a cid a nd pr opa na l is conver ted to a cr y lic a cid a nd to
pr opionic a cid. W ith this a cr olein oxida tion ca ta ly s t, pr opa na l
is conver ted a t a s imila r r a te a s a cr olein, a nd pr opa na l is
ma inly conver ted to pr opionic a cid. The conver s ion of pr o
pa na l into a cr y lic a cid is ver y loW ( 3% ) , a nd the a cr y lic a cid
thus obta ined conta ins a ver y pr opionic a cid content a nd
it ha s to be pur i? ed by cr y s ta lliza tion to r emove pr opionic
a cid.
[ 0025] Als o, it ha s been pr opos ed to r emove pr opionic a cid
fr om a n a cr y lic a cid s tr ea m, in pa r ticula r fr om a n a cr y lic a cid
mixed g a s obta ined by va por - pha s e oxida tion of pr opy lene
a nd/or pr opa ne, by r ea cting the a cr y lic a cid s tr ea m in the
pr es ence of a mixed meta l oxide conta ining a t lea s t Mo a nd/or
Bi ( J P 10- 218831) or in the pr es ence of a pr opionic a cid
r eduction meta l mixed oxide ca ta ly s t conta ining a t lea s t one
element s elected fr om the g r oup of Mo a ndW ( EP 2 039 6 74) .
Thes e methods either involve a hig h temper a tur e ( 300- 500
C. in J P 10- 218831) , or lea d to a s ig ni? ca nt los s of a cr y lic
a cid ( mor e tha n 6 % in EP 2 039 6 74) .
[ 0026 ] Other W is e, the ca ta ly tic oxida tive dehy dr og ena tion
of s a tur a ted a ldehy des in uns a tur a ted a ldehy des is W ell
knoW n in pr ior a r t.
[ 0027] For exa mple, Ha r g is et a l, in I&EC pr oduct r es ea r ch
a nd development, V ol 5, N o. 1, Ma r ch 19 6 6 , pp 72- 75 pr opos e
to us e a n oxide of a r s enic, a ntimony or bis muth to conver t
s ome s a tur a ted a ldehy des into the cor r es ponding uns a tur a ted
a ldehy des . Pr opiona ldehy de is conver ted into a cr olein by
us ing Sb2O4 a s oxida nt, but only W ith a s electivity of 6 2% for
a conver s ion of 5% .
[ 0028] The oxy dehy dr og ena tion of s a tur a ted a ldehy des to
uns a tur a ted a ldehy des ha s been a ls o des cr ibed, mor e s peci?
ca lly for the pr oduction of metha cr olein fr om is obuty r a lde
hy de in US. Pa t. N o. 4, 381, 411, us ing ir on phos phor ous
oxide conta ining a t lea s t one pr omotor . Conver s ion r a tes of
100% ha ve been obta ined for metha cr olein y ields r a ng ing
betW een 52% a nd 80% .
[ 0029 ] In Kinetics a nd Ca ta ly s is , V ol 44, N o. 2, ( 2003) pp
19 8- 201, is obuty r a ldehy de ha s been conver ted in metha c
r olein on a ir on phos pha te ca ta ly s t W ith a conver s ion of 80%
a nd a s electivity of 82% . Mor eover , it ha s been s hoW n tha t the
a ddition of a ver y s ma ll a mount of moly bdenum to FeiP
US 2013/0324758 A1
ca ta ly s t enha nces the oxida tion a ctivity W ithout modify ing
the hig h s electivity tha t or ig ina tes fr om ir on phos pha te. This
effect ha s not been s tudied in oxy - dehy dr og ena tion of pr opa
na l into a cr olein, but it ha s been obs er ved tha t W hen the
a mount of moly bdenum is la r g er tha t 4% in the ca ta ly s t, the
s electivity fa lls , tea ching a W a y to us e moly bdenum ba s ed
ca ta ly s t.
[ 0030] The document J P 54- 046 705 dis clos es a pr oces s for
pr epa r ing uns a tur a ted a ldehy des s uch a s a cr olein or metha c
r olein, a nd ca r boxy lic a cids s uch a s a cr y lic a cid or meth
a cr y lic a cid, by the va por pha s e oxida tion of C3 a nd C4
s a tur a ted a ldehy des s uch a s pr opa na l or is obuty r a ldehy de, in
the pr es ence of ca ta ly s ts conta ining Mo, P oxides a nd one or
tW o elements chos en a mong Z n, Cu or Ag , s uppor ted on a
ca lcined ca r r ier ha ving a s peci? c s ur fa ce a r ea of a t lea s t 10
m2/g . In ca s e of pr opa na l, a y ield of 53. 1% of a cr olein a nd
a cr y lic a cid is obta ined a t a conver s ion level of 72. 6 % , mea n
ing tha t hig h conver s ion of pr opa na l combined W ith a hig h
s electivity in a cr olein is dif? cult to obta in.
[ 0031] In J our na l ofCa ta ly s is 19 5, 36 0- 375 ( 2000) , J i Hu et
a l ha ve s tudied the oxida tive dehy dr og ena tion of is obuty r a l
dehy de to metha cr olein over PiMo ca ta ly s t. FIGS. 1 a nd 2
illus tr a te the effect of temper a tur e on the r ea ction. They s hoW
tha t the conver s ion of is obuty r a ldehy de r ea ches a ma ximum
of a bout 9 5% even a t hig h temper a tur e. It a ppea r s tha t it is
dif? cult to conver t mor e tha n a bout 9 5% of is obuty r a ldehy de
W ithout a ffecting the s electivity in metha cr olein.
[ 0032] In Rea ct. Kinet. Ca ta l. Lett. V ol 81, N o. 2, 383- 39 1
( 2004) , the s a me r ea ction ha ve been s tudied over Cs PMo
ca ta ly s t by Cicma nec et a l. FIGS. 3 a nd 4 illus tr a te the depen
dence of the conver s ion of is obuty r a ldehy de a nd the y ield of
metha cr olein on conta ct time. It a ppea r s tha t the conver s ion is
limited to 9 0% even W ith hig h conta ct time.
[ 0033] Pr ior a r t on the W hole tea ches a W a y to conver t s a tu
r a ted a ldehy des pr es ent a t loW level in the cor r es ponding
uns a tur a ted a ldehy des s ince the ma n of the a r t W ould expect
a deg r a da tion of the ca ta ly s t pr oper ties a nd a decr ea s e of
s electivity in uns a tur a ted a ldehy des .
[ 0034] In W O09 /127, 889 , a 16 . 3% a cr olein y ield W a s
obta ined fr om g ly cer ol a t 9 1. 3% conver s ion W ith a het
er opoly a cid conta ining moly bdenum. It s hoW s tha t het
er opoly a cids conta ining moly bdenum a r e ba d ca ta ly s ts for
the pr oduction of a cr olein fr om g ly cer ol. For tha t r ea s on, the
ma n of the a r t is not tempted to us e thos e ca ta ly s ts to elimina te
pr opa na l a s a n impur ity in a cr olein.
[ 0035] It is ther efor e a n obj ective of the pr es ent invention to
pr ovide a pr oces s for s electively r emoving pr opa na l a s a n
impur ity fr om a n a cr olein- r ich s tr ea m W ithout a ffecting
a cr olein. As a r es ult, it ha s unexpectedly been found tha t the
mos t s elective ca ta ly s ts for pr opa na l elimina tion in a n
a cr olein- r ich s tr ea m compr is e a t lea s t the element moly bde
num.
[ 0036 ] It is a nother obj ective of the pr es ent invention to
pr ovide a pr oces s for ma nufa ctur ing a cr olein a nd/or a cr y lic
a cid conta ining loW a mount of pr opa na l a nd/or pr opionic
a cid.
[ 0037] It is a nother obj ective of the pr es ent invention to
pr ovide a pr oces s for ma nufa ctur ing a cr y lic a cid fr om g ly c
er ol including a s tep of s elective elimina tion of pr opa na l,
W hile pr oviding a cr y lic a cid es s entia lly ba s ed on a non- fos s il
na tur a l ca r bon s our ce a nd over coming the dr a wba cks of the
exis ting ca ta ly s ts for the dehy dr a tion of g ly cer ol.
Dec. 5, 2013
SUMMARY OF THE IN V EN TION
[ 0038] One s ubj ect of the pr es ent invention is ther efor e a
pr oces s for ma nufa ctur ing a cr olein cha r a cter ized in tha t it
compr is es s elective elimina tion of pr opa na l in a n a cr olein
r ich s tr ea m by pa s s ing the s a id s tr ea m in g a s pha s e in the
pr es ence of oxy g en thr oug h a ca ta ly s t compr is ing a t lea s t
moly bdenum a nd a t lea s t one element s elected fr om P, Si, W ,
Ti, Z r , V , N b, Ta , Cr , Mn, Fe, Co, N i, Cu, Z n, Ga , In, Tl, Sn,
Ag , As , Ge, B, Bi, La , Ba Sb Te, Ce, Pb.
[ 0039 ] In the pr es ent invention, s elective mea ns tha t pr o
pa na l is mor e conver ted tha n a cr olein on the bed of ca ta ly s t
a nd tha t pr opa na l is not conver ted into pr opionic a cid to a n
extent hig her tha n 50% . The conver s ion ( % ) of a ma ter ia l is
de? ned a s the r a tio betW een the mole number of ma ter ia l
r ea cted on the ca ta ly s t divided by the mole number of ma te
r ia l s upplied to the ca ta ly s t.
[ 0040] The a cr olein- r ich s tr ea m in the pr es ent invention
ma y be pr oduced by a ny conventiona l techniq ue knoW n by
thos e of or dina r y s kill in the a r t. Additiona lly , a ny conven
tiona l r a W ma ter ia l feed ma y be us ed to pr oduce a cr olein s o
long a s the a cr olein pr oduct s tr ea m conta ins s ome a mount of
pr opa na l.
[ 0041] Another s ubj ect of the invention is a pr oces s for
ma nufa ctur ing a cr y lic a cid compr is ing the oxida tion of
a cr olein obta ined a fter elimina tion of pr opa na l a ccor ding to
the a bove- mentioned pr oces s .
ma nufa ctur ing a cr y lonitr ile compr is ing the a mmoxida tion of
a cr olein obta ined a fter elimina tion of pr opa na l a ccor ding to
the a bove- mentioned pr oces s .
ma nufa ctur ing methy lmer ca ptopr opiona ldehy de us ed for
pr oducing methionine, compr is ing the a ddition of methy l
mer ca pta n to a cr olein obta ined a fter elimina tion of pr opa na l
a ccor ding to the a bove- mentioned pr oces s .
[ 0044] The pr es ent invention pr ovides fur ther a pr oces s for
ma nufa ctur ing bio- s our ced a cr y lic a cid conta ining a loW
a mount of pr opionic a cid fr om g ly cer ol, W hich is a r a W ma te
r ia l independent of petr oleum.
[ 0045] The invention W ill be mor e clea r ly under s tood on
r ea ding the folloW ing deta iled des cr iption, fr om the non
limiting exa mples of embodiments ther eof.
DETAILED DESCRIPTION
[ 0046 ] The ca ta ly s t for s elective elimina tion of pr opa na l
us ed in the pr oces s of the invention compr is es a t lea s t moly b
denum.
[ 0047] Adva nta g eous ly , the pr oces s for ma nufa ctur ing
a cr olein is cha r a cter ized in tha t it compr is es s elective elimi
na tion of pr opa na l in a n a cr olein- r ich s tr ea m by pa s s ing the
s a id s tr ea m in g a s pha s e in the pr es ence of oxy g en thr oug h a
ca ta ly s t compr is ing a t lea s t moly bdenum a nd a t lea s t one
element s elected fr om P, Si, W , Ti, Z r , V , N b, Ta , Cr , Mn, Fe,
Co, N i, Cu, Z n, Ga , In, Tl, Sn, Ag , As , Ge, B, Bi, La , Ba Sb Te,
Ce, Pb, chos en in the g r oup for med by the mixed meta l oxides
conta ining a t lea s t moly bdenum a nd heter opoly a cids con
ta ining a t lea s t moly bdenum.
[ 0048] In one embodiment of the invention, the ca ta ly s t
compr is es a t lea s t moly bdenum a nd a s ing le element s elected
fr om P, Si, W , Ti, Z r , V , N b, Ta , Cr , Mn, Fe, Co, N i, Cu, Z n, Ga ,
In, Tl, Sn, Ag , As , Ge, B, Bi, La , Ba Sb Te, Ce, Pb.
[ 0049 ] In one embodiment, the ca ta ly s t a ccor ding to the
invention ma y be a mixed meta l oxide ba s ed on moly bdenum
US 2013/0324758 A1
tha t is us ed W ith other feeds tocks tha n s a tur a ted a ldehy de, for
exa mple for metha nol oxida tion to for ma ldehy de ( Fei
M040 doped or not) a nd pr opy lene oxida tion to a cr olein
( ba s ed on bis muth moly bda te, for exa mple W ith a g ener a l
for mula des cr ibed in EP 19 87877: Mo l2Bia FebAcB dCeDfO, C
W her ein A is a t lea s t a n element s elected fr om coba lt a nd
nickel, B is a t lea s t a n element s elected fr om a lka li meta ls ,
a lka line ea r th meta ls a nd tha llium, C is a t lea s t a n element
s elected fr om tung s ten, s ilicon, a luminum, Z ir conium a nd
tita nium; D is a t lea s t a n element s elected fr om phos phor us ,
tellur ium, a ntimony , tin, cer ium, lea d, niobium, ma ng a nes e,
a r s enic a nd Z inc, pota s s ium) .
[ 0050] Exa mples of FeiMoiO ir on moly bda te ca ta ly s ts
a r e des cr ibed in Ca ta ly s is Review, V ol 47 ( 2004) , pp 125- 174.
[ 0051] Ir on moly bdenum ba s ed ca ta ly s ts a r e commer cia lly
a va ila ble. For exa mple Siid Chemie s upplies s ever a l g r a des of
s uch ca ta ly s ts under the tr a de na me FAMAX: FAMAX J 5,
FAMAX MS, FAMAX HS, FAMAX TH.
[ 0052] Exa mples of pr opy lene oxida tion ca ta ly s ts to
a cr olein a r e des cr ibed in EP 9 00774, EP 11259 11, EP
19 87877, EP 10749 38, US. Pa t. N o. 6 , 26 8, 529 , US. Pa t. N o.
4, 837, 9 40.
[ 0053] Pr efer a bly , the ca ta ly s t compr is es moly bdenum a nd
a t lea s t one element s elected fr om P, Si, W , Cr , Mn, Fe, Co, N i,
Bi, Sb, Ce.
[ 0054] In one embodiment, the ca ta ly s t a ccor ding to the
invention compr is es a t lea s t one heter opoly a cid conta ining a t
lea s t moly bdenum.
[ 0055] Adva nta g eous ly , pr oton in the heter opoly a cid con
ta ining a t lea s t moly bdenum, ma y be pa r tia lly excha ng ed by
a t lea s t one ca tion s elected fr om elements belong ing to Gr oup
1 to 16 of the Per iodic Ta ble of elements .
[ 0056 ] The ca ta ly s t a ccor ding to the invention ma y be r ep
r es ented by the g ener a l for mula :
Aa XbYcZ dOe
in W hich
[ 0057] A is mor e tha n one ca tion s elected fr om elements
belong ing to Gr oup 1 to 16 of the Per iodic Ta ble of Elements
a nd la ntha nides , pr efer a bly one a lka li meta l ca tion s uch a s
ces ium, r ubidium or pota s s ium.
[ 0058] X is P or Si, pr efer a bly P
[ 0059 ] Y is Mo
[ 006 0] Z is mor e tha n one element s elected fr om the
g r oup compr is ing W , Ti, Z r , V , N b, Ta , Cr , Mn, Fe, Co,
N i, Cu, Z n, Ga , In, Tl, Sn, Ag , As , Ge, B, Bi, La , Ba , Sb,
Te, Ce a nd Pb, pr efer a bly Fe, Bi, Co, N i, W , V , Cr , Sb,
Mn, Ce
[ 006 1] a , b, c a nd d s a tis fy ing folloW ing r a ng es :
[ 006 2] 0s a s 9 , pr efer a bly 0< a s 9
[ 006 3] 0s bs 2 pr efer a bly 0. 1s bs 1. 5
[ 006 4] 0< cs 12 pr efer a bly 5< cs 12
[ 006 5] 0s d< 12 pr efer a bly 0s ds 4
[ 006 6 ] a nd e is a number deter mined by the oxida tion of the
elements .
[ 006 7] Exa mples of effective ca ta ly s ts a r e mixed oxides or
heter opoly a cid s a lts of FeMo, Cs PMo, Cs PW Mo or BiMoFe
ca ta ly s ts .
[ 006 8] The ca ta ly s t us ed in the pr es ent invention ca n be
pr epa r ed by a ny knoW n techniq ue, for exa mple a s des cr ibed
in W O/09 / 128, 555 ( heter opoly a cids ) or in Ca ta ly s is RevieW ,
V ol 47 ( 2004) , pp 125- 174 a nd the r efer ences des cr ibed
ther ein. Gener a lly , the r es ulting s olid component is ? na lly
Dec. 5, 2013
? r ed or ca lcined to obta in the ca ta ly s t for s elective elimina
tion of pr opa na l a ccor ding to the pr es ent invention.
[ 006 9 ] The ca lcina tion ca n be ca r r ied out in a ir or under
iner t g a s s uch a s nitr og en, helium a nd a r g on or under a n
a tmos pher e of mixed g a s of oxy g en a nd iner t g a s , us ua lly in
a fuma ce s uch a s muf? e fur na ce, r ota r y kiln, ? uidized bed
fur na ce. Ty pe of the fur na ce is not limited s pecia lly . The
ca lcina tion ca n be effected even in a r ea ction tube tha t is us ed
for the g ly cer in dehy dr a tion r ea ction. The ? r ing temper a tur e
is us ua lly 150 to 9 00 C. , pr efer a bly 200 to 800 C. a nd mor e
pr efer a bly 200 to 6 00 C. The ca lcina tion is continuedus ua lly
for 0. 5 to 10 hour s .
[ 0070] The ca ta ly s t in the pr oces s a ccor ding to the inven
tion ma y be a bulk a nd is us ed, in this ca s e, W ithout a ny
s uppor t.
[ 0071] The ca ta ly s t ma y a ls o be loa ded on a s uppor t ( or
ca r r ier ) , the a mount of s uppor t g ener a lly r epr es enting fr om 0
to 9 0% , pr efer a bly a t lea s t 5% of the tota l W eig ht of the
ca ta ly s t.
[ 0072] The ca r r ier ca nbe g r a nule a nd poW der a nd ma y ha ve
a ny s ha pe s uch a s s pher e, pellet, cy lindr ica l body , holloW
cy linder body , tr ilobe a nd q ua dr ilobe a nd ba r W ith optiona l
molding a id.
[ 0073] It is pos s ible to us e, a s a s uppor t, a ny ma ter ia l s uch
a s s ilica , a lumina , ma g nes ia , tita nium oxide, Z ir conia , s ilicon
ca r bide, s ilica / a lumina mixtur e, s ilica tes , dia toma ceous
ea r th, bor a tes or ca r bona tes on condition tha t thes e pr oducts
a r e s ta ble under the r ea ction conditions to W hich the ca ta ly s t
W ill be s ubj ected. Pr efer a bly , the ca ta ly s t is not a s uppor ted
ca ta ly s t.
[ 0074] The ca ta ly s t ma y ha ve a ny s ha pe a nd ca n be g r a nule
or poW der . It is pr efer a ble to mold the ca ta ly s t into a s ha pe of
s pher e, pellets , cy linder , holloW cy linder , ba r or the like,
optiona lly W ith a dding a molding a id. The ca ta ly s t ca n be
s ha ped into the a bove- con? g ur a tions tog ether W ith ca r r ier
a nd optiona l a uxilia r y a g ents . The molded ca ta ly s t ma y ha ve
a pa r ticle s iZ e of for exa mple 1 to 10 mm for a ? xed bed a nd
of les s tha n 1 mm for a ? uidized bed.
[ 0075] The a cr olein- r ich s tr ea m in the pr oces s a ccor ding to
the invention ca n be s peci? ca lly the pr oduct s tr ea m of a
pr opy lene ( or other non- petr oleum ba s ed s our ces of hy dr o
ca r bons ) ca ta ly tic oxida tion pr oces s , or the pr oduct s tr ea m of
g ly cer ol dehy dr a tion in liq uid pha s e or in g a s pha s e, pr efer
a bly in g a s pha s e or in a s tr ea m of hy dr oxy pr opa na l dehy dr a
tion. Gener a lly , the a cr olein- r ich s tr ea m r es ults a s a g a s mix
tur e tha t is s ubmitted dir ectly for the pr oces s a ccor ding to the
invention
[ 0076 ] Exa mples of oper a ting conditions for dehy dr a ting
g ly cer ol into a cr olein a r e des cr ibed in the inter na tiona l pa tent
a pplica tions W O 06 /087083, W O 06 /087084, W O 09 /128,
555 or W O 10/046 , 227 of the Applica nt. Speci? ca lly , the
ca ta ly s t us ed for the r ea ction of dehy dr a tion is a ca ta ly s t
ha ving Ha mmett a cidity loW er tha n + 2. Speci? ca lly , the ca ta
ly s t us ed for the r ea ction of dehy dr a tion is a ca ta ly s t conta in
ing no moly bdenum.
[ 0077] Exa mples of oper a ting conditions for oxida tion of
pr opy lene into a cr olein a r e des cr ibed in Pr oces s Economic
Pr og r a m n 6 D fr om SR1 cons ulting a nd the r efer ence cited
ther ein.
[ 0078] The a mount of pr opa na l in the a cr olein- r ich s tr ea m
is g ener a lly les s tha n 0. 2, expr es s ed by the moles of pr opa na l
r ela tive to the moles of a cr olein pr es ent in the s tr ea m. It ma y
US 2013/0324758 A1
r a ng e fr om 1/4000 to 1/ 5 expr es s ed by the moles of pr opa na l
r ela tive to the moles of a cr olein pr es ent in the s tr ea m, pr ef
er a bly fr om 1/1000 to 1/ 10.
The a cr olein- r ich s tr ea m in the pr oces s a ccor ding to the
invention conta ins W a ter , oxy g en, a nd eventua lly by - pr oducts
s uch a s hy dr oxy pr opa none, a ceta ldehy de, a cetone, a ddition
pr oducts of a cr olein to g ly cer ol, poly condens a tion pr oducts
of g ly cer ol, cy clic g ly cer ol ether s , hy dr oxy pr opa na l, phenol
a nd poly a r oma tic compounds , pr opy lene, a cr y lic a cid, a nd
iner t g a s es s uch a s ca r bon oxide, ca r bon dioxide, nitr og en,
helium, a r g on, pr opa ne. The na tur e of the by - pr oducts a nd the
compos ition of the a cr olein- r ich s tr ea m depend of cour s e on
the r a W ma ter ia l us ed to pr oduce a cr olein.
[ 0079 ] Thus , in the ca s e W her e pr opy lene is the ma in r a W
ma ter ia l in a n oxida tion r ea ction to pr oduce a cr olein, the
a cr olein- r ich s tr ea m ma y conta in pr opa ne a s ther ma l ba lla s t.
[ 0080] In the ca s e W her e g ly cer ol is the ma in r a W ma ter ia l
in a dehy dr a tion pr oces s to pr oduce a cr olein, the mixtur e of
a cr olein a nd pr opa na l ma y conta in a la r g e a mount of W a ter
depending of the concentr a tion of g ly cer ol in the feed.
[ 0081] In the pr oces s a ccor ding to the invention, the con
centr a tion of a cr olein in the g a s mixtur e tha t is pa s s ed thr oug h
the ca ta ly s t r a ng es fr om 1 to 12 mole % , pr efer a bly fr om 4 to
10 mole % .
[ 0082] The pr oces s a ccor ding to the invention is ca r r ied out
in the pr es ence of oxy g en, or a n oxy g en- conta ining g a s s uch
a s a ir . Gener a lly , oxy g en is a lr ea dy pr es ent in the g a s mixtur e,
but fur ther oxy g en ma y be inj ected if the oxy g en concentr a
tion is too loW . Oxy g en content is compr is ed betW een 1 a nd
10% ( mol) a nd pr efer a bly betW een 3 a nd 7% ( mol) .
[ 0083] The concentr a tion of W a ter of the a cr olein- r ich
s tr ea m ma y va r y la r g ely . W a ter content is compr is ed betW een
3 a nd 9 0% ( mol) a nd pr efer a bly betW een 8 a nd 80% ( mol) .
[ 0084] The s elective elimina tion of pr opa na l oper a tes a t a
temper a tur e betW een 250 C. a nd 400 C. , pr efer a bly
betW een 280 a nd 350 C. , a nd a t a pr es s ur e betW een 1 a nd 5
ba r a bs olute a nd pr efer a bly betW een 1 a nd 2 ba r .
[ 0085] A feed r a te of the g a s r ea cta nt is a dva nta g eous ly
1000 to 40, 000 h' 1 in ter m of GHSV ( g a s hour ly s pa ce veloc
ity in nor ma l m3/h/volume of ca ta ly s t in m3) , pr efer a bly 3000
to 30000 h_ 1, mor e pr efer a bly 5000 to 20000 h_ l. If the
GHSV becomes loW er tha n 1000 h_ l, the s electivity W ill be
loW er ed. On the contr a r y , if the GHSV exceeds 40, 000 h_ 1,
the conver s ion W ill be loW er ed.
[ 0086 ] For ea ch ca ta ly s t ther e is a n optimum of temper a tur e
a nd GHSV for W hich a hig h conver s ion of pr opa na l is
obta ined a t a loW conver s ion of a cr olein.
[ 0087] The s elective elimina tion of pr opa na l in a n a cr olein
r ich s tr ea m a ccor ding the invention ca n be ca r r ied out in a
va r iety of r ea ctor s s uch a s ? xed bed, ? uid bed, cir cula ting
? uid bed a nd moving bed. Among them, the ? xed bed a nd the
? uid bed a r e pr efer a ble.
[ 0088] W hen a ? uid bed or cir cula ting ? uid bed r ea ctor is
us ed a s a ? r s t r ea ctor for the pr oduction of the a cr olein- r ich
s tr ea m, the pr opa na l elimina tion ca ta ly s t ca n be us ed a s a
? xedbed doW ns tr ea m of the s a id ? r s t r ea ctor , or it ca nbe us ed
a s a compa r tmenta lized ? uid bed r ea ctor . This ty pe of r ea ctor
ca n be ma de by us ing a g r id or a mes h W ithin the ? uid bed tha t
keep the ? r s t ca ta ly s t in the loW er pa r t of the ? uid bed a nd the
pr opa na l elimina tion ca ta ly s t in the upper pa r t of the ? uid
bed.
[ 0089 ] In a ? r s t embodiment of the invention, the pr oduc
tion of the a cr olein- r ich s tr ea m a nd the s elective elimina tion
of pr opa na l a r e ca r r ied out in a ta ndem- ty pe r ea ctor compr is
Dec. 5, 2013
ing tW o r ea ctor s linked to ea ch other , W her e the tW o r ea ctor s
a r e ? lled W ith a ca ta ly s t for the pr oduction of a cr olein a nd a
ca ta ly s t for the s elective elimina tion of pr opa na l r es pectively ,
a nd W her e the pr oduction of a cr olein a nd the elimina tion of
pr opa na l a r e s epa r a tely conducted in their r es pective r ea ctor s .
[ 009 0] In a s econd embodiment of the invention, the pr o
duction of the a cr olein- r ich s tr ea m a nd the s elective elimina
tion of pr opa na l a r e ca r r ied out in a s ing le- r ea ctor - ty pe, W her e
the r ea ctor ? lled W ith a ca ta ly s t for the s elective elimina tion
of pr opa na l on the r ea ction g a s outlet s ide a nd W ith a ca ta ly s t
for the pr oduction of a cr olein on the r ea ction g a s inlet s ide,
thus conducting in the s ing le r ea ctor the pr oduction of
a cr olein folloW ed by the s elective elimina tion of pr opa na l. It
is pr efer a ble tha t the r ea ctor ha s differ ent Z one of temper a tur e
contr ol s o tha t elimina tion of pr opa na l ca n be oper a ted a t a
differ ent temper a tur e fr om the pr oduction of a cr olein. In ca s e
of a ? xed bed r ea ctor , a pr efer r ed con? g ur a tion is W hen the
g a s is moving upW a r d thr oug h the bed a nd the pr opa na l
elimina tion ca ta ly s t is pla ced on top of the ca ta ly s t for the
pr oduction of a cr olein.
[ 009 1] In the ca s e of ? xed beds , W hen a multitubula r r ea ctor
is us ed for the a cr olein pr oduction a pr efer r ed con? g ur a tion
for the s elective elimina tion of pr opa na l is a la y er of ca ta ly s t
on top of the tubula r pla te, a bove the r ea ctor tubes conta ining
the a cr olein pr oducing ca ta ly s t. This con? g ur a tion is pr e
fer r ed to r epla ce mor e ea s ily the pr opa na l elimina tion ca ta ly s t
by va cuum unloa ding .
[ 009 2] Acr olein thus obta ined by the pr oces s a ccor ding to
the invention conta ins les s tha n 5000 ppm, even les s tha n
1000 ppm of pr opa na l.
[ 009 3] Another s ubj ect of the invention is the us e of a
ta ining a t lea s t moly bdenum, to r educe the content of pr opa
na l loW er tha n 5000 ppm, pr efer a bly loW er tha n 1000 ppm, in
a n a cr olein- r ich s tr ea m.
[ 009 4] Acr olein obta ined by the pr oces s a ccor ding to the
invention ca n be a dva nta g eous ly fur ther s ubj ected to knoW n
oxida tion methods to pr oduce a cr y lic a cid W ith a loW content
of pr opionic a cid, ty pica lly conta ining les s tha n 5000 ppm,
even les s tha n 1000 ppm of pr opionic a cid, W hich is a ty pica l
s peci? ca tion level for a br oa d r a ng e of a pplica tions .
[ 009 5] Thus , a nother s ubj ect of the invention is the us e of a
ta ining a t lea s t moly bdenum to pr oduce a cr y lic a cid W ith a
loW content of pr opionic a cid, ty pica lly conta ining les s tha n
5000 ppm, even les s tha n 1000 ppm of pr opionic a cid.
[ 009 6 ] Gener a lly , the oxida tion r ea ction is ca r r ied out in the
pr es ence of molecula r oxy g en or of a mixtur e compr is ing
molecula r oxy g en, a t a temper a tur e r a ng ing fr om 200 C. to
350 C. , pr efer a bly fr om 250 C. to 320 C. , a nd under a
pr es s ur e r a ng ing fr om 1 to 5 ba r , in the pr es ence of a n oxida
tion ca ta ly s t compr is ing a t lea s t one element chos en fr om the
lis t Mo, V , W , Re, Cr , Mn, Fe, Co, N i, Cu, Z n, Sn, Te, Sb, Bi,
Pt, Pd, Ru a nd Rh, pr es ent in the meta llic for m or in the oxide,
s ulfa te or phos pha te for m. Us e is ma de in pa r ticula r of the
for mula tions compr is ing Mo a nd/or V a nd/or W a nd/or Cu
US 2013/0324758 A1
a nd/ or Sb a nd/or Fe a s ma in cons tituents . The oxida tion ca ta
ly s t ma y be s uppor ted on a ca r r ier s uch a s Z ir conia , s ilica ,
a lumina , s tea tite a nd combina tion ther eof a nd s ilicon ca r bide.
Acr olein g a s s tr ea m conta ins the s a me kind of components a s
the s elective elimina tion s tep of pr opa na l, s uch a s W a ter , or
iner t g a s es s uch a s ca r bon oxide, ca r bon dioxide, nitr og en,
helium, a r g on, pr opa ne or or g a nic impur ities .
a mmoxida tion methods to pr oduce a cr y lonitr ile W ith a loW
content of pr opionitr ile, ty pica lly conta ining les s tha n 5000
ppm, even les s tha n 1000 ppm of pr opionitr ile, W hich is a
ty pica l s peci? ca tion level for a br oa d r a ng e of a pplica tions .
condens a tion r ea ction to pr oduce g luta r a ldehy de, for
exa mple a ccor ding to the pr oces s des cr ibed in the document
W O 2011/055051.
[ 009 9 ] Acr olein obta ined by the pr oces s a ccor ding to the
a ddition W ith methy l mer ca pta n to pr oduce methy lmer ca pto
pr opiona ldehy de us ed for ma nufa ctur ing methionine or its
s a lt or its hy dr oxy l a na log ue, 2- hy dr oxy - 4- methy lthio- bu
ty r ic a cid. Adva nta g eous ly , a cr olein is pur i? ed by a bs or ption
in W a ter a nd fur ther dis tilla tion befor e being r ea cted W ith
methy lmer ca pta n to y ield methy lmer ca ptopr opiona ldehy de.
Ins ofa r a s pr opa na l a mount is r educed to a minimum va lue,
methy lmer ca ptopr opiona ldehy de ca n be us ed W ithout pur i?
ca tion for the pr oduction of methionine or its s a lt or its
hy dr oxy a na log ue.
[ 0100] Another obj ect of the pr es ent invention is a pr oces s
for ma nufa ctur ing a cr y lic a cid fr om g ly cer ol cha r a cter ized in
tha t it compr is es a t lea s t the folloW ing s teps :
[ 0101] a ) dehy dr a tion of g ly cer ol to g ive a n a cr olein- r ich
s tr ea m conta ining pr opa na l,
[ 0102] b) s elective elimina tion of pr opa na l by pa s s ing the
s a id s tr ea m in g a s pha s e in the pr es ence of oxy g en thr oug h a
Co, N i, Cu, Z n, Ga , In, Tl, Sn, Ag , As , Ge, B, Bi, Cr , La , Ba Sb
Te, Ce, Pb;
[ 0103] c) oxida tion of the a cr olein to g ive a cr y lic a cid.
[ 0104] The ? r s t s tep a ) ma y be ca r r ied out in the g a s pha s e
or in the liq uid pha s e, pr efer a bly in the g a s pha s e. W hen the
dehy dr a tion r ea ction is ca r r ied out in the g a s pha s e, va r ious
pr oces s technolog ies ma y be us ed, na mely a ? xed bed pr o
ces s , W ith one or s ever a l r ea ctor s in pa r a llel, a ? uid bed
pr oces s or a cir cula ting ? uid bed pr oces s . It is a ls o pos s ible to
us e r ea ctor s of the pla te hea t excha ng e ty pe.
[ 0105] The exper imenta l conditions of the g a s - pha s e r ea c
tion a r e pr efer a bly a temper a tur e betW een 180 C. a nd 5000
C. , pr efer a bly betW een 250 a nd 400 C. a nd a pr es s ur e
betW een 1 a nd 5 ba r s . In the liq uid pha s e, the r ea ction is
pr efer a bly ca r r ied out a t a temper a tur e betW een 150 C. a nd
350 C. a nd a pr es s ur e W hich ma y r a ng e fr om 3 to 70 ba r .
[ 0106 ] Us e is g ener a lly ma de of g ly cer ol, or a mixtur e of
g ly cer ol a nd W a ter ha ving a W eig ht r a tio W hich ca n va r y
W ithin W ide limits , for exa mple fr om 0. 1 to 100, pr efer a bly
betW een 0. 5 a nd 4, in the r ea ctor .
[ 0107] The mixtur e of g ly cer ol a nd W a ter ma y be us ed in
liq uid for m or in g a s eous for m, pr efer a bly in the g a s pha s e
for m.
[ 0108] Accor ding to one embodiment of the invention, it is
pos s ible to us e >9 5% pur e g ly cer ol, tha t is to s a y W ith < 5%
Dec. 5, 2013
W a ter , a nd to blend the s a id g ly cer ol W ith a g a s mixtur e
compr is ing va por ized W a ter a nd iner t g a s , pos s ibly coming
for m a r ecy cle g a s , s o a s the r ea ction of conver ting g ly cer ol
into a cr olein is conducted in g a s pha s e.
[ 0109 ] Pr efer a bly , the s tep a ) is ca r r ied out in the pr es ence
of oxy g en, or a n oxy g en- conta ining g a s , a s des cr ibed in
a pplica tions W O 06 /087083 or W O 06 /114506 . The mola r
r a tio of the molecula r oxy g en to the g ly cer ol is g ener a lly
a r ound 0. 1 to 1. 5, pr efer a bly fr om 0. 5 to 1. 0.
[ 0110] The g ly cer ol dehy dr a tion r ea ction is g ener a lly ca r
r ied out over s olid a cid ca ta ly s ts . The ca ta ly s ts tha t a r e s uit
a ble a r e homog eneous or heter og eneous s ubs ta nces W hich
a r e ins oluble in the r ea ction medium a nd W hich ha ve a Ha m
mett a cidity , denoted HO, of les s tha n + 2. The ca ta ly s t W ill be
chos en a mong s uita ble ca ta ly s ts conta ining no moly bdenum.
[ 0111] A key pa r a meter lies in the concentr a tion of g ly cer ol
in the cha r g e. Expr es s ed in mole per cent, the concentr a tion of
g ly cer ol va r ies W idely fr om 0. 1 to 20. As is common in
r ea ctions of this ty pe, the y ield of the des ir ed pr oduct is a n
inver s e function of the concentr a tion. Fr om the point of vieW
of obta ining a r ea s ona ble ? oW r a te combined W ith a n a ccept
a ble y ield, the concentr a tion of g ly cer ol in the cha r g e is
a r ound 3 to 16 mol % . The concentr a tion is contr olled by the
a mount of W a ter a nd of iner t g a s pr es ent in the feed s tr ea m.
The pr efer r ed g a s eous diluent is nitr og en a lthoug h other
g a s es s uch a s ca r bon dioxide, helium, a r g on, etc. a r e a ls o
s uita ble. Of cour s e, W hen the des ir ed concentr a tion of g ly c
er ol per mits it, a ir r epr es ents a s uita ble diluted oxida nt.
[ 0112] The conta ct time expr es s ed in s econds is the r a tio
betW een the volume of the ca ta ly s t bed a nd the volume ( cor
r ected for nor ma l pr es s ur e a nd nor ma l temper a tur e) of the
g a s eous r ea cta nts convey ed per s econd. The a ver a g e temper a
tur e a nd pr es s ur e conditions in a bed ma y va r y depending on
the na tur e of the ca ta ly s t, the na tur e of the ca ta ly s t bed a nd the
s iZ e of the ca ta ly s t. In g ener a l, the conta ct time is fr om 0. 1 to
20 s econds a nd pr efer a bly fr om 0. 3 to 15 s econds .
[ 0113] In the pr oces s for ma nufa ctur ing a cr y lic a cid fr om
g ly cer ol of the invention, the s tep b) cons is ts in the s elective
elimina tion of pr opa na l a ccor ding to the a bove- des cr ibed
pr oces s , in the a cr olein- r ich s tr ea m coming fr om the s tep a ) to
g ive a n a cr olein- r ich s tr ea m W ith a loW content of pr opa na l,
fur ther oxidiZ ed in s tep c) into a cr y lic a cid.
[ 0114] Pr efer a bly , the ca ta ly s t us ed in the s tep b) is chos en
in the g r oup for med by the mixed meta l oxides conta ining a t
lea s t moly bdenum a nd heter opoly a cids conta ining a t lea s t
moly bdenum.
[ 0115] The g a s mixtur e r es ulting fr om the s tep c) is com
pos ed, a pa r t fr om a cr y lic a cid:
[ 0116 ] of lig ht compounds W hich a r e non- condens a ble
under the temper a tur e a nd pr es s ur e conditions nor ma lly
employ ed: nitr og en, unconver ted oxy g en, ca r bon monoxide
a nd ca r bon dioxide, W hich a r e for med in a s ma ll a mount by
? na l oxida tion or by r ecy cled in the pr oces s ,
[ 0117] of condens a ble lig ht compounds : in pa r ticula r
W a ter , g ener a ted by the dehy dr a tion r ea ction or pr es ent a s
diluent, unconver ted a cr olein, lig ht a ldehy des , s uch a s for m
a ldehy de a nd a ceta ldehy de, for mic a cid a nd a cetic a cid,
[ 0118] of hea vy compounds : fur fur a ldehy de, benZ a lde
hy de, ma leic a cid, ma leic a nhy dr ide, benZ oic a cid,
2- butenoic a cid, phenol, pr otoa nemonin, a nd the like.
[ 0119 ] Then, the pr oces s for ma nufa ctur ing a cr y lic a cid
a ccor ding the invention fur ther compr is es the s teps of collect
ing the r es ulta nt a cr y lic a cid a s a s olution by us ing W a ter or a
s olvent, a nd then of pur ify ing the r es ulta nt s olution conta in
US 2013/0324758 A1
ing a cr y lic a cid by us ing for exa mple a dis tilla tion s tep for
r emoving loW - a nd hi g h- boiling point ma ter ia ls a nd/ or a cr y s
ta lliZ a tion s tep for pur ify ing a cr y lic a cid by cr y s ta lliZ ing it.
[ 0120] The a cr y lic a cid thus obta ined ca n be us ed to pr o
duce for exa mple poly a cr y lic a cids or s a lts a s W a ter - s oluble
poly mer s or W a ter - a bs or bent r es ins , by knoW n methods .
[ 0121] Accor ding to one pa r ticula r embodiment of the
invention, us e is ma de of a n inter media te s tep of pa r tia l con
dens a tion of W a ter a nd of the hea vy by - pr oducts der ived fr om
the dehy dr a tion s tep a ) , a s is des cr ibed for exa mple in the
pa tent a pplica tion W O 08/087, 315.
[ 0122] The s a id inter media te s tep ha s the a im of r emoving
mos t of the W a ter pr es ent a nd the hea vy by - pr oducts befor e
s ending the g a s eous s tr ea m compr is ing the a cr olein a nd a ll
non- condens a ble g a s es to the pr opa na l elimina tion s tep or to
the s tep for the oxida tion of a cr olein to g ive a cr y lic a cid. This
pa r tia l condens a tion of the W a ter thus ma kes it pos s ible to
a void da ma g e to the ca ta ly s t of the oxida tion of a cr olein to
g ive a cr y lic a cid a nd to a void, dur ing the s ubs eq uent s ta g es ,
the r emova l of la r g e a mounts of W a ter , W hich could W ell be
expens ive a nd r es ult in los s es of a cr y lic a cid. In a ddition, it
ma kes it pos s ible to r emove a por tion of the hea vy impur i
ties for med dur ing the dehy dr a tion of the g ly cer ol a nd to
fa cilita te pur i? ca tion oper a tions .
[ 0123] This inter media te s tep is ca r r ied out on a s epa r a ting
unit W hich is a condens a tion pla nt compr is ing a n a bs or ption
column coupled or not coupled to a n eva por a tor , one or mor e
hea t excha ng er s , one or mor e condens er s , a dephleg ma tor ,
a nd a ny item of eq uipment W ell knoW n to a per s on s killed in
the a r t W hich ma kes it pos s ible to ca r r y out a pa r tia l conden
s a tion of a n a q ueous s tr ea m.
[ 0124] It is ca r r ied out under conditions s uch tha t the
a cr olein- r ich s tr ea m is s epa r a ted into a n a cr olein- r ich g a s
eous pha s e a nd a n a cr olein- poor a q ueous pha s e.
[ 0125] Fr om 20 to 9 5% , pr efer a bly fr om 40 to 9 0% , of the
W a ter pr es ent in the s tr ea m is r emoved in the liq uid s tr ea m a nd
the a cr olein- r ich pha s e g ener a lly compr is es mor e tha n 80%
a nd pr efer a bly mor e tha n 9 0% of the a cr olein initia lly pr es ent
in the s tr ea m This r es ult is g ener a lly obta ined by loW er ing the
temper a tur e to a temper a tur e of 6 0 to 1200 C.
[ 0126 ] In one embodiment, the s tep of pa r tia l condens a tion
of W a ter a nd of the hea vy by - pr oducts der ived fr om the dehy
dr a tion s tep a ) is ca r r ied out befor e oper a ting the s tep b) of
s elective elimina tion of pr opa na l. In this embodiment, it is
pr efer r ed tha t the ca ta ly s t for pr opa na l elimina tion a nd the
ca ta ly s t for the oxida tion of a cr olein into a cr y lic a cid a r e
ins ta lled in the s a me r ea ctor . Gener a lly tW o s epa r a te r ea ction
Z ones W ith tW o s epa r a te cooling s y s tems a r e us ed for the 2
ca ta ly s ts . It is a ls o pos s ible tha t ca ta ly s ts a r e oper a ted in 2
s epa r a te r ea ctor s .
[ 0127] In a n a lter na tive for m, the s tep of pa r tia l condens a
tion of W a ter a nd of the hea vy by - pr oducts der ived fr om the
dehy dr a tion s tep a ) is ca r r ied out a fter oper a ting the s tep b) of
s elective elimina tion of pr opa na l. In this embodiment, pr opi
onic a cid der ived fr om the dehy dr a tion r ea ction a nd the pr o
pa na l elimina tion r ea ction ma y be ea s ily r emoved by the
pa r tia l condens a tion of W a ter fr om the a cr olein- r ich s tr ea m
befor e the oxida tion s ta g e. As mos t pa r t of a cr y lic a cid is a ls o
r emoved by the pa r tia l condens a tion of W a ter , r ea ction con
ditions a r e chos en to limit a s fa r a s pos s ible the conver s ion of
a cr olein in the pr opa na l elimina tion s tep.
[ 0128] Accor ding to the pr oces s of the invention, it is pos
s ible to obta in a cr y lic a cid ha ving a content of pr opionic a cid
loW er tha n 500 ppm.
Dec. 5, 2013
[ 0129 ] N oW , the pr es ent invention W ill be expla ined in
much deta il W ith r efer r ing s ever a l exa mples , but this inven
tion s hould not be limited to thos e des cr ibed in folloW ing
exa mples . In the folloW ing Exa mples a nd Compa r a tive
Exa mples , % mea ns mole % .
EXAMPLES
Pr epa r a tion of Ca ta ly s t
Exa mple 1
Cs PMo
[ 0130] 100 g of phos phomoly bdic a cid W a s dis s olved in
200 mL of deioniZ ed W a ter to obta in a n a q ueous s olution of
pho s phomoly bdic a cid, a nd then W a s mixed a t r oom temper a
tur e for 2 hour s .
32. 7 g of 48. 5 W t % Cs OH a q ueous s olution W a s diluted W ith
20 mL of deioniZ ed W a ter . The r es ulting Cs OH a q ueous s olu
tion W a s dr opped in the a bove a q ueous s olution of phos pho
moly bdic a cid, a nd then W a s mixed a t r oom temper a tur e for 2
hour s .
The r es ulting y elloW s lur r y W a s eva por a ted a t 6 00 C. by us e of
r ota r y - eva por a tor .
The obta ined poW der W a s dr ied a t 1200 C. for 10 hour s .
The compos ition of the r es ulta nt dr ied s lur r y is :
CS2. 5P1. 0MO 12
Subs eq uently , the r es ulta nt pr oduct W a s ca lcined in a ir a t 250
C. for 3 hour s .
Exa mple 2
Cs PW Mo
[ 0131] 50 g of phos photung s tomoly bdic a cid W a s dis s olved
in 20 mL of deioniZ ed W a ter to obta in a n a q ueous s olution of
phos photung s tomoly bdic a cid, a nd then W a s mixed a t r oom
temper a tur e for 2 hour s .
13. 4 g of 48. 5 W t % Cs OH a q ueous s olution W a s diluted W ith
50 mL of deioniZ ed W a ter . The r es ulting Cs OH a q ueous s olu
tion W a s dr opped in the a bove a q ueous s olution of phos pho
tung s tomoly bdic a cid, a nd then W a s mixed a t r oom temper a
tur e for 2 hour s .
The r es ulting y elloW s lur r y W a s eva por a ted a t 6 00 C. by us e of
r ota r y - eva por a tor . The obta ined poW der W a s dr ied a t 1200 C.
for 10 hour s .
The compos ition of the r es ulta nt dr ied s lur r y is :
CS2. 5P1. OW 6 MO6
Subs eq uently , the r es ulta nt pr oduct W a s ca lcined in a ir a t 250
C. for 3 hour s .
Exa mple 3
MoV PCuAs
[ 0132] 100 g of moly bdenum tr ioxide, 6 . 3 g of va na dium
pentoxide, 1. 1 g of copper oxide a nd 8. 0 g of 85 W t % or tho
phos phor ic a cid a nd 1. 8 g of 6 0 W t % a r s enic a cid W er e
dis per s ed in 1000 mL of deioniZ ed W a ter . The mixtur e W a s
r e? uxed for 6 hour s W hile a dding hy dr og en per oxide to y ield
a r eddis h- br oW n, tr a ns pa r ent s olution. After a little ins oluble
US 2013/0324758 A1
compound W a s r emoved fr om the obta ined s olution, the s olu
tion thus for med W a s eva por a ted to dr y nes s on a W a ter ba th.
The compos ition of the dr ied pr oduct is :
Subs eq uently , the r es ulta nt pr oduct W a s ca lcined under a ? oW
of a ir a t 310 C. for 5 hour s .
Exa mple 4
MoV PCuAs Sb
[ 0133] 300 g of moly bdenum tr ioxide, 11. 37 g of va na dium
pentoxide, 3. 31 g of copper oxide, 8. 32 g of copper a ceta te,
28. 82 g of85 W t % or thophos phor ic a cid a nd 24. 6 4 g of 6 0 W t
% a r s enic a cid W er e dis per s ed in 19 00 mL of deioniZ ed W a ter
a nd hea ted a t r e? ux a t 9 5 to 100 C. for s ix hour s to y ield a
r eddis h- br oW n, tr a ns pa r ent s olution. Subs eq uently , to the
s olution W a s a dded 1. 52 g of a ntimony tr ioxide a nd the r es ult
a nt s olution W a s fur ther hea ted a t r e? ux a t 9 5 to 100 C. for
thr ee hour s .
Then, the r es ulta nt s lur r y W a s hea ted in a W a ter ba th to be
eva por a ted a nd dr ied.
The compos ition of the dr ied pr oduct is :
Exa mple 5
MoV PCuSbCs
[ 0134] To 1200 mL of pur i? ed W a ter W er e a dded 200 g of
moly bdenum tr ioxide, 8. 84 g of va na dium penta oxide a nd
17. 6 1 g of 85 W t % or thophos phor ic a cid, a nd the s olution W a s
hea ted a t r e? ux a t 9 0 to 100 C. for ? ve hour s to y ield a
r eddis h- br oW n, tr a ns pa r ent s olution.
Subs eq uently , to the s olution W a s a dded 6 . 07 g of a ntimony
tr ioxide a nd the r es ulta nt s olution W a s fur ther hea ted a t r e? ux
a t 9 0 to 100 C. for tW o hour s to obta in a n a ntimony tr ioxide
dis s olved, hig hly da r k blue s olution.
Then, the r es ulting s olution W a s cooled to fr om 15 to 20 C.
To the s olution W er e g r a dua lly a dded a s olution of 13. 33 g of
ces ium a ceta te dis s olved in 150 mL of pur i? ed W a ter a nd a
s olution of 16 . 06 g of a mmonium a ceta te dis s olved in 150 mL
of pur i? ed W a ter a t the s a me time W ith a g ita tion. Then, to the
s lur r y W a s fur ther a dded a s olution pr epa r ed by dis s olving
11. 09 g of cupr ic a ceta te monohy dr a te in 170 mL of pur i? ed
W a ter a nd the r es ulta nt s olution W a s a g ed a t 15 to 20 C. for
one hour to y ield a g r eenblue s lur r y . Then, the r es ulta nt s lur r y
W a s hea ted in a W a ter ba th to be eva por a ted a nd dr ied. The
compos ition of the r es ulta nt dr ied s lur r y is :
M9 10V 0. 7P1. 1Cu0. 4Sb0. 3CSo. 5( N H4) 1. 5
Eva lua tion a nd Res ults
Exa mple 6
Selective Elimina tion of Pr opa na l in a n Acr olein
FloW
[ 0135] A s a mple of Cs PMo ca ta ly s t fr om exa mple 1 W a s
compa cted a nd cr us hed a nd s ieved to obta in pa r ticle s iZ e of
Dec. 5, 2013
35 to 48 mes h. A s ta inles s s teel tube ( inter na l dia meter 13
mm) W a s loa ded W ith 2. 0 ml of ca ta ly s t to for m a ? xed
ca ta ly tic bed.
An a q ueous s olution of a cr olein a nd pr opa na l W a s fed to a n
eva por a tor tog ether W ith nitr og en a nd W ith oxy g en a t 270 C.
in or der to for m a feed g a s W hich W a s pa s s ed thr oug h the ? xed
ca ta ly tic bed a t a tmos pher ic pr es s ur e. The ? xed ca ta ly tic bed
W a s hea ted W ith a n electr ic oven a t a temper a tur e of 270 C.
Feed g a s ha d a folloW ing compos ition in mol % : a cr olein:
pr opa na l: oxy g en: nitr og en: W a ter : 6 . 0: 0. 06 0: 3. 8: 14: 76 . Tota l
feed g a s ? oW W a s 31 nor ma l liter per hour . Ga s Hour ly Spa ce
V elocity ( GHSV ) W a s 15, 000 h_ l. GHSV is the r a tio of the
? oW of feed g a s ( expr es s ed in nor ma l liter per hour ) by the
volume of ca ta ly s t ( expr es s ed in liter ) . Fixed bed W a s oper
a ted for 5 hour s W ithout pr es s ur e incr ea s e in the r ea ctor .
In or der to cha r a cter ize the compos ition of the g a s ? oW out the
r ea ctor , pr oducts W er e condens ed in a condens er cha r g ed W ith
deminer a liZ ed W a ter . Liq uid a q ueous pha s e a nd g a s eous
vents W er e q ua ntita tively a na ly Z ed by g a s chr oma tog r a phs
( HP 6 89 0 Ag ilent, FFAP column, FID detector , CP49 00
V a r ia n, Silica plot a nd Molecula r Sieve 5 A, TCD detector s ) .
Pr opor tions of pr oducts W er e cor r ected in fa ctor s fr om the
r es ults of the g a s chr oma tog r a ph to deter mine a bs olute
a mounts of pr oducts .
The conver s ion ( % ) of ma ter ia l ( a cr olein or pr opa na l) , a nd the
y ield of obj ective s ubs ta nce ( % ) a nd the r ela tive r a te of con
ver s ion a r e deter mined by folloW ing eq ua tions :
The conver s ion( % ) ofma ter ia l: ( mole number of ma te
r ia l r ea cted/mole number of ma ter ia l s upplied) ><
100
The y ield( % ) of a cr y lic a cid: ( mole number of a cr y lic
a cid obta ined/mole number of a cr olein s up
plied) >< 100
The y ield( % ) ofpr opionic a cid: ( mole number ofpr o
pionic a cid obta ined/mole number ofpr opa na l
s upplied) >< 100
The r ela tive r a te of pr opa na l elimina tion: conver s ion
ofpr opa na l/conver s ion of a cr olein
Res ults a r e s hoW n in ta ble 1.
Exa mple 7
[ 0136 ] The s a me exper iment a s in exa mple 6 W a s r epr o
duced, W ith a g a s hour ly s pa ce velocity of 14, 000 h' 1 a nd
va por iZ er a nd oven temper a tur es of 300 C. Fixed bed W a s
oper a ted for 5 hour s W ithout pr es s ur e incr ea s e in the r ea ctor .
Exa mple 8
[ 0137] The s a me exper iment a s in exa mple 6 W a s r epr o
duced, W ith a g a s hour ly s pa ce velocity of 4, 400 h- 1 a nd
Exa mple 9
US 2013/0324758 A1
Exa mple 10
duced, W ith Cs PW Mo ca ta ly s t of exa mple 2 a nd W ith a g a s
hour ly s pa ce velocity of 5, 500 h- 1 a nd va por is er a nd oven
temper a tur es of 250 C. Fixed bed W a s oper a ted for 5 hour s
W ithout pr es s ur e incr ea s e in the r ea ctor .
Exa mple 11
duced, W ith MoV PCuAs ca ta ly s t of exa mple 3 a nd W ith a g a s
hour ly s pa ce velocity of 5, 000 h- 1 a nd va por is er a nd oven
Dec. 5, 2013
TABLE 2
Exa mple 12 13 14
Ca ta ly s t MoV PCuAs MoV PCuAs Sb MoV PCuSbCs
GHSV h' l 4, 700 4, 400 5, 500
V a por is er a nd oven 385 345 250
temper a tur e ( C. )
Pr opa na l conver s ion ( % ) 9 7 14 9 8
Pr opionic a cid y ield ( % ) 14 14 13
Acr olein conver s ion ( % ) 23 < 5 29
Acr y lic a cid y ield ( % ) 20 1 15
Rela tive r a te ofpr opa na l 4. 2 >3 3. 4
elimina tion
Exa mple 15
duced, W ith FeMo ca ta ly s t fr om MAPCO, r efer ence MFM3
MS, a nd W ith a g a s hour ly s pa ce velocity of 10, 000 h- 1 a nd
TABLE 1
Exa mple 6 7 8 9 10 11
Ca ta ly s t Cs PMo Cs PMo Cs PMo Cs PMo Cs PW Mo MoV PCuAs
GHSV 1151 15, 000 14, 000 4, 400 4, 400 5, 500 5, 000
V a por is er a nd oven 270 300 270 300 250 350
Pr opa na l conver s ion ( % ) 9 0 82 9 9 100 9 2 6 5
Pr opionic a cid y ield ( % ) 10 12 11 9 13 15
Acr olein conver s ion ( % ) 11 25 28 6 5 53 < 5
Acr y lic a cid y ield ( % ) 7 22 13 6 4 36 5
Pr opa na l elimina tion ( r ela tive r a te) 7. 9 3. 2 3. 5 1. 5 1. 7 >13
Exa mple 12 va por is er a nd oven temper a tur es of 305 C. Fixed bed W a s
[ 0141] The s a me exper iment a s in exa mple 6 W a s r epr o- Res ults a r e s hown in ta ble 3,
duced, W ith MoV PCuAs ca ta ly s t of exa mple 3 a nd W ith a g a s
hour ly s pa ce velocity of 4, 700 h' 1 a nd va por is er a nd oven
Exa mple 13
duced, W ith MoV PCuAs Sb ca ta ly s t of exa mple 4 a nd W ith a
g a s hour ly s pa ce velocity of 4, 400 h' 1 a nd va por is er a nd oven
Exa mple 14
duced, W ith MoV PCuSbCs of exa mple 5 a nd W ith a g a s
hour ly s pa ce velocity of 5, 500 h' 1 a nd va por is er a nd oven
W ithout pr es s ur e incr ea s e in the r ea ctor . Res ults a r e s hoW n in
ta ble 2.
Exa mple 16
va por is er a nd oven temper a tur es of 330 C. Fixed bed W a s
Exa mple 17
duced, W ith a feed g a s compos ition in mol % : a cr olein: pr o
pa na l: oxy g en: nitr og en: W a ter : 6 . 2: 0. 06 2: 6 . 7: 6 9 : 18. In this
exper iment a much loW er concentr a tion of W a ter W a s us ed
compa r ed to exa mple 16 . Fixed bed W a s oper a ted for 5 hour s
Exa mple 18
duced, W ith pr opy lene oxida tion ca ta ly s t ba s ed on BiMoFe
tha t W a s pr epa r ed a ccor ding to exa mple 1 of Eur opea n Pa tent
EP 807 46 5 B1. Ga s hour ly s pa ce velocity W a s 5, 800 h- 1 a nd
va por is er a nd oven temper a tur es W er e s et to 325 C. Fixed
US 2013/0324758 A1
bed W a s oper a ted for 5 hour s W ithout pr es s ur e incr ea s e in the
r ea ctor .
Res ults a r e s hown in ta ble 3.
Exa mple 19
Compa r a tive
duced W ith TiO2 ca ta ly s t ( ST31119 fr om N or pr o s a int
Goba in) . Fixed bed W a s oper a ted for 5 hour s W ithout pr es s ur e
incr ea s e in the r ea ctor .
The s a me exper iment W a s a ls o r epr oduced W ith a g a s hour ly
s pa ce velocity of 3, 700 h' 1 a nd va por is er a nd oven temper a
tur es of 300 C. Fixed bed W a s oper a ted for 5 hour s W ithout
pr es s ur e incr ea s e in the r ea ctor .
W e obs er ved tha t pr opa na l is not s electively elimina ted a s
a cr olein is mor e conver ted tha n pr opa na l.
TABLE 3
Fxa mnle
19
15 16 17 18 ( Compa r a tive)
Ca ta ly s t FeMo BiMoFe TiO2
GHSV h l 10, 000 20, 000 20, 000 5, 800 15, 000, 700
V a por is er a nd oven 305 330 330 325 270 300
Pr opa na l conver s ion 9 8 9 9 9 9 9 6 < 5 16
( % )
Pr opionic a cid y ield 3 6 6 8 0 8
( % )
Acr olein conver s ion 9 < 6 11 < 5 < 5 30
( % )
Acr y lic a cid y ield 0. 5 2 2 3 0 1
( % )
Rela tive r a te of 11 >15 9 >19 0 6
pr opa na l elimina tion
Exa mple 20
Compa r a tive
duced W ith FePSr ca ta ly s t pr epa r ed a ccor ding to exa mple 3 of
W O2009 /44081, W ith a g a s hour ly s pa ce velocity of 4, 000
h' 1 a nd va por is er a nd oven temper a tur es of 280 C.
Fixed bed W a s oper a ted for 2 hour s , a nd the exper iment ha d to
be s topped beca us e of s ever e pr es s ur e incr ea s e in the ca ta ly tic
bed, due to ta r like pr oducts for ma tion.
Exa mple 21
Acr olein Pr oduction fr om Gly cer ol
[ 0150] A PW /Ti dehy dr a tion ca ta ly s t W a s pr epa r ed a s fol
loW s : 89 mg of 85% phos phor ic a cid ( Aldr ich) a nd 2. 33 g of
a mmonium meta tung s ta te ( Fluka ) W er e dis s olved in 7. 5 g of
deioniZ ed W a ter to obta in a n a q ueous s olution of tung s to
phos phor ic a cid. 7. 6 g of the r es ulting a q ueous s olution W a s
then s pr a y ed onto 1 5. 4 g of TiO2 poW der obta ined by g r inding
a na ta s e ty pe TiO2 pellets ( ST31119 fr om N or pr o Sa int
Goba in) to 35 to 48 mes h. The r es ulting poW der W a s dr ied a t
1 10 C. for 2 hour s a nd then W a s ? r ed in nitr og en a tmos pher e
a t 5000 C. for 3 hour s to obta in a tita nia ca r r ier s uppor ting
Dec. 5, 2013
10% of tung s tophos phor ic a cid. This tita nia ca r r ier W a s
s ieved to obta in a pa r ticle s iZ e of 35 to 48 mes h.
A s ta inles s s teel tube ( inter na l dia meter 13 mm) W a s loa ded
s ucces s ively W ith 2. 4 ml of Cs PMo ca ta ly s t fr om exa mple 1
a nd W ith 9 . 6 ml of PW /Ti ca ta ly s t to for m a ? xed ca ta ly tic
bed.
An a q ueous s olution of g ly cer in ( a t a concentr a tion of 50% by
W eig ht) W a s fed to a n eva por a tor a t a How r a te of 12. 4 g /hr
tog ether W ith nitr og en ( 14. 4 N L/hr ) a nd W ith oxy g en ( 0. 9 5
N L/hr ) a t 280 C. s o tha t g ly cer in W a s g a s i? ed a nd the r es ult
ing g a s i? ed g ly cer in W a s pa s s ed thr oug h the ? xed ca ta ly tic
bed, ? r s t thr oug h the PW / Ti ca ta ly s t bed then thr oug h Cs PMo
ca ta ly s t bed. The ? xed ca ta ly tic bed W a s hea ted W ith a n
electr ic oven a t a temper a tur e of 280 C. Feed g a s ha d a
folloW ing compos ition in mol % : g ly cer ol: oxy g enznitr og en:
W a ter : 6 . 2: 3. 5: 58. 5: 31. 5. Ga s Hour ly Spa ce V elocity
( GHSV ) of the ? r s t ca ta ly s t W a s 2, 500 h- 1 a nd tha t of the
s econd ca ta ly s t W a s 10, 000 h_ l. GHSV is the r a tio of the How
of feed g a s ( expr es s ed in nor ma l liter per hour ) by the volume
of ca ta ly s t ( expr es s ed in liter ) . Pr es s ur e in the r ea ctor W a s 1 . 7
ba r g a ug e.
In or der to cha r a cter ize the compos ition of the g a s ? oW out the
r ea ctor , pr oducts W er e condens ed in a condens er cha r g ed W ith
deminer a liZ ed W a ter . Liq uid a q ueous pha s e a nd g a s eous
vents W er e q ua ntita tively a na ly Z ed by g a s chr oma tog r a phs
( HP 6 89 0 Ag ilent, FFAP column, FID detector , CP49 00
V a r ia n, Silica plot a nd Molecula r Sieve 5 A, TCD detector s ) .
Pr opor tions of pr oducts W er e cor r ected in fa ctor s fr om the
r es ults of the g a s chr oma tog r a ph to deter mine a bs olute
a mounts of pr oducts .
The conver s ion ( % ) of ma ter ia l, the s electivity of obj ective
s ub s ta nce a nd the y ield of obj ective s ub s ta nce a r e deter mined
by folloW ing eq ua tions :
The conver s ion( % ) ofma ter ia l: ( mole number ofma te
r ia l r ea cted/mole number of ma ter ia l s upplied) ><
100
The s electivity ( % ) of obj ective s ubs ta nce: ( mole num
ber of obj ective s ubs ta nce obta ined/mole number
of ma ter ia l r ea cted) >< 100
The y ield( % ) of obj ective s ubs ta nce: ( mole number of
obj ective s ubs ta nce obta ined/mole number of
ma ter ia l fed) >< 100
The pr opa na l/a cr olein mola r r a tio( % ) : ( mole number
ofpr opa na l obta ined/mole number of a cr olein
obta ined) >< 100
Res ults a r e s hoW n in Ta ble 4.
Exa mple 22
Compa r a tive
duced by us ing only one s ing le ca ta ly s t in the ca ta ly tic bed:
9 . 6 ml of PW /Ti ca ta ly s t W a s loa ded in the ca ta ly tic bed.
Res ults a r e s hoW n in Ta ble 4.
TABLE 4
Exa mple 21 22( compa r a tive)
Gly cer ol conver s ion ( % ) >9 9 >9 9
Acr olein y ield ( % ) 49 76
Acr y lic a cid y ield ( % ) 25 0. 3
Pr opa na l y ield ( % ) 0. 02 0. 7
Pr opionic a cid y ield ( % ) 0. 2 0. 13
Acetic a cid y ield ( % ) 8. 6 0. 4
US 2013/0324758 A1
TABLE 4- continued
Exa mple 21 22 ( compa r a tive)
Aceta ldehy de y ield ( % ) 2. 3 1. 6
Hy dr oxy pr opa none y ield ( % ) 0 0. 2
Pr opa na l/a cr olein mola r r a tio ( % ) 0. 04 0. 9 2
Exa mple 23
Acr y lic Acid Pr oduction fr om Gly cer ol W ith a Step
of Selective Elimina tion of Pr opa na l
[ 0152] A s imula tion us ing the ASPEN PLUS s oftwa r e
W a s us ed to illus tr a te the method a ccor ding to the invention.
In this exa mple, % W t mea ns % by W eig ht a nd ppmW t mea ns
pa r t per million by W eig ht.
W e mentioned only the components a t a concentr a tion a bove
1% W t.
A g a s s tr ea m a t 320 C. under 2. 8 ba r ( 82. 5 t/h, 20. 8% W t
g ly cer ol, 51. 7% W t W a ter , 21. 8% W t ca r bon dioxide, 5. 3% W t
oxy g en) is s ent to a multitube ? xed bed r ea ctor conta ining a
heter og eneous dehy dr a tion ca ta ly s t coupled W ith a molten
s a lt ba th.
A g a s s tr ea m lea ves this r ea ctor a t 320 C. under 1. 8 ba r ( 82. 5
t/h, 59 . 8% W t W a ter , 4. 2% W t oxy g en, 10. 2% W t a cr olein,
22. 4% W t CO2) . This g a s s tr ea m conta ins 6 50 ppmW t of
pr opa na l. This s tr ea m is cooled to 102 C. in a s er ies of hea t
excha ng er s . A liq uid pha s e ( 26 . 7 t/h, 9 7% W t W a ter ) is
r emoved a nd the g a s pha s e is s ent to the loW er pa r t of con
dens a tion column, tha t compr is es a condens er a t its top to
g ener a te a liq uid r e? ux in the column. Another g a s eous How
is inj ected a t the bottom of the column ( 35. 9 t/h, 123 C. ,
76 . 3% W t CO2, 16 . 5% W t W a ter , 3. 0% W t CO, 1. 9 % W t O2) .
The g a s pha s e tha t g oes out the condens er ( 6 9 . 5 t/h, 74 C. ,
1. 7 ba r , 6 5. 9 % W t CO2, 12. 1% W t a cr olein, 10. 8% W t W a ter ,
6 . 0% W t O2, 2. 4% W t CO, 1. 3% W t a ceta ldehy de, 770 ppmW t
pr opa na l) is hea ted to 240 C. in a hea t excha ng er .
This s tr ea m is s ent to the top of a multitubula r ? xed bed
r ea ctor tha t compr is es 2 s ections . Ea ch s ection is coupled
W ith a s peci? c molten s a lt ba th. The upper s ection conta ins a
ca ta ly s t for s elective elimina tion of pr opa na l a nd the s a lt ba th
of this s ection is kept a t 300 C. The loW er s ection conta ins a
ca ta ly s t for the oxida tion of a cr olein to a cr y lic a cid a nd the
s a lt ba th of this s ection is hea ted to 26 0 C.
After the ? r s t s ection, the g a s ? oW conta ins 6 6 . 6 % W t CO2,
11. 8% W t a cr olein, 11. 0% W tW a ter , 5. 4% W t O2, 2. 4% W t CO,
1. 3% W t a ceta ldehy de, 120 ppmW t pr opa na l.
At the outlet of the r ea ctor , the g a s s tr ea m conta ins 6 7. 2% W t
CO2, 14. 4% W t a cr y lic a cid, 11. 2% W t W a ter , 1. 1% W t O2,
2. 6 % W t CO, 1. 1% W t a cetic a cid, a nd 70 ppm pr opionic a cid.
This s tr ea m is cooled to 16 0 C. a nd inj ected in a n a bs or ption
column. At the top of this column, W a ter ( 6 . 5 t/h) is inj ected.
The liq uid tha t is r ecover ed a t the bottom of the column is
s end to a s econd column tha t is oper a ted under va cuum. A
s tr ea m of a cr y lic a cid is r ecover ed a t the bottom of this
column ( 15. 5 t/h, 6 3. 6 % W t a cr y lic a cid, 27. 7 W t % W a ter ,
4. 9 % W t a cetic a cid, 3. 0 W t % for mic a cid a nd 300 ppmW t
pr opionic a cid) .
11
Dec. 5, 2013
Exa mple 24
( Compa r a tive) : Acr y lic Acid Pr oduction fr om
Gly cer ol W ithout Selective Elimina tion of Pr opa na l
[ 0153] The s a me s imula tion a s in exa mple 23 W a s r epr o
duced W ith a s econd multitubula r ? xed bed r ea ctor tha t com
pr is es only one s ection. This s ection conta ins a ca ta ly s t for the
oxida tion of a cr olein to a cr y lic a cid a nd the s a lt ba th of this
s ection is hea ted to 26 0 C. The s tr ea m of a cr y lic a cid tha t is
r ecover ed a t the bottom of the la s t column conta ins 6 3. 8% W t
a cr y lic a cid, 27. 7 W t % W a ter , 4. 9 % W t a cetic a cid, 3. 0 W t %
for mic a cid a nd 2000 ppmW t pr opionic a cid.
Exa mple 25
Methy lmer ca ptopr opiona ldehy de Pr oduction fr om
Gly cer ol W ith Selective Elimina tion of Pr opa na l
[ 0154] The s a me exper iment a s in exa mple 21 is r epr o
duced. The hot a cr olein g a s es out of the r ea ctor a r e q uenched
in cold W a ter in or der to g et a n a q ueous pha s e conta ining
a r ound 3% W t a cr olein. This a q ueous pha s e is fur ther dis
tilled. Acr olein conta ining 9 6 % W t a cr olein, 0. 4% W t a ceta l
dehy de, 3% W t W a ter a nd 0. 04% W t pr opa na l is r ecover ed. A
r ea ction mixtur e cons is ting of 25 g of methy lmer ca ptopr opi
ona ldehy de a nd 0. 85 g of a mixtur e of 48% W t of py r idine in
a cetic a cid is intr oduced in a 250 ml r ea ctor , At 6 0 C. , 89 . 4 g
of the obta ined a cr olein a nd 74. 9 g of 9 9 . 5% W t methy lmer
ca pta n a r e s imulta neous ly intr oduced in this r ea ction mixtur e
over a 30 minute per iod a nd r ea ction is continued for 10
minutes then the mixtur e is cooled. Methy lmer ca ptopr opi
ona ldehy de is obta ined a nd ca n be us ed W ithout fur ther pur i
? ca tion or W ith a pur i? ca tion by dis tilla tion under r educed
pr es s ur e for methionine or 2- hy dr oxy - 4- ( methy lthio) buty r ic
a cid s y nthes is .
W ha t is cla imed is :
1. Pr oces s for ma nufa ctur ing a cr olein cha r a cter ized in tha t
it compr is es s elective elimina tion of pr opa na l in a n a cr olein
r ich s tr ea m by pa s s ing the s a id s tr ea m in g a s pha s e in the
pr es ence of oxy g en thr oug h a ca ta ly s t compr is ing a t lea s t
moly bdenum a nd a t lea s t one element s elected fr om P, Si, W ,
Ti, Z r , V , N b, Ta , Cr , Mn, Fe, Co, N i, Cu, Z n, Ga , In, Tl, Sn,
Ag , As , Ge, B, Bi, La , Ba Sb Te, Ce, Pb.
2. Pr oces s a ccor ding to cla im 1 cha r a cter ized in tha t the
ca ta ly s t is chos en fr om the g r oup cons is ting of the mixed
meta l oxides conta ining a t lea s t moly bdenum a nd heter opoly
a cids conta ining a t lea s t moly bdenum.
ca ta ly s t is one mixed meta l oxide conta ining a t lea s t moly b
denum.
ca ta ly s t conta ins ir on moly bda te mixed oxide.
ca ta ly s t is one heter opoly a cid conta ining a t lea s t moly bde
num.
6 . Pr oces s a ccor ding to cla im 5 cha r a cter ized in tha t the
ca ta ly s t compr is es a t lea s t one heter opoly a cid conta ining a t
lea s t moly bdenum in W hich pr oton in the heter opoly a cid ma y
be pa r tia lly excha ng ed by a t lea s t one ca tion s elected fr om
elements belong ing to Gr oup 1 to 16 of the Per iodic Ta ble of
elements .
US 2013/0324758 A1
ca ta ly s t is r epr es ented by the g ener a l for mula :
AQ XbYCZ J OE
in W hich
A is mor e tha n one ca tion s elected fr om elements belong
ing to Gr oup 1 to 16 of the Per iodic Ta ble of Elements
a nd la ntha nides
X is P or Si
Y is Mo
Z is mor e tha n one element s elected fr om the g r oup com
pr is ing W , Ti, Z r , V , N b, Ta , Cr , Mn, Fe, Co, N i, Cu, Z n,
Ga , In, Tl, Sn, Ag , As , Ge, B, Bi, La , Ba , Sb, Te, Ce a nd
Pb,
a , b, c a nd d s a tis fy ing folloW ing r a ng es :
0s a s 9 ,
a nd e is a number deter mined by the oxida tion of the
elements .
ca ta ly s t is loa ded on a s uppor t.
9 . Pr oces s a ccor ding to cla im 1 cha r a cter ized in tha t the
a mount of pr opa na l r a ng es fr om 1/4000 to l/ 5 expr es s ed by
the moles of pr opa na l r ela tive to the moles of a cr olein pr es ent
in the a cr olein- r ich s tr ea m.
concentr a tion of a cr olein r a ng es fr om 1 to 12 mole % in the
g a s s tr ea m W hich is pa s s ed thr oug h the ca ta ly s t.
a cr olein- r ich s tr ea m is obta ined by ca ta ly tic oxida tion of
pr opy lene.
a cr olein- r ich s tr ea m is obta ined by dehy dr a tion of g ly cer ol in
the pr es ence of a ca ta ly s t conta ining no moly bdenum.
pr oduction of the a cr olein- r ich s tr ea m a nd the s elective elimi
na tion of pr opa na l a r e ca r r ied out in a ta ndem- ty pe r ea ctor .
pr oduction of the a cr olein- r ich s tr ea m a nd the s elective elimi
na tion of pr opa na l a r e ca r r ied out in a s ing le- ty pe r ea ctor .
12
Dec. 5, 2013
15. Us e of a ca ta ly s t compr is ing a t lea s t moly bdenum a nd
a t lea s t one element s elected fr om the g r oup cons is ting of P,
Si, W , Ti, Z r , V , N b, Ta , Cr , Mn, Fe, Co, N i, Cu, Z n, Ga , In, Tl,
Sn, Ag , As , Ge, B, Bi, La , Ba Sb Te, Ce, Pb, to r educe the
content of pr opa na l loW er tha n 5000 ppm in a n a cr olein- r ich
s tr ea m.
16 . Pr oces s for ma nufa ctur ing a cr y lic a cid compr is ing the
oxida tion of a cr olein obta ined a ccor ding to the pr oces s of
cla im 1.
17. ( ca nceled)
18. Pr oces s for ma nufa ctur ing a cr y lonitr ile compr is ing the
a mmoxida tion of a cr olein obta ined a ccor ding to the pr oces s
of cla im 1.
19 . Pr oces s for ma nufa ctur ing methy lmer ca ptopr opiona l
dehy de us ed for pr oducing methionine or its s a lt or its
hy dr oxy l a na log ue, compr is ing the a ddition of methy l mer
ca pta n to a cr olein obta ined a ccor ding to the pr oces s of cla im
1.
20. Pr oces s for ma nufa ctur ing a cr y lic a cid fr om g ly cer ol
compr is ing the s teps of:
a ) dehy dr a tion of g ly cer ol to g ive a n a cr olein- r ich s tr ea m
conta ining pr opa na l,
b) s elective elimina tion of pr opa na l by pa s s ing the s a id
s tr ea m in g a s pha s e in the pr es ence of oxy g en thr oug h a
ca ta ly s t compr is ing a t lea s t moly bdenum a nd a t lea s t
one element s elected fr om the g r oup cons is ting of P, Si,
W , Ti, Z r , V , N b, Ta , Cr , Mn, Fe, Co, N i, Cu, Z n, Ga , In,
Tl, Sn, Ag , As , Ge, B, Bi, Cr , La , Ba Sb Te, Ce, Pb, a nd
c) oxida tion of the a cr olein to g ive a cr y lic a cid.
a ccor ding to cla im 20 cha r a cter ized in tha t it compr is es a s tep
of pa r tia l condens a tion of the W a ter a nd hea vy by - pr oducts
coming fr om the dehy dr a tion s tep befor e the s elective elimi
na tion of pr opa na l.
22. ( ca nceled)
a ccor ding to cla im 20 fur ther compr is ing the s teps of collect
ing the r es ulta nt a cr y lic a cid a s a s olution by us ing W a ter or a
s olvent a nd then of pur ify ing the r es ulta nt s olution conta ining
a cr y lic a cid us ing dis tilla tion a nd/or cr y s ta lliza tion.
* * * * *

(2013) US20130324758 Process For Manufacturing Acrolein-Acrylic Acid

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( 19 ) United Sta tes

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