CA1133505A

CA1133505A - Process for the oxidation of olefins

Info

Publication number: CA1133505A
Application number: CA306,381A
Authority: CA
Inventors: Andrew T. Guttmann; Robert K. Grasselli
Original assignee: Standard Oil Co
Current assignee: Standard Oil Co
Priority date: 1977-07-28
Filing date: 1978-06-28
Publication date: 1982-10-12
Also published as: IT1118241B; ES472082A1; EP0000663B1; IT7826141A0; PT68313A; EP0000663A1; NO151083B; RO75319A; AT359055B; ATA551778A; IN148201B; NO782583L; DE2861192D1; DD140034A5; YU182978A; BR7804848A; NO151083C

Abstract

PROCESS FOR THE OXIDATION
OF OLEFINS USING CATALYSTS
CONTAINING VARIOUS PROMOTER ELEMENTS

ABSTRACT OF THE DISCLOSURE

Iron-bismuth-molybdate catalysts further containing specific promoter elements have been found to exhibit excellent redox stability even under high stress conditions in the cataly-tic oxidation of olefins to unsaturated aldehydes and acids.

Description

BACKGROUND OF THE INVENTION
The process for oxidizing olefins by contacting the olefins to~ether with an oxidiæïng agent with multicomponent catalysts is known. Grasselli and Hardman, in U.S. 3,642,930 disclose that certain complex catalysts based on iron, bismuth and molybdenum can be employed in the oxidation of olefins to obtain unsaturated aldehydes and acids. Also, see U.S. 4,001,317.
Also see British Patent 1,437,235, which discloses catalysts based on oxides of bismuth and molybdenum, which further contain at least one of indium, gallium, lanthanum and aluminum.
The catalysts described in these patents and applications are indeed very desirable for the oxidation of olefins to unsatur-ated aldehydes and acids. Unfortunately, some of these catalysts exhibit a less than desired redox stability when subjected to stressful conditions. More specifically, it occasionally happens in a commercial facility that the amount of oxygen fed to the reactor along with ,., ~33~05 the olefin feed is either much greater or much less than the desired value. ~hen this happens, it has been found.that the catalysts may exhibit a significant decrease in catalytic actiu-ity. This, of course, is very disaclvantageous. :
Accordingly, it is an object of the present invention ~ :
to provide a new process for the catalytic oxidation of olefins to unsaturated aldehydes and acids which employs catalysts having .-high redox stability so that the catalysts can withstand major deviations in redox conditions without significant decreases in catalytic activity.
SUM~IARY OF THE INVENTION
This and other objects are accomplished by the present - .~
invention in accordance with which unsaturated aldehydes and acids `
are produced by the vapor phase oxidation of propylene or iso-butylene with molecular oxygen at a temperature of about 200 to ~
600 C in the presence of a catalyst represented by the following .
:, :~ . .
formula~
AaBbFeCxdMeMol2ox wherein A is alkali metal, thallium, silver or mixtures ~ ~
thereof; ~ .
wherein B is cobalt, nickel, zinc, cadmium, beryllium, calcium, strontium, barium, radium or mixtures thereof;
X is Bi, Te or mixtures thereof; and wherein M is selected from at least one of~
(1) Cr + W, Ge + W, Mn + Sb, Cr + P, Ge + P, .~
Cu + W, Cu + Sn, Mn + Cr, Pr + W, Ce + ::
W, Sn + Mn, Mn + Ge or combinations thereof;

(2) Cr, Sb, Ce, Pb~ Ge, B, Sn, Cu or sombinations thereof; and `

(3) Mg + P, Mg + Cu, Mg + Cr, Mg + Cr + W, .~
Mg + W, Mg + Sn, or combinations thereof; and :;:-:
fur:t~er .
wherein 0 - a - 5, 0 - b < 20, 0 - c -~ 20; 0 -~ d < 20, ~
0.01 ~ e -~ 12, and ~.:

-2~
: ~ ., :
,~:
.: -~i33505 x is a number such that the valence requirements for the other elements ~or oxygen are satisfied.

In one embodiment of the invention, the catalyst above- :
described is free of indium, gallium, lanthanum and aluminum when M is B, Cr, Cr + W, Sn, Pb, Ge and/or Cu In another embodiment, the catalyst as generically described above is free of indium, gallium, lanthanum and aluminum. ~:
Preferably, the relative amounts of the various ingredients in the foregoing catalysts are such that the following inequalities apply: 0 - a - 0.5, 0.1 -~ b - 20, 0.1 - c -~ 20, 0.1 -~ d c 20 and 0.01 - e - 6.
The catalysts of this invention preferably contain K, Rb, ;
and/or Cs. Also, in the catalysts of the invention X is preferably ` ;
Bi. -In particularly preferred emobdiment, the catalysts ..
employed in the inventive process are represented by the formula:
AaBbFeCBicMeMol2 x ` :'..'.-~
wherein A is an alkali metal, preferably K, Rb, Cs or ` .
mixtures thereof; .:
B is Co, Ni or mixtures thereof; and ;
M is the same as described above; and further , ::
0.03 ~ a - 0.5, 0.1 - b ~ 20, 0.1 - c -~ 20, 0.1 - d - 20, and 0.1 c e -< 6.
These catalysts are preferably free of IN, Ga, La and Al.
Of particular note are those catalysts falling within :
the foregoing generic descriptions in which M is selected from ;
the group consisting of Cr + W, Ge + W, Cr + P, Ge + P, Cu + W, .`
. ~ i,.!S
Cu + Sn, Mn + Cr, Sn + Mn, Mn ~ Ge, Pb, B, Sn and Mg + Sn.

In the foregoing generic descriptions in which the M

component is a speci.fic two-or-three-element system as . ~-: ` ,. , -3~

described in subparagraphs (l~ and (3~, the minimum amount of each element in the system is 1 r preferably 5~ atom percent based on the total number of atoms in the system. ;

.
DETAILED DESCRIPTION
.. ~
Processes for the oxidation of propylene and/or isobutylene to form the corresponding unsaturated aldehyes and acids are well known in the art. Broadly, a mixture of the ~;
olefin and molecular oxygen r optionally in the presence of steam or other diluent, is contacted with a catalyst at an elevated -~
temperature of about 200 to 600C for a contact time sufficient to convert the olefin to the desired aldehydes and/or acids.
Normally, the products of these reactions contains a very large portion of the aldehyde and a smaller byproduct amount of the unsaturated acid. The contact time may vary widely from a few seconds to ten or twenty seconds or more. The reaction can be -conducted under atmospheric, superatomospheric or subatmospheric pressure with the use`of a superatmospheric pressure normally being used on a commercial scale. `;
~.: ,. . :
An lmportant aspect of the present invention is the particular catalysts employed. The catalyst employed may be any of the catalysts delineated by the formula described above.
. 1 ~, Preferred are those catalysts falling within the foregoing gen-eric description which contain potassium, rubidium, cesium or `~
mixtures thereof and those contain cobalt or nickel or mixtures `
thereof, and catalysts containing potassium, rubidium, ~esium or mixtùres thereof as well as nickel or cobalt or mixtures thereof are particularly preferred.

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~33S05 The catalysts of the present in~ention can be prepared by techniques well known in the art. In this connection, techniques for preparing analogous catalysts are thoroughly described in the patents and application referred to in the Background of the Invention. Such catalysts are most conveniently prepared by ~he coprecipitation of soluble salts, although any other conventional technique can be employed. More ~ specific information on the preparation of catalysts is given in the following specific examples.
The catalysts of the present invention may be employed in unsupported form or they may be supported on a suitable carrier. Suitable carriers include silica, alumina, Alundum, titania, zirconia, silicon carbide and the like. The catalyts may also be used in various physical forms. For example~ the catalysts can be employed in a form suitable for carrying out the inventive reaction in a fixed-bed mode or the catalyst can be employed in a form suitable for carrying out the invention re- ~
action in a fluid-bed form. ~ ;
As indicated above, a remarkable feature of the present invention is that the catalysts employed exhibit significant redox stability. In a commercial plant for producing unsaturated aldehydes and acides from propylene and isobutylene, mishaps inevitably occur. If the amount of molecular oxygen relative to the amount of olefin contacting the catalysts at any particular time significantly drops below the desired value, a noticeable decrease in catalytic activity of the catalyst may occur. In accordance with the present invention, the catalysts employed exhibit a far reduced tendency to lose their catalytic activity when subjected to unfavorable reaction conditions. From a commercial stanclpoint, therefore, the inventive process using the catalysts described herein has significant advanta~es o~er presently commercially practiced processes.

WO~KING EX~IPLES
In order to more thoroughly illustrate the present invention, the following working examples are presented: ~ ;
Various fixed-bed catalysts of the invention containing 20% SiO2 were prepared by the procedures described below. Also prepared were a number of catalysts not included within the pre-sent invention, which were provided for comparative purposes.
Reference Catalyst A - 80% Ko lNi2 5Co4.5Fe3Bi- ~
P0 5Mol2Ox & 20% SiO2 ~;
An aqueous slurry (referred to a solution A) containing 37.00 grams (NH4)6Mo7O24.4H2O, 8.56 grams of a 0.10 g./ml. aqueous ' sdlution of H3PO4, 38 ml. of water and 25.43 grams of a 40% silica sol was prepared. An aqueous solution (referred to as solution B) ~ ~
containing 21.17 grams Fe(NO3)3.9H2O, 8.47 grams Bi(NO3~3.5H2O, ~;
12.7 grams Ni(NO3)2.-6H2O, 22.87 grams Co(NO3)2.6H2O and 1.75 ml.
of a 0.10 g./ml. aqueous solution of KNO3 was separately prepared.
Solution A was then heated initially to 45-55C and solution B `~,~
added dropwise to solution A with stirring. During addition of solution B, the temperature of the composition was increased so as to reach 75-80C at the end of the solution B addition. Stirring was continued and the temperature of the composition maintained between about 80 and 85C until sufficient water had evaporated so that a thick paste was obtained. `~
The thick paste was placed in an oven at 120C and heated -for about 2 1/2 hours, the paste being stirred every 1/2 hour.
Heating was then continued until the paste was dry. The dried paste was then heated in air at 290C for 3 hours and then at 425C -for 3 hours. The heated paste was then additionally heated in air at 550C for 16 hours to produce the indicated catalyst.

, . .

~.~L3350S

Reference Catalyst B - 80% Ko lNi2.5Co4.5 3 0.5 12 x&

20% SiO2 The procedure described above for the preparation of ~ -Reference Catalyst A was repeated except that an appropriate 5 amount of (NH4)6W7O24.6H2O was substituted for the H3PO4 in solu~
tion A.
Catalysts 1 to 21 . :
Catalysts having the general formula~

r 0.1 i2~5C4 5FeqBiz0 5Mol2 wherein L is Cr, Ge, Mn or Cu;

Z is W, Sb, P, Sn, Cr, Cr, Pb, Ge or B: and wherein q = 2 or 3;
r - 0 or 1; and ~
q + r=3 `
were prepared by the general method described above in connection with the preparation of Reference Catalyst A.

These catalysts, which are composed of a base catalyst Ko lNi2 5Co4 5BiMol2Ox and a promoter system FeqLrZ0 5, are des-cribed in the following Table I. In this table, only the promoters are identified, the catalysts of course being composed of the identified promoters plus the base catalyst.
Oxidation of Propylene to Acrolein and Acrylic Acid In order to illustrate the excellent redox stability of the catalysts of the present invention when employed in the inventive ~`
process, each of the catalysts described in Table I was subjected to a redox test in the following manner. 5 cc. of each catalyst prepared above was charged into a fixed-bed reactor. The temper-ature of the catalyst in the reactor was raised to a predetermined value and a feed comprising propylene/oxygen (in the form of air) /water in a ratio of 1/2.3/4 was fed to the reactor at a rate :,' '. :
""''`~`
~7- `
~ , ':

~13350~

such that the apparent contact time was 3 seconds and a WWH of about 0.07. Once the reaction had commenced, a sample of the product was recovered and analyzèd for acrolein and acrylic acid so that the initial catalytic activity of the catalyst could be ~ -~
determined. Thereafter, the ratio of the ingredients in the feed as indicated above was changed to 1/0.7/4, and the temperature of the catalyst was raised to 400C. This low oxygen feed was fed to ' the reactor under these conditions for a period of 2 hours. Next, the catalyst was reoxidized by feeding a feed of oxygen (in the form of air)/steam in a ratio of 2.3/4 to the catalyst at the reaction temperature indicated in Table I for 1 hour. Thereafter, the propylene flow was resumed to its initial value, and a product sample taken after the reaction had proceeded to steady state.
The results of these experiments are given in the following Table I. In this Table, the following definitions are used:
Moles of Propylene Reacted Per Pass ConverSatln = Moles of Propylene Fed x100 Selectivity = Moles of Product Formed x 100 Moles of Propylene Reacted ~

Performance Number = 1/2 {(PPC to ACR. + AA) + (SEL. TO ;, ACR. + AA)} -In table I, ACR is acrolein, and AA is acrylic acid. The ~-`
performance number as defined above is a measure of the cataytic `
activity of a catalyst in that it is a function of both the selectivity and per pass conversion.
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w w~ ~ ~ a n ~ ~ O a o ~D:r ~ s rt y rt i` a ~-~ ~ 3 ? ; ? ? ? ~ cn -~:
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n 3 3 n 3_~ w ~w w w w ~ w ~ w ~3 O o o oo~ o ~ ~ ~ o o o ~ ~,tn oo e ~ 3~1 D ~ ~n ~D1~O~ 15` ~ ~D W O~O CO ~ rl ~n o ~ 1~ I _ ~ w ~o D Cr~ ~1~ ~ O W ~ ` ~ ~ U~
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W ~ n ~CO ~ ~J O ~Q ~ O O 3~ Z

+ + I I I I I I I I I I I ~
w Yl~ y CO lo~ o o r o ~O ~n O ~ O O1-- Y ~a + ' + ~ + y + i- 1- + + 1- P~
o ~ a~ ~ w ~ n ~ ~ rD
C~ ~I Ul Y W ~ ~D ~n~ ~ ~ ~O ~ Il) 1~33~;05 From the foregoing, it can be seen that the catalysts of the present invention in the inventive reaction show a much smaller loss in performance number ~and indeed some of the catalysts even show an improvement in performance number) over the reference catalysts. This means that the inventive catalysts when employed in the inventive reaction exhibit a far greater redox stability when subjected to unfavorable reaction conditions as compared to conventional catalysts. -Although only a few embodiments of the present invention have been described above, it should be appreciated that many modifications can be made without departing from the spirit and scope of the invention. All such modifications are intended to be included within the scope of the present invention, which is :~
to be limited only by the following claims:

.. . - . . . ... . . .

Claims

(5024) WE CLAIM:

1. In a process for the preparation of unsat-urated aldehydes and acids from propylene or isobutylene by the vapor phase oxidation of propylene or isobutylene with molecular oxygen at a temperature of about 200° to 600°C in the presence of a catalyst the improvement comprising using as the catalyst a catalyst of the formula AaBbFecXdMeMo12Ox wherein A is alkali metal, thallium, silver or mixtures thereof, wherein B is cobalt, nickel, zinc, cadmium, beryl-lium, calcium, strontium, barium, radium or mixtures thereof;
X is bismuth, tellurium or mixtures thereof;
and wherein M is a two-or-more-element system selected from the group consisting of Ge + W, Cr + P, Ge + P, Cu + Sn, Pr + W, Ce + W, Sn +
Mn, Mn + Ge, Mg + Sn or combinations thereof;
and further wherein 0 ? a ? 5, 0 ? b ? 20, 0 ? c ? 20, 0 ? d ? 20, 0.01 ? e ? 12, and x is a number such that the valence require-ments for the other elements for oxygen are satisfied, and wherein the minimum amount of each element in M is 1 atom percent based on the number of atoms in component M, said catalyst being free of the combination of Cr + Cu.

(5024)

2 . The process of claim 1 wherein M is selected from the group consisting of Ge + W, Cr + P, Ge + P, Cu + Sn, Sn + Mn, Mn + Ge, and Mg + Sn.

3 . The process of claim 2 wherein X is Bi.

4 . The process of claim 3 wherein the elements of said catalyst are present such that 0 ? a ? 0.5, 0.1 ? b ? 20, 0.1 ? c ? 20, 0.1 ? d ? 20 and 0.01 ? e ? 6.

5 . The process of claim 2 wherein the elements of said catalyst are present such that 0 ? a ? 0.5, 0.1 ? b ? 20, 0.1 ? c ? 20, 0.1 ? d ? 20 and 0.01 ? e ? 6.

6 . The process of claim 1 wherein X is Bi.

7 . The process of claim 1 wherein A is at least one of K, Rb and Cs and further wherein B is Ni + Co.

8 . The process of claim 6 wherein M is Ge + W.

9 . The process of clalm 8 wherein A is at least one of K, Rb and Cs and further wherein B is Ni + Co.

10. The process of claim 1 wherein A is alkali metal, B is Co, Ni or mixtures thereof, X is Bi 0.03 ? a ? 5 0.1 ? b ? 20 0.1 ? c ? 20 (5024) 0.1 ? d ? 20, and 0.1 ? e ? 6.

11. The process of claim 10 wherein M is selected from the group consisting of Ge + W, Cr + P, Ge + P, Cu + Sn, Sn + Mn, Mn + Ge, and Mg + Sn.

12. In a process for the preparation of unsaturated aldehydes and acids from propylene or isobutylane by the vapor phase oxidation of propylene or isobutylene with molecular oxygen at a temperature of about 200° to 600°C in the presence of a catalyst, the improvement comprising using as the catalyst a catalyst of the formula:
AaBbFeCXdMeMo12Ox wherein A is an alkali metal;
wherein B is cobalt, nickel, zinc, cadmium, beryllium, calcium, strontium, barium, radium or mixtures thereof;
X is bismuth, tellurium or mixtures thereof; and wherein M is a two-or-more-element system selected from the group consisting of Ge + W, Cr + P, Ge + P, Cu + Sn, Pr + W, Ce + W, Sn + Mn, Mn + Ge, Mg + Sn or combinations thereof; and further wherein 0 ? a ? 5, 0 ? b ? 20, 0 ? c ? 20, 0 ? d ? 20, 0.01 ? e ? 12, and x is a number such that the valence requitements for the other elements for oxygen are satisfied, said catalyst being free of the combination of Cr + Cu.

13. In a process for the preparation of unsaturated aldehydes and acids from propylene or isobutylene by the vapor phase oxidation of propylene or isobutylene with molecular oxygen at a temperature of about 200° to 600°C in the presence of a catalyst, the improvement comprising using as the catalyst a catalyst of the formula:
AaBbFecXdMeMo12Ox wherein A is alkali metal, thallium, silver or mixtures thereof;
wherein B is cobalt, nickel, zinc, cadmium, beryllium, calcium, strontium, barium, radium or mixtures ? thereof;
X is bismuth, tellurium or mixtures thereof; and wherein M is a two-or-more-element system selected from the group consisting of Mg + Cr, Mg + Cr + W and Ge + Mn.
wherein 0 ? a ? 5, 0 ? b ? 20, 0 ? c ? 20, 0 ? d ? 20, 0.01 ? e ? 12, and x is a number such that the valence requirements for the other elements for oxygen are satisfied, and wherein the minimum amount of each element in M is 1 atom percent based on the number of atoms in component M.