CA1065340A - Process for the preparation of acrylic acid and methacrylic acid from corresponding aldehydes - Google Patents

Abstract

PROCESS FOR THE PREPARATION OF ACRYLIC
ACID AND METHACRYLIC ACID FROM THE
CORRESPONDING ALDEHYDES

ABSTRACT OF THE DISCLOSURE
Catalysts containing tungsten, phosphorus, vanadium and molybdenum have been round to be especially effective for the oxidation of unsaturated aldehydes to form the corresponding unsaturated acid. These catalysts may optionally contain one or more of tin, antimony, arsenic, copper, cerium, boron, chromium, iron, nickel, cobalt, uranium, manganese, strontium, silver, rubidium, rhodium, cadmium, bismuth, indium, zinc, lanthanum.

Description

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 (4739_A~
10f~53 o ~
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? , (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~

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,,,~ 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.
/

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5~3413 ( 4739-A

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_ 14 -

Claims (6)

WE CLAIM:

1. A process for the production of acrylic acid or methacrylic acid comprising reacting acrolein or methacrolein with molecular oxygen at a temperature of 200° to 600°C. in the presence of a catalyst and optionally in the presence of steam, the improvement comprising using a catalyst consisting essentially of tungsten, phosphorus, vanadium, molybdenum and oxygen, said catalyst having the formula Wa Pb Vc Mo12 Ox wherein a and c are about 0.1 to about 12;
b is a positive number less than about 6; and x is the number of oxygens required by the valence states of the other elements present and said catalyst optionally containing one or more of tin, antimony, arsenic, copper, cerium, boron, chromium, iron, nickel, cobalt, uranium, manganese, silver, rubidium, rhodium, cadmium, bismuth, indium, zinc, lanthanum.

2. The process of Claim 1 wherein b is about 0.5 to about 3.

3. The process of Claim 1 wherein antimony is present in the catalyst at a level of 0.1-6.

4. The process of Claim 1 wherein acrylic acid is produced.

5. The process of Claim 1 wherein methacrylic acid is produced.

6. The process of Claim 1 wherein the catalyst contains one or more of tin, antimony, arsenic, copper, cerium, boron, chromium, iron, nickel, cobalt, uranium, manganese, silver, rubidium, rhodium, cadmium, bismuth, indium, zinc, lanthanum.