CA1075669A - Oxidation catalysts - Google Patents

Abstract

OXIDATION CATALYSTS

ABSTRACT OF THE DISCLOSURE

The invention is an oxidation catalyst which contains at least a Group IIA or Group IIB element or manganese plus as required elements, chromium, bismuth and molybdenum.
The catalysts can optionally contain a number of other elements and are useful for various oxidation reactions, especially the ammoxidation of propylene or isobutylene to obtain acrylonitrile or methacrylonitrile, the oxidation of propylene or isobutylene to obtain acrolein or methacrolein and the oxidative dehydrogenation of olefins containing 4 or 5 carbon atoms to obtain the corresponding diolefin.

Description

BACKGROUND OF THE I~VENTION
Oxldation cataly~ts ~imllar to those o~ the ~n~r~ntlon are ~cnown although the cataty~t~ of` the lnventlon h~ a 15 different compo~itlon ~rom any of the catalyst~ in the Brt, ~he catalysts o~ the inven1;ion ~re prepared accordlne to tec~n~ques that are generally ~pplicable to the c~taly~t~ o~
the artO
The oxld~tion r~actlon~ in which the~ cataly~t,~
20 ~re e~peclally ~ultable are well Icnown. Bro~dly9 ~hese r~action~ are a vapor ph~e resctlon u~lng the ~olld c~Galy8t of the lnventlon. The reactant9 are pa~sed over thc catalyst ln ~Ghe presence Or moleclllQr oxygen at an elev~ted temperature to obtaln the de~ired product.

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3L~75669 SU~.ARY OF THE INVhrNTION
_ _ _ Thi s lnvention i~ new oxidation cataly~ts of the ~ormula Aa C~ Dd Cre Bl~ M12 x wherein A is an alkall met~l, Cu, Sn, Rare earth metal or mixture thereof';
C is a Group IIA or Group IIB element, man~ane~e or mixture thereofi;
D l~ Ni, Co3 P, A~, Sb, Ge, B~ or mixture thereof';
and wherein a i~ 0-4;
. c 1~ 0.5 to 20;
d 18 O-29 e Qnd f are Q . l-12 and x i~ the number o~ oxygens requlred to satis~y the valence requlremen~ I
o~ the other elemen~9 pre~entO .
These oxidatlon catalyst~ are u~e~ul for a number o~ oxld~t~on . ~ ~.
reactlon~ described below.
The catalyst~ covered by the present in~ention ~re any o~ those that are delimi~ed by the rormula aboYe . o~
~pecial int~rest in the ln~ention are tho~e cataly~ whlch contaln calcIum, magne~iumJ mangane~e~ cadm~ zinc or ~ ¦ ~
mixture thereo~. Thi 8 i~l accompll~hed ln the formula set I ;
~orth above by setting C equal to the~e recl~e~ el~ment~
. Al~o o~ particular lnterest in the ln~entlon are tho~
cataly8t8 that cont~ln pot~sluDI~ copper, tin or mixture ~her~o~,, Thl~ i8 accompll~hed ln the rormula ~ettlng Q equal to the~ element~ and pro~riding that i8 greater than zero. . ~:
~he catalyst~ of the invention are prepared 1n mann~r whlch i~ ~imllar to the prep~ratlons conduc~ed in the art ~or rel~ted caltaly~ts. See f'or example, UO 5. ~"642jg3û.

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1~7566~ (4787) Normally, the catalysts are pr~pared by eoprecipîtatlon of solubl~ salt~ f'rom an aqueou3 ~olution, The preclpitate 1B then dried and heat treatad ln air to ~orm ~ catalytlc oxlde st2~ucture .
In the for;Qul~ de~crlblng the cataly3t~ o~ the lnventlon, lt i8 Been that the number o~ oxygens i~ ~e~lgrlated by "x". Thl~ x 18 of variable nature becau~e in actu~l operatlon o~ the~e oxidation catalysts, the catRly~t~ are contlnually gainlng and 108ing oxygen, and the sett~ng of a - lO etrict number on these ~at~lysts accordingly would be an imprecl~e ~tatement. Broadly, the value ~scrlbed to x would ~all wlth~ n the ranee o~ the number o~ oxygen~ r~quired in the hl~hest oxldation state to ~v~lue ere~ter than 50% o~
that number o~ oxy~enatlon to signlfy the reduced Btate~
Althou~h the reactions ln whlch the~e catalysts are especially ~ultable are known ln the ~rt, the ~ollow~ng discussion glves some broad parameters ln whlc~ ths reactionc . are normally conducted. For the ~mmoxidation o~ propylene ~nd lcobutylene, the reactlon 19 conducted ln t~e presence Or ~ cat~lyst descrlbed Qbove at a temperature ot' about 200 to ~:bout 600C. The cont~ct time may range f`rom le8s tt~an a aecond to 20 seconds or more. Ihe reactlon can be conducted wlth the cat~lyst o~ the inventlon elther ln a flxed be~
~o~m or a fluid bed form at atmo~pheric, subatmospherie or superatmospherlc preseure.
The other reactions ~or whlch thes~ cataly~t~ are e~pecially use~ul, the oxidatlon of other ole~lns~ are well known in the ~rt and the parameterB applled to the ammoxldation ~', re~t~on would apply Ql~o to these rea~tions.

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( 47~7 ) lg~75G69 ~P~CIrlO IVYO IM S
_ Preparation o~ varlous catalyst~.
Variou~ cataly~ts eonsistl,n6 o~ 80% of the active m~terlal and 20% o~ Biliea were prepared a~ described below.

Example 1 ;
snd 20~ SiO2 - A alurry con~lAting of water and 63.56 g. (NH4)6Mo7024-4H20; 4~,37 g.
Nalco, 40~ 3illca sol; and 3.46 g. H3P04, 42.5% solution; wa~
prepared and comblned wlth a ~olutlon o~ 9.00 g. CrO3; 53.85 g.
g- M~(N3~2~6H2; 3-03 ~. KN03, 10~ 801ution; and 14.55 g.
Bl~N03)3-5H20, The slurry was evaporated to drynes~ and the resultlng solld was furth~r drled o~ernight at 120 C, m e solld w~s then heated ln air at 290C. ~or three hour~J 425C.
~or three hours and at 550C. for 16 hours to form the active catalytic complex.

Example_2 J

m ie catalyst wa~ prepared in the same manner a~ de~cribed ~bo~e usln~ a 81urry contalning 63.56 g. (NH4)~Mo7P24-4~20;
49,50 g. Nalco~ 40% slllca 801; and 3.46 g. of a 42.5~ ~olutlon o~ H3P04; and a 801ution containlng 22.24 g. Cr(C2~32)3'~2;
57.70 g, Mg(No3)2-6H2o; 4.36 g. Nl(N3)2-6H2; 3-3 g- ~ ~
10~ solution of KN03; and 14.55 g. Bi~N03~3r5H20. The ~olid ~ep~rated was h~at treated in the m~nner described abo~e~

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~ ample 3.
80% K0.1Mn7Cr3BiPo.5Mol20~ and 20% SiO2 _ Thl~
cataly~t Wa3 prep~red ln the ~ame m~nner as described ~n ExHmple 1 u~lng a slurry containin~ 63.56 g, (NH4)sMo7024~4HzO;
52.42 g. Nalc~, 40~ ~iliea ~ol; and 3.46 g. H3PO4J 42.5~
eolutlon; ~nd a ~olution cont~inlng 9.00 g. CrO3; 75.18 g.
Mn(NO3)29 50~ solution; 3.03 e. KN039 10% solutlong ~n~
14.55 g. Bi(N03~3~5H20~ The solid Heparated wa~ heat treated 1n the manner described ~bo~e~

Example 4 80~ K0.1N10.5Mn6.5~r3B1Po~Mol20x and 20~ S102 ~
ml 8 cat81y9t wa~ prepared in the same manner a~ de~crlbed in Example 1 u~ing a 81urry containlng 63.56 ~. (N~4)5Mo~ 24-4H20; 51.13 ~. N~lco~ 40~ S10~; and 3.46 g. H3P04~ 42.5%
solution; and a solution con~aining 9~00 g~ CrO3; 69.79 g.
Mn(N03)2~ 50% solution; 4.36 e. ~l(N~3)2-6H20~ 14-55 g-Bl(N03)3~5H20~ and 3.03 g. ~N03. The ~ol~ ~epar~t~d was heat treated in the manner descilbed above.

~0% Ko.8M~3~ ~ ~3.scr3~lp~ 12x ~nd 20% SiO2 _ Thl~ ~taly~t was prep~red in the ~ame manner as d~`~crib~
in Exampl~ 1 u~lng ~ ~lurry contalning 63.56 ~D (N~4)6Mo~24-~H203 50~43 g. Nal~o~ 40% ~lic~ 801~ and 3~6 g. H3P04~ 4205%
~olution; and ~ ~olutlon containin~ 9.00 g. CrO3; 26z92 g~
Mg(~o3)26M2~; 37-6~ g- Mh(~03)2~ 50~ solution; 3.03 B. ~
: 45% K0~ solution; and 14.55 B. ~ Q3)3-5H2~ The 8011 . separate~ wa~ heat treated ln the manner descrlbe~ a~oY~.

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1~7S66~ (4787) ~e~
80,~ C~0 lCoO sMe~6.sCr3l3isbo.5~ol2Qx ~d 20% ~i~)2 ___ mls ~at~lyst was prepared ln the saDIe m~nn~r de~cribed ~bove u~inæ a slurry containlng 63-56 g~ (~4)6M~7024'4H203 4~-28 ~-Naleo, 40% S102; 2.19 g. Sb203; arld a solutlon containlng 9.00 g, CrO3; 50.00 ~. Mg(No3)2-6H2o; 4,,37 g. Co(N0332-6H20;
14.55 g. Bi~N03)3-5H20; and o.58 e. Cs2~03. me solld s~par~ted was heat tre~ted in the manner d~cribed above, 80~ M~Crl.5Cu1,5}~1Po.5Mol20x and 20% S102 _ mlg _ _ __ _ _ _ _ _ catalyst was prepared in the s~ne manner described above u81ng Q ~lurr~r cont~lnine 63,5~ g. (NH4)6Mo7o24~4H2o; 47-78 g-~alco, 40~ sllica ~ol; Qnd 3.46 g,, H3P04~ 42.59t ~olution; And a ~olutlon eontain~n~; 53.83 g. Ilg(N03)2~6H~0; 10.8a g.
Cu(NQ3)2 3H20; 4.50 g, CrO3; and 14.55 g. Bi(N03)3-5H20, Th~ solld separ~ted wa~ heat tr~te~ in the manner de~crlbed above O

~e~
~I
~- ffl~
~atalyst was prepared in th~ ~ame m~nner described ~bov~
u~ing Q ~lurry cont~lnlng 63.56 ~ )6Mo7o2l~4H2o~ 49,78 g~
N~lco~, 40% ~lllc~ 801; and 3.46 g. oP a 42~5% eolutlon os"
~I~P04~ and A ~olution contalnlllg 53.83 ~,0 Mg(N3)2'~2~
14.55 e~ Bi(No3)3.5H2o; 4.50 g. CrO3, ~nd 6.78 gO SnO2.
m~ sol~d ~par~ted wa~ he~t tre~ted 'In the manner de~cr~b~d above.
.~
.

~ (4787) ':
.' ~ .
,~
80~ CalCrO SnO Blo 2Mo~O and 20% SiO2 - This .5 _ . _ c x catalyst WA 9 prepared in the ~ame manner de~crlbed above u9~ne ~ ~lurry containing 22.95 g, (N~4)6Moro24-4H2o~ ~1-09 g-Nalco~ 40% ~illca sol; ~nd A solutlon contalning 15.35 gO
Ca(N03)2o4H?0; 3.25 g. CrO3; 6.31 g. Bl(N03)3-5H~O; and 4,90 g.
SnO2, The solid sep~rated wa~ heat treated in the m~nner descrlbed above.

Example 10 ~-~; Thi~ catalyst was prepared ln the ~me manner de~crlbed above ; u~lng a ~lurry containlng 63.56 g. (NH4)6Mo7o24-4H2o; 53-20 ~-: N~lco~ 40g S102; and 3.46 g. of ~ 42.5% 801ution o~ H3P04; Rnd a solutlon contalnlng 9.00 g. CrO3; 14.55 g. Bi(N03)3.5H20;
32,39 g. Cd(N03)2-4H20; 2Ç.92 g, Mg(No3)2-6H~o; and 1.52 g.
KN03, me solld separated w~ heat treated in the manner deacribed above.

Ex~mple 10-a _ Thi8 cataly8t.was prepared in the same manner described abo~e u~ing a slurry cont~ining 63.56 g. (NH4)6Mo702~-4H20; 57003 g. Nalco, 40% S102; and 3.46 g. o~ a 42.5~ solutlon of H3P04; and a ~olutlon containlng 9.00 g. CrO3; 43.65 gO Bi~N03)3.5H20;
7.32 g, ZnO~ 4.3~ g. Ni(No3)2-6~2o; and 4~55 g. KN03. T~e : 25 slu~ry was evaporated to dryne~ and hea~ treated ln the manner de~crlbed above, .: . ~ ~ . . . .

~ 7566~ (4787) Example 11 - Preparatlon of ~ cataly~t wlthout silica, The preparation of a catalyst o~ Ca2Sno,sCro.sBiMo2o~ was attempted a~ ~ollow~:
In 20 cc~ of water 24.93 g~ of Ca(N03)2.4H20 was dis~olved and 2~65 ~. CrO3 and 3.g9 g~ SnO2 were added. To thl~ mixture wa6 added dropwl~e a solution of 18.72 g, (NH4)6Mo7024.4H20 di~solved in 50 ec. of a 9.3% ammonia 801u~10n, and then 25.36 g~ Bl(N03)3 5H20 dlssolved in 40 cc. o~ a 13.8% HN03 ~olution w~s added. The pH o~ the mlxture wa~
brought to 4.0-4.5 wlth about 10 cc. of ammonium hydroxide, The mixture wa~ stirred ~or 30 minutes an~ aged ~or 48 hours.
The cat~ly~t was wa~hed with 1440 ml. of w~t~r, ~lltered an~
drled at 120C. ~he c~taly~t wa~ heat tre~ted at 540C.
~or 16 hours. Due to the leaching o~ calclum during the c 15 washing, the ~lnal compositlon of the catalyst wa0 determlned to be Cal~8sn3cr3Bl6~ol2ox.

_e ~ - Preparatlon o~ acrylonltrile, The cat~lyst~ employed ln Example~ 1-10 were teste~
in the ammoxldatlon of propylene. m e fe~d employ~d had ratio o~ propylene/ammonia/air/steQm o~ 1~1.1/10~4. The cRtalyst in each o~ the reactlon~ wa~ groun~ ~nd ~creened and ch~rged to th~ 5 cc. reaction zon0 o~ a kubular reaetor constructed o~ a 1 cm. in~lde dlameter stainleB3 at~el ~ub~.
T~ble 1 shows the cataly~t employed and the re~ction temperature and eont ct time ~nd the result~ used wlth t~e ca~aly t~.
The re8ultB ar~ expre~6ed in the followlng te~mB:
n~erB~on = amount o~ reactant re~cted x 100 9~ selectl~lty - = =
~IOWlt 0 rea~ ~n rea~ e 9~ gle pa98 ~leld = ~
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: (4787) ~7566~31 _ Preparatlon of acrylonltr~llg u~ing a 100%
active catalyRt.
The cataly~t prepared ln Ex~nple 10 w~s u~ed ln the produ~tion o~ acrylonitrile u~in~ ~ dlf~erent react~nt ~
of propylene~ammonia/air/~team ln the ratio o~ 8/2. The te~perQture o~ 450 C. and apparent cont~ct time of three seeond~ were u~ed. Thl~ reaction gave a 68.4% B~ ngle paa3 yleld to acrylonltrile at a 7g~ selectivlty.

_ Ammoxi~tion of isobutyleneO
~arious c~taly8t8 prepared above were t~ste~ in : the ~mmoxldation of isobutylene using a contac~ tlm~ o~
3 scconds und R reQCtant ~eed of leobutylene/Qmmonl~/air/
steQm of 1/~.1/10/4. The re~ult~ o~ the~e experim~nts ~re ~hown ln Teble 2.

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(4787) ~ 7~ 6 Exam~le_37 - Oxydehydrogen~tion o~ butene-l.
The catalyst of ExAmple 2 wa~ employed in the oxydehydrogenatlon Or butene-l u~in~ a ratlo Or butene-l~air of 1/14. The reactlon wa~ conducted at 400 C. ufiing ~ cont~ct time of 3 seconds. The slngle pass yleld to but~diene wa~
77.6%, the converslon Qf the butene-l was 86,9~ and the ~electlvlty to butadlene wa~ 90~.
.

Example_38 - Oxydehydrogenatlon o~ butene-20 Using the catalyst o~ Example 5, butene-2 was ~0 con~erted to butadlene u~ing a reQctfl.nt ratlo of cl~/tr~ns butene-2 (42.5~ cl~ ~ 57.5% trRns)~air o~ 1/11. A re~ction temperature of 490C. and an apparent contact tlme o~ 3 seconds were used. The single pass yield to butQdiene was 68.1%. The converslon o~ butene-2 wa~ 73.1~ and the selecti~ity was 93~.

; In the same manner as shown above, other cat~l~sts within the scope of the ~ormula may be prepared ~nd u~ed ~n ammoxidationg oxydehydrogenation and oxidation reactlons.

Claims (7)

WE CLAIM:

1. An oxidation catalyst having the formula Aa Cc Dd Cre Bif Mo12 ox wherein A is an alkali metal, cu, Sn, rare earth metal or mixture thereof;

C is a Group IIA or Group IIB element, manganese or mixture thereof;
D is Ni, Co, P, As, Sb, Ge, B, or mixture thereof;
and wherein a is 0-4;
c is 0.5 to 20;
d is 0.2;
e and f are 0.1-12 and x is the number of oxygens required to satisfy the valence requirements of the other element present.

2. The oxidation catalyst of Claim 1 wherein C
is calcium, magnesium, manganese, cadmium, zinc or mixture thereof.

3. The oxidation catalyst of Claim 1 wherein A
is potassium, copper, tin or mixture thereof and a is greater than zero.

4. In the process for the ammoxidation of propylene or isobutylene in the vapor phase to product acrylonitrile or methacrylonitrile by contacting propylene or isobutylene, ammonia and molecular oxygen with a catalyst at a temperature of about 200° to about 600°C., the improvement comprising using as the catalyst a catalyst of the formula Aa Cc Dd Cre Bif MO12 ox wherein A is an alkali metals Sn, rare earth metal or mixture thereof;

C is a Group IIA or Group IIB element, manganese or mixture thereof;
D is Ni, Co, P, As, Sb, Ge, B, or mixture thereof;
and wherein a is 0-4;
c is 0.5 to 20;
d is 0-2;
e and f are 0.1-12; and x is the number of oxygens required to satisfy the valence requirements of the other elements present.

5. The process of Claim 4 wherein C is calcium, magnesium, manganese, cadmium, zinc or mixture thereof.

6. The process of Claim 4 wherein A is potassium, copper, tin or mixture thereof and a is greater than zero.

7. The process of Claim 4 wherein the product is acrylonitrile.