Note: Descriptions are shown in the official language in which they were submitted.
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.
2-
,....
... ~ .. . .. ... .. . . .
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~
;
~ , , , - . . . - . . . .
~7 ~6~
~ 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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ll
~ .
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,
- 7
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~ 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 = ~
;
(4~87)
~751669
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~47~7)
1~756~
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- 10 -
. .
: (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.
.~ :
.. 11 --
( 4787 )
~7566~
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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.
- 13 -
