Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
BACKGROUND OF THE INYENTION
A number Or c~tslyJts are ~nown for the oxl~atlon
Or un~atur~ted ~ldehydes to the correspondln6 scld, ~ee
~or example, U. S. 3,567,773. Al~hough most of the dt~clo~ures
suRgest that the cat~lysts are use~ul for oxidlzln~ meth~croleln
to methacryllc ~c~d, lt ha~ been round that the ylelds Or
methacryllc acld sre low and that special catalyst~ are
rcqu~red ln thl~ reactlon.
(4739_A)
10~i53~0
SUMMARY OF THE INVENTIO~
It hss now been dlsco~ered a proccs~ ~or the productlon
Or acryllc acld or methacryllc acid comprialng reactlng
acr~l~ln or methacroleln wlth molecular oxygen at a temperature
o~ 200 to 600C.~ ln the presence o~ a cAtaly~t snd optionally
ln the presence Or ste~m, the lmprovement comprislng
~lng fi CQtaly8t consl~tlng es~entlally o~ tungsten,
phosphorus, v~nadium, molybdenum and oxyg~n, said catalyst
havlng the ~onmula
W~l Pb VC M12 x
whereln a and c are about 0.1 to about 12
b iB a po~ltlve number les~ than
~bout 6; and
x ifi the number of oxygens requlred
by tho valence statcs Or the other
elements present
snd said catelyst optlonally containlng one or more Or tln,
sntlmony, ar~enlc, copper, cerlum, boron, chromlum, lron, nlckel,
cobalt, uranium, manganese, ~llver, rubldium, rhodium, csdmlum,
blsmuth, strontlum, lndium, zlnc, lanthanum. ffl e cataly~t~ o~
tho lnvontion gl~ high single psss yield~ to methacryllc acid
snd aPa very stable under the requlred operating condltlons.
Tho central ~eature Or the prosent lnventlon 18
the catalyst. Thls cAtalyst le used in tho known process
~or prepsring unoaturated acid~ from the corrc~pondlng slaehydes.
Ibe catalyst~ may be any one o~ the catalysts de~lgnat~d by
the rormula abo~e. m e catalyst m~y be prepared by ~arlous
technlques that are broadly described ln the srt and ~hich
are more ~ully taught by the pres~t ~pecl~ication.
3o In the catAly~t prcparatlons, the varlous elements
o~ t~e catalyst are comblned, and the rlnal product is dried
. _ ., . _ .. _ . . . .
(4739_A)
3 0~5340
normally at a te~perature of about 100-150C. In some prep~ratlon~,
lt 1B help~ul to calcl~ the catalyst at an elevated temperature
Or about 300-600C., but ~uch calclnatlon i9 normally not
required. A n~mber of methods o~ combinlng the elements of
the cataly~t~ are known. The oxides o~ the elements could
be calcined ln a ~lurry, and th~ resultln~ slurry refluxed
and finally evaporated to rorm the catalyst. Alternatlvely
and preferred preparations lnvolve the relf~x Or a solutlon
Or a soluble molybdenum, tungeten and vanadium co~pound,
and then th~ addltlon o~ a phosphorus compound. me pre~erred
prepar~tlons are those that glve th~ best results ln the
Specl~lc ~mbodlments below.
In the catalyst composltion ~ormula above, there
are prererred ranges. Pre~erred are catalysts whereln the
phosphoru~ 18 present ln the range Or about 0.5 to about 3,
l.e., those cataly~ts wheretn b~ls about 0.5 to about 3.
Also pre~erred ln the pre~ent inventlon are those catalysts
whlch contaln at leaet one o~ copper, tln, antlmony, arsenlc,
cerlum, boron, chromium, lron, nlckel, cobalt, uranlum,
mangane~e, sllver and rubldlum. or speclal importance wlthln
thlo group are those catalysts~hlch contaln antSmony at a
lovel Or about 0.1 to about 6 ln the ~ormulB.
~ ho catRlyst of the lnventlon may be used aB pure
actlve lngredlents or lt may be comblned physlcally wlth a
support materlal. A number Or ~ultable supports are well
~nown ln the art ln an experlmental study on supports. It
~as round that slllca, zlrconla, dlatomaceou~ earth, tltanla
~nd alumlna ~upports ~enerally tcnded to malntaln the actlvlty
Or the cataly~t whlle elllca gel and alumlna gel tended to
(4739-A )
10ti5340
reduce the errect~vensss of the cst&lysts. The cstalysts o~
the present lnventlon can be u6ed w~th any of these ~upport
materlals,
The catalysts of the inventlon may al~o be co~ted
on ~ m~sslve lnert support. Th18 coetlng technlque 1~
speclflcslly ~hown in Examples 8-14. Broadly, th~ B technlque
involves wetting a poroue m~lve support wlth water to the
extent th~t water does not remaln on the sur~ace o~ the
ma~slve support and then contacting a powder o~ the actlve
c~telytlc mnterlal with the masclve support whllc rotatlng
the massive support in a contalner such aB a slmple glas~
J~r. Coated catslysts have been ~ound to be especlally
effectlve ln thls resctlon to control the temperature o~ the
reaction. As lndlcated above, the proce~s of the lnventlon
whereln the unsaturated aldehyde 18 oxidized to the correspondlng
uncsturated ~cid 19 well known ln the srt. Brosdly, the
resctlon lnvolves a react~nt feed o~ the unsatursted ~ldehyde
and molecular oxygen over the cstaly~t. The rc~ctant feed may
al80 contaln 8 dlluent whlch 18 normally steam. Tho rstlo
o~ the reactants ln the feed may vary wldely. Nor~ally
~bout 0.2 to about 4 moles o~ mdlecular o~ygen sre present
per mole o~ the unsaturated aldehyde. The amount o~ dlluent
employcd msy also vary wldely, but norm~lly ~118 wlthln the
renge Or about 1 to about 10 moles of dlluent per mole o~
tho unsatursted sldehyde.
A~ noted above, the reactlon 18 norm~lly conducted
at a reactsnt temperature Or 200 to 600~C., wlth temporaturea
of about 300 to 400C. belng o~ spcclal lnterest. The resctlon
can b~ conducted under ~ubstmospherlc, ~uperAtmospherlc or
~tmoepherlc pres~ure~ at a cont~ct time rsnglng rrom A
_ _
(473g_A)
~ O~S340
~ractlon o~ a ~econd to ten ~econde or more. Reactlon ean
be conducted ln ~ n uld bed or more commonly ln a ~lxed bed
re~ctor.
A~ noted, t~e proce88 Or the lnventlon 1A relate~
to the preparatlon o~ ~crylic ~ld or mothacryllc ~eld ~rom
t~e correspondlng unsaturated aldehyde. Of ~p~clal lnterest
~n t~e lnvcntlon i8 the productlon of meth~cryllc acld fro~
mothacrol~ln becauDe o~ the v~ry hlgh yield~ obtalned and
the ~m~ll omounte Or by-product~ formed.
SPECIFIC EMEO M MENTB
~m~les_1_7 _ Productlon Or m~thacryl~c aci~ ~rom
m~thacroleln,
Varlou~ cat~lyst~ o~ the lnvcntion were pr~pared
as descrlbed below and te~ted ~n the oxldatlon o~ m~t~acroleln
to mcthacryllc acld.
ExQmRlee 1 ~ 2
Wo gPl 3V2Mol20x An aqueou~ ~lurry contslnlng
86.2 g. MoO3, 7.7 g. o~ 85~ H3P04, 7.5 g. V203 and 10.8 B.
a~monlum paratung~tate WR8 prepared. The slurry ~a~ r~ n u~ed
ovornlght, evaporfited and dried st 120C. ov~rnlBht~
Example~ 3 & 4
W3Pl 5V3Mol20x An aqueous 801utlon 0~ 11.5 g. 85~
3 4, 1-2 g- (NH4)6Mo7o24~4H2o~ And 53.9 g. of (NH4)6W ~ 4-
~ 0 ln 1500 ml. o~ wnter, To thlg ~olutlon wa~ added 23.4 g,
~ N~4V3~ m e re~ultlng ~lurry wa~ d~ep red and on a contlnuod
~atlng b~cam~ orange. m e r~Jultlng mlxture was evaporatcd
and drled at 120C. overnlght,
(4739-A~
lOf~S340
Wl 2PV3Ml2QX A solution oP 17.Ç g. NH4V03 dlssol~e~
ln one llter o~ w~tor wa~ prop~r~d. To thl~ solution was
~dded 105.7 e. (N~4)6Mo7024~4H20, and the mlxture wa~ heatod
with ~tlrring unt11 th~ aolld wa~ dis~olved. ~o 'cho rosultin~
~olutlon 5.76 ~. Or 85% H3P04 wa~ added, and the ~olutlon
turned red. To thls m~xture wa~ added 16.2 B. ~o~olum
para'cung~t~ Qnd ~11 sollds appeared to be dissolv~. me
cat~ly~t ~ vRpor~ted to d~ne~, and tha reeultlng soll
0 W~8 drled at 110C. overnight. The sol1d WBB ground to
'chrough 20 on 30 U. S. Standard ~sh, and tho screened solld
wae heated Bt 430C. ~or two hour~.
Wl.2P2V~120ac m~ prepQration 0~ unple 5 ~ta~
~ollowed oxcept th~t 11.52 g. o~ 85% H3P04 ws~ Qdded r~ther
than 5 . 76 g.
~:Z
W1 2P3V3Mol20x ffle prephrat~on os' Example 5 W~8
~ollowed exeept that 17.30 g. o~ 85~ H3P04 wa~ add~d r~tl~or
th~ 5 . 76 g .
A roactor Wl!13 con6tructed of 8 1 cm. ln~lao dl~noter
~t~lnles~ steel tub~ hAYlng a reactlon zone o~ 20 cc. A
mlxturo o~ m~thacroleln, filr and ate~m were ed o~cr t~o
cat61y~t ln a ratlo o~ 1/6,3/5.2 at the tempera~ure and
apparcnt contAct tl~ Ehown ln the T~blc. ~he compo~ltlon~
o~ thes~ oa~lyots and th~ rcsule~ uslng the~c cataly~t~ aro
~o~n ln Tsblo I. The redUlt8 are ~t~t~d aA ~ollow6:
( 4739_A ~ '
10~5340 1-
mcs~es o~ produc~ ~ormed x 100
lngle p~8e ylcld c mol28 Or m~thacroleln ~ed
eonvor~lon ~
~oles of mQthscrol~ln ~ed
moles of methacrYllc acld ~ormed x 100
colec~-vlty ~olec o~' methacrol~ln reacted
-- 7 --
(4739_A~
10f~53
o ~
S~ ~ ~ O U~ ~D
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,¢ b ~ U ~ a~ CU ~ ~1 0~ N
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~ ~ ~ ~ O~
~ 8 ~1 N U~ 1~ ~I C~J C~J
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-- 8 --
? , (4,39_A)
53~V
amples 8-14 - Actlve cat~lytlc mater~al co~ted o~ e.
~upport.
An act~w catalytlc m~terial havlng the ~or~ula
W3P2V2Mol20x was prepared by dlssolvlng 706,26 8. ~
(NH4)6Mo7o24c4H2o~ Z80.91 g, (NH4~6W4024-8H2o ~nd 78-oo g-
NH4V03 ~n 3 llters of boilln~ dlstilled wat2r, After three
hou~a, the bolllng WQ8 dlscont~nued and stlrr~ne wa3 contlnued
o~er thc weekend. To t~e resultlng ~olution was then added
76.86 g, Or 85% ~3P04, the mlxture wa8 bolled down snd the
solid drled ~t 110C. and calclned at 415C. for ono hour.
mi~ actlve catalytlc powder wss coated on Alundum
partlcles sold as Norton SA_5209. The psrtlcle~ were
pl~ced ln ~ gla~s Jar and wetted ulth water, The wster
con~cnt was reduced to 2.4 g,/25 e. of partlcles wlt~ the
rlow o~ alr Srom ~ hot alr eun. The actlve catal~tlc powder
w~ ground to a 81zc of less than 50 U. S. Standard me~h.
While the ~lass ~ar was rot~ted on ~n ~ngle sbout 17 ~. Or
ectlve powder per 25 g. o~ Alundum W25 add~d in ~lYe ceparate
portlons. Between eac~ addltlon, the rotatlon o~ the J~r Wa8
continued rrom 15-45 ~inute~. The catAly~t produced was an
Alundum cupport w~th a strongly ad~erlng coat of act4ve
catalytic materlal. The eatalyst was then drled ln an o~en
at 110C. o~er the weekend. The resulting cataly~t wss
39.8~ W3P2~2Mol20x and 60.2~ Alundwm. In the ~m~ m~nner,
a coatad cat~ly~t contalnlng 34.8~ W3P2V2Ml20x and 65-2%
Alundum sold as Norton SA_203 and ~ catalyst conta1nln6
20.4% W3P2V2Mol20x and 79.6% Alundum SA_203 were sl~o prepared.
U~ln6 the ~ame reactor snd feed as shown ~bove, these
cstaly~ts were te~ted ln the productlon o~ methacrylic acld
~rom methacroleln. The re6ults sre shown ln Table 2.
(4, 39-A~
U'~ N 0~
U~
C
~R o u~
0 N ~ ~ u~ N ~0 N
:~ a~ 0 a~
O
~ C~
~ ~; ~
, ~
U~ t~
0 ,( ~ U~ ; ~ ~ C~J U~
~Uc C~ ~
~ 1: ~
C~l '~ ~ ~;
0 .,
~ ~: ~ ~
E~ ~ o c~v~ C~J C`J
~ # c
o o ^
C N 0 0~~ O ~ o O O C)
~u t~E-
'O ~N
~ r) ~ g~ C ~ ;: ' C
h , ~ ¢ ~ ¢ ¢ ¢ ¢
0 ~i C~O N J- N
C~ ¢ ~ ~ ~o O 1
C~.
~ 0 CJ~ O
1~
,,,~ 10 -
) (l~739-~)
ampl~ 15 CAt*ly~t~ Or the inventlon contalnln6 optional
ele~ents.
~ arlou~ cataly~t3 o~ tho lnv~ntion containln6 dir~er~nt
~lem~nts w~r~ pr~pared ~ 3hown b~lo~.
Exampl~ 15
RbQ.?5W~Pl.5~2.2sMl20X A 3Qlutton of 141.2 g,
(NH4)6Mo7024-4H20 and 11.52 B. 85~ ~ PO ln 2 llter~ o~ water
wa8 pr~p~red. To ~hl0 ~olut~on was added~3.9 g. of (NH4)6W~ 24-
2H20 ~nd. tb~n 17.6 g. Or NH4~03. To t~ mlxture wa~ t~n
8dd~d 7.2 B. a~ RbC2H302~ m e mlxture was bolled dry, an~
the ~olld wa~ drled ~t 110C. o~ernlght.
ample 16
Sno.5cu2wl.2Py~ol2ox A ~lurry was prep~r~d by
tho ~ddltlon to o^00 ml. o~ wst~r 72.0 g. o~ ~oO3, '1.36 B-
25' 3.13 g. SnO2 ~nd 5.65 ~. 85% H3P04. m~ Blurry ~8
heated to re M ux with stlrring o~ernl8ht, To the ~lurry w~
~ben sdded 9.19 g. o~ rinely divided tungst~n metal and ~er
two hours o~ re~lux 16.63 g. of cuprlc acetate ~a~ ~dd~
and r~luxing contlnued for 1.5 hours. The ~lurry wa8 e~por~ted
to dryness snd dried at 110C. overnlght.
33-3% ~nO.5CU2wl.2pv3Mol2ox ~nd 66.7~ Alundum Tho
~cti~e cat~lyst Or Ex~mple 16 W~8 co~ted ~ccordlng to the
procedure sho~n ln Example8 8_14 to obtaln ~ cat~ st having
1/3 act1~e catalytic mat~rlal and 2/3 Alundum.
~ 4739_A ~
l~)fà,S340
Ex~m~les 19 and 20
~ The procedur~ of ~xa~ple ~6
wa~ repQated except that twlce the ~ount o~ H3P04 w~ u~ed.
~ sbW3P2V2Mol2oX m~ BolUt~on w~ prep~r~d u~lng
500 ml~. o~ water and se~uentlQlly dlAsolvlng there~n ô~.3 g.
( 4)6M724 4H20- 35-1 g- ( NH4)6W4013-8~o end 9,7 g.
NH4V03, m e ~olutlon wa~ bolled for rlve hour~ snd allowed
to stan~ overnlght wlth contlnuous stirrlng, To the cool
solutlon wAs sdded 9.6 g. of 85~ H3P04, After ~bout one hour
Or ~tlrrlng, hestlng was resumea. To thl~ hot solut~on ~as
added 6.o5 g. Sb203. The mlxture w~8 bolled dry, and the
~olld was drled in an over over the weekend.
Examples 22_32
The cstalyst~ were prep~red ln the ~ame manner aB
Example 21 to glve c~talyata o~ MlW3P2V2M120x (~xcept ~or
rhodlum cat~lyet whlch used Rho 25~ ~nd lron whlCh ~aA Fe2
by ~d~lng t~e app~oprlate amounts of the ~ollo~lng chemlcsl~
ln ~ach prepQration rather thsn the antlmQny co~pound:
9123, ~1203~ Cr(C2H302) H20; Co(C2H302)-4H20; RhC13 3 2 ;
Cd(C2H302)2.2H20; Fe(No3)3-9H2o; AgC2H32; Sr(H)2 2 ;
Uo2(c2H3o2)2-2H2o; Ce(C2H32)3~1-5~20
These c~talyet~ were employed in the productlon Or
imet~eryllc ~cid ln the manner shown ~bove~ ~nd the re~ulte
l ~ these exp~rlment~ ~re ~hown ln Table 3.
/
- 12 _
(4739-A)
10~53~0
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5~3413 ( 4739-A
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_ 14 -
