DE2735414A1 - OXYDATION OF OLEFINS - Google Patents

Description

Dr. F. Zumstein Sr. - Dr. E. Assmann - Dr. R. Koenigsberger Dipl.-Phys. R. Holzbauer - Dipl.-Ing. F KJi. .öse s «η - Dr. F. Zumstein jun.

PATENT LAWYERS TELEPHONE: COLLECTIVE NO. 229341

TELEX 929978

TELEGRAMS: ZUMPAT CHECK ACCOUNT: MONKS 91139-809. BL? ΤΟΟ «Χ> 80 BANK ACCOUNT: BANKHAUS H. AUFHÄUSER

ACCOUNT NO. 397997. BLZ 70030600

27354U

β MUNICH 2.

BRAUHAUSSTRASSE 4

Case F5065-K103 (Zeon) / HF

NIPPON ZEON CO., LTD., Tokyo / Japan

Oxidation of olefins

The invention relates to a catalyst for the oxidation of olefins and a process for the production of unsaturated ones Aldehydes by oxidation of olefins in the presence of the aforementioned catalyst.

Some of the terms used here are defined as follows:

The "olefins" refer to olefins that have 3 carbon atoms in straight chain, such as propylene, isobutylene and isoamylene.

The "1 * oxidation stage ¹¹ denotes the catalytic gas phase reaction of olefins with molecular oxygen at high temperatures in the presence of a catalyst to form the corresponding unsaturated aldehydes.

The "2nd oxidation stage · ¹ denotes the catalytic gas phase reaction of unsaturated aldehydes with molecular oxygen at high temperatures in the presence of a catalyst to form the corresponding unsaturated carboxylic acids.

709886/0989

^ 2735AU

The "continuous 1st and 2nd stage process" means a process for the production of unsaturated carboxylic acids from olefins by the gaseous reaction mixture, which was formed in the 1st oxidation stage, is fed directly to the zone of a 2nd oxidation stage, around the 2nd oxidation stage perform.

The "catalyst for the oxidation of olefins" or the "catalyst for the 1st oxidation stage ¹¹ denotes a catalyst which is used in the 1st oxidation stage.

The "catalyst for the 2nd oxidation stage" refers to a catalyst which is used in the 2nd oxidation stage.

It is known to use unsaturated aldehydes, such as acrolein and methacrolein, by oxidation of the corresponding olefins, such as propylene and isobutylene, to form, and unsaturated carboxylic acids, such as acrylic acid and methacrylic acid, by oxidation of the corresponding unsaturated aldehydes. Acquaintance Previous techniques for the production of unsaturated carboxylic acids from the corresponding olefins include a process that is, the separation of an unsaturated aldehyde from the reaction mixture obtained in the 1st oxidation stage has been, and after the purification of which includes the subjecting of the same to a second oxidation stage, and a process, the successive implementation of the 1st oxidation stage and the 2nd oxidation stage without working up the reaction mixture the 1st stage includes (GB-PS 939 713). The latter is considered commercially advantageous as it does not involve a treatment stage, such as the separation and purification of unsaturated aldehyde, requires and therefore advantages in terms of the apparatus, the process and the economy.

However, the process provides continuous 1st and 2nd stage in general far inferior results compared to those in which the 2nd oxidation stage independently Use of unsaturated aldehyde as a starting material

709886/0989

-Sr-

S "27354U

is carried out. This tendency is particularly evident in manufacturing of methacrylic acid from isobutylene. For this reason, no recommendation has been made so far, the one commercial production of methacrylic acid by a continuous 1st and 2nd stage process.

The underlying difficulties are believed to be due to by-product impurity formation and retention of unreacted isobutylene in the 1st oxidation stage. The present inventors have these difficulties carefully examined and found that the reaction mixture obtained in the 1st oxidation stage was unsaturated Hydrocarbons such as diisobutylene, benzene, toluene, xylene and ethylbenzene in addition to the unreacted isobutylene and contains a tarry by-product and that the presence of these hydrocarbons is a major cause of the poorer reaction results in the 2nd oxidation stage are.

In the production of methacrylic acid from isobutylene by a process of continuous 1st and 2nd stage it is it is desirable to develop a new oxidation catalyst which simultaneously meets the following two requirements, which do not seem to be compatible with each other.

(1) It should give a high conversion of isobutylene and thus decrease the amount of unreacted isobutylene.

(2) It shouldn't just cause the formation of a tarry by-product reduce, but also of unsaturated hydrocarbons such as diisobutylene, benzene, toluene, xylene and ethylbenzene.

In addition to these requirements, such a catalyst should also the usual requirements for industrial catalysts, such as a high selectivity towards methacrolein (MAL) (which is associated with a high level of

709886/0989

& 27354U

prey in a single pass) and a long active lifespan, correspond.

Accordingly, it is an object of the invention to provide a new catalyst For the oxidation of olefins to create the unsaturated aldehydes from olefins with high selectivity and a high yield can result in a single pass and has a long active life.

Another object of the invention is to provide a new catalyst for the oxidation of olefins which is similar to the two above corresponds to the requirements described.

Another object of the invention is to provide a process for producing unsaturated aldehydes with high selectivity and to provide high yield using such a catalyst for the oxidation of olefins.

According to the invention, a catalyst is provided which can meet these objectives, this catalyst having the composition

^Mo a ^Bi b ^Fe c ^Co d ^Ni e ^Be f ^Q g ^R h ^X i ^Z j ° g

owns what

Q at least one element selected from the group Au and Nd, means;

R is at least one element selected from the group consisting of K, Rb, Cs and Ti or Tl;

X is at least one element selected from the group consisting of P, As and B;

Z at least one element, 'selected from Ce, Ti, Te, Zn, Ge, Sn, Cr, Ga, La, In, Al, Cd, Pd, Mn, V, Pb, Nb, Ag, Zr, Cu and U, represents;

709886/0989

> 2735AU

a, b, c, d, e, f, g, h, i and j the respective number of Mo, Bi, Fe, Co, Ni, Be, Q, R, X and Z atoms and when a is 12, b is 0.1 to 10, c is 0.5 to 40, d is 0 to 12, e is 0 to 12 below The prerequisite is that the sum of d and e is 0.5 to 15, f is 0 to 35, g is 0 to 8, provided that that the sum of f and g is 0.1 or above, h is 0.01 to 5, i is 0 to 5 and j is 0 to 12 and

k represents the number of oxygen atoms that saturate the atomic valencies of the other elements.

A catalyst of the general formula above, wherein when a is 12, b is 0.5 to 7, c is 1 to 35, d is 0 to 10 e is 0 to 10 with the proviso that the sum of d and e is 0.5 to 12, f is 0 to 30, g is 0 to 6 below provided that the sum of f and g is 0.1 or more, h is 0.01 to 4, i is 0 to 4 and j is 0 to 8, represents a preferred embodiment of the invention.

A catalyst of the general formula above, wherein when a is 12, b is 0.5 to 7, c is 8 to 30, d is 0 to 10 e is 0-10 with the proviso that the sum of d and e is 0.5-12, f is 0-20, g is 0.1-4 provided that the sum of f and g is 0.1 or more, h is 0.01 to 3, i is 0 to 3 and j is 0 to 8, represents a particularly preferred embodiment of the invention.

Although the exact structure of the catalyst of the present invention is not clear, it is believed that the composition of the constituents forming the catalyst can in principle be expressed by the above general formula.

The use of these catalysts according to the invention can Methacrolein can be obtained in high yield with high selectivity even if the conversion of isobutylene into its Oxidation product is high, and can significantly reduce the amounts of

709886/0989

* 2735AU

Unsaturated hydrocarbons formed as by-products, such as diisobutylene, benzene, toluene, xylene or ethylbenzene, reduce. Accordingly, the catalysts of the invention are very suitable for the production of methacrolein, and when they as a catalyst for the 1st oxidation stage in the process the continuous 1st and 2nd stage are used, they hinder the reaction of the 2nd oxidation stage during one essentially not for a long period of time. Furthermore, the catalysts of the invention can use acrolein in high yield result in the catalytic oxidation of propylene and are very effective in the process of the continuous 1. and 2p stage for the production of acrylic acid from propylene.

Such an effect of the invention can be specifically achieved by including Be, Au or Nd in the catalyst components such as shown in the general formula above. If these components are not present, the activities are of the catalysts is low, and the formation of unsaturated hydrocarbons formed as by-products decreases to a large extent. This is presumably due to the fact that the presence of Be, Au or Nd changes the structure of the active nucleus in the catalysts of the invention compared to that of other known catalysts with similar Composition makes different. For example, the X-ray diffraction pattern of a catalyst according to the invention which contains Be, by no means a peak based on crystals of geryllium oxide. One takes on the basis of this fact that beryllium oxide in the catalysts of the invention does not exist alone.

fjs were different catalysts with one through general Composition expressed by formulas which are similar to those which describe the catalysts according to the invention, known. However, as shown in the comparative examples below, show catalysts that contain other elements of group II of the periodic table (to which beryllium belongs) instead of beryllium, catalytic

709886/0989

9 2735AU

Activities that are completely different from those of the catalysts of the invention, and cannot achieve the objects of the invention.

Known catalysts with a similar composition to that of the catalysts according to the invention show one good performance only when the number of Fe atoms is within a very narrow range of 0.5 to 3 taking the number of Mo atoms as 12 (e.g., JA Patent Publication No. 17253/73). In contrast to this the catalysts of the invention show a high activity when the number of Fe atoms is within a wide range Range from 0.5 to 40, and show the best performance when the number of Fe atoms is within the Range from 8 to 30.

The catalysts according to the invention can by numerous methods known from the prior art, such as evaporation s method, the oxide mixing method and the coprecipitation method, getting produced. The starting materials for the individual elements in the catalyst can not only their oxides, but any other compounds which give the catalyst of the invention by calcination. Examples for these starting materials, salts containing these elements (such as ammonium salts, nitrate salts, carbonate salts, Salts of organic acids and halides), free acids, acid anhydrides, condensed acids and containing molybdenum Heteropoly acids, such as phosphomolybdic acid or silicomolybdic acid, and their salts such as ammonium salts or metal salts. The use of a silicon containing compound, such as silicomolybdic acid, does not adversely affect the activity of the obtained catalyst.

The calcination for catalyst preparation, catalyst activation etc. is usually conducted at 300 to 900 ⁰ C, preferably 450 to 700 ° C, for about 4 was carried out to 16 hours. If desired, a primary calcination

709886/0989

OK 2735AU

calcination treatment at a temperature lower than the aforesaid calcination temperature before the above calcination treatment be performed.

The catalysts of the invention can be used directly as they are prepared and also deposited on a support having a suitable shape or thinned with a support (Diluents) in the form of powders, sols, gels, etc. can be used. Known carriers can be used for this purpose will. Examples include titanium dioxide, silica gel, silica sol, diatomaceous earth, silicon carbide, aluminum oxide, Pumice stone, silicon dioxide-aluminum oxide, bentonite, zirconium oxide, Zeolite and refractories. Silicon-containing supports are particularly suitable.

The amount of the carrier can be appropriately selected. The catalyst is in a suitable form, such as powder or Tablets, transferred and can be used in both a fixed bed, a fluidized bed and a fluidized bed will.

The catalysts of the invention are for the oxidation of olefins with 3 carbon atoms in a straight chain, such as propylene, Isobutylene and isoamylene, especially isobutylene, can be used. These olefins do not have to be of high purity, but they can contain impurities. However, the oxidation is carried out according to the method of a continuous 1st and 2nd stage carried out, so is the inclusion of large amounts of impurities, which may be unsaturated Hydrocarbons in the converted gas from the 1st oxidation stage included, undesirable. Molecular oxygen can be used alone, but is for commercial use Practices the use of air. Furthermore, in this reaction, the molecular oxygen with an inert Be diluted gas that does not adversely affect the reaction, such as water vapor, nitrogen, argon or gaseous Carbon dioxide. It is particularly preferred to dilute with steam.

709886/0989

~% ~ 2735AU

In the preparation of unsaturated aldehydes from the corresponding olefins using the catalysts of the invention, the reaction temperature is 250 to 700.degree. C., preferably 250 to 550.degree. The reaction pressure is usually atmospheric pressure up to 10 atmospheres. The space velocity (SV) of the total gases used is 200 to 10,000 hours " ¹ , preferably 300 to 6000 hours"" ¹ (based on standard temperature and standard pressure). The olefin concentration in the starting gases supplied is 0.5 to 25 % By volume, and the olefin to oxygen ratio is 1: 0.5 to 7. The preferred composition for the starting gas mixture is olefin: air: steam 1: 3 to 30: 5 to 90 (molar ratio).

The reaction conditions in the 1st oxidation stage in the process of the continuous 1st and 2nd stage can easily be determined experimentally if a catalyst is used for the 2nd oxidation stage. Therefore, the reaction conditions for the 1st oxidation stage cannot be finally determined. However, usually the reaction temperature is 250 to 700 ° C, preferably 250 to 550 ° C. The reaction pressure is normal atmospheric pressure up to 10 atmospheres. . The space velocity of the total starting gases is 200 to 10,000 hours " ¹ , preferably 300 to 4000 hours". ¹ , The olefin concentration is 0.5 to 10% by volume, preferably 0.5 to 8% by volume. The olefin to oxygen ratio is 1: 1.5 to 7 and the preferred composition for the gas mixture is olefin: air / water vapor = 1: 7.5 to 30: 5 to 90 (molar ratio).

For the 2nd oxidation stage in the continuous process 1st and 2nd stage, any known catalysts can be used. Examples include P-Mo-R (R is at least one of Tl, the alkali metals and alkaline earth metals) -type oxidation catalysts. Oxidation catalysts having compositions resulting from the incorporation of the above P-Mo-R type oxidation catalysts with at least one element,

709886/0989

chosen from Si, Cr ₁ Al, Ge, Ti, V, W, Bi, Nb, Ga, Pb, Sn, Co, Pd, As, Zr, Sb, Te, Fe, Ni, In, Cu, Ag, Mn, La, Nb, Ta and Sm result; P-Mo-As type oxidation catalysts; P-Mo-As alkali metal type oxidation catalysts; Oxidation catalysts having compositions resulting from the incorporation of P-Mo-As alkali metal type catalysts with at least one element selected from V, W, Cu, Fe, Mn and Sn; P-Mo-Sb type oxidation catalysts; Oxidation catalysts with compositions consisting of the incorporation of P-Mo-Sb type catalysts with at least one element selected from W, Fe, Co, Al, Pb, Cr, Sn, Bi, Cu, Ni, Mg, Ca, Ba and Zn, result; P-Mo-Pd-type oxidation catalysts, P-Pd-Sb-type oxidation catalysts, oxidation catalysts with compositions resulting from the incorporation of P-Pd-Sb-type catalysts with at least one element selected from Bi, Pb, Cr , Fe, Ni, Co, Mn, Sn, U and Ba result; and oxidation catalysts having compositions resulting from the incorporation of the aforesaid oxidation catalysts with ammonium.

The 2nd stage of oxidation is essentially the same Conditions as for the 1st oxidation stage carried out, however, as described above, according to the one used Catalyst special conditions selected. Preferably that is obtained under the aforementioned reaction conditions Reaction mixture of the 1st stage fed directly as the starting material of the 2nd oxidation stage and used for the Reacted catalyst suitable conditions.

The following examples illustrate the invention in detail. In these examples the conversion, the selectivity and the yield calculated in a single pass according to the following equations. All analyzes were determined by gas chromatography. For the sake of simplicity, the specification of oxygen is in the catalyst composition did not take place.

709886/0989

4L 27354U

In the following description, i-B stands for isobutylene j MAL for methacrolein and MAA for methacrylic acid. The using reaction results obtained from propylene instead of isobutylene can be calculated by using propylene instead of i-B, acrolein instead of MAL, and acrylic acid instead of MAA in the following equations.

[The calculation of the equations for the results of the 1st oxidation stage]

Implemented i-B (Mole)

i-B conversion (%) = χ

Delivered i-B (Mole)

Percentage of unsaturated hydrocarbons

t Diisobutylene formed

Unreacted iB (moles) (based on carbon) Supplied iB (moles) Supplied iB

(based on carbon)

Benzene formed (based on carbon) Delivered iB (based on carbon)

+ Toluene formed (based on carbon) added iB (based on carbon)

Xylene formed (based on carbon) Supplied iB (based on carbon)

. Ethylbenzene formed (based on carbon) j _χ Supplied iB (based on carbon)

Yield in a single MAL (Mole)

gen passage at MAL (%) ^s Supplied iB (Mole) ^{x 10} °

Selectivity of the MAL (%) = _{χ 1QQ}

Implemented i-B (Mole)

[Equations for calculating the results of the 2nd oxidation stage]

MAL Conversion (%) "= Converted MAL ( _{Moles ) χ 1QQ}

Delivered MAL (Mole)

Yield of MAA in one

single pass = formed MAA (moles) _{χ 1QQ}

(based on MAL) (%) MAL supplied (MoIe)

709886/0989

2735AU

Selectivity of the MAA _β MAA formed (moles) (based on MAL) (%) ** MAL converted (moles) ^X

Conversion of unsaturated hydrocarbons (%)

Reacted unsaturated hydrocarbons (based on carbon)

Unsaturated hydrocarbons added (based on carbon)

χ 100

Yield of MAA in a single pass (based on i-B) (%)

Formed MAA (Mole) es> _________________________________ — ___ χ

I-B (moles) fed to the zone of the 1st oxidation stage

example 1

A. Preparation of the catalyst

48.5 g of bismuth nitrate, 116.5 g of cobalt nitrate, 29.1 g of nickel nitrate, 484.8 g of ferric nitrate, 56.1 g of beryllium nitrate were added and 10.1 g of potassium nitrate to 150 ml of water and dissolved with heat to form a solution (solution A). One solved 212 g of ammonium molybdate in 400 ml of water with heating and added 5.76 g of 85% phosphoric acid to form a Solution (solution B) too. Solution B was added to solution A, which was stirred at an elevated temperature. Under After careful stirring, the mixture was evaporated to dryness and dried at 120 ° C. for 8 hours. Then the dried mixture calcined in a muffle furnace at 600 ° C. for 16 hours. The obtained solid was pulverized and sieved to form particles having a particle size of 2.4 to 4.8 mm (4 to 8 mesh). The composition of the obtained catalyst was as follows:.

B. Implementation Process

The reaction was carried out by a continuous 1st and 2nd stage method in the following manner.

709886/0989

A * 2735AH

(1) Reaction in the 1st oxidation stage

100 ml of the catalyst obtained were filled into a stainless steel reaction tube with an internal diameter of 2.5 cm and a length of 60 cm and the mixture was heated over a metal bath.A starting gas mixture of isobutylene, air and steam in a molar ratio of 4:55 was passed in: 41 with a space velocity of 2000 hours.
through the catalyst layer.

(2) Reaction in the 2nd oxidation stage

As a catalyst for the 2nd oxidation stage, 100 ml of the in the description of the JA patent publication was filled
No. 10846/75 described in Example 1 Mo: P: Cs: Cr catalyst [Mo: P: Cs: Cr = 1: 0.16: 0.16: 0.16 (atomic ratio);
calcined at 450 ° C; Catalyst particle diameter 2.4 to 4.8 mm (4 to 8 mesh)] into a stainless steel reaction tube having an inner diameter of 2.5 cm and
a length of 60 cm and heated over a metal bath. The converted gas obtained by the 1st oxidation stage was passed directly through the catalyst layer.

Those obtained from the oxidation in the 1st and 2nd stages
Results are given in Table I. In Table I, the reaction temperatures relate to those of the metal bath that were held constant (the same
applies to the following statements).

Examples 2 to 12

The catalysts for the 1st oxidation stage were prepared by the same procedure as in Example 1, except that the composition of the catalyst of Example 1 was changed. Using these catalysts, the same reaction was carried out in a continuous 1st and 2nd stage as in Example 1 with changing the reaction temperatures
carried out.

709886/0989

- 14 -

Λ 27354U

The reaction temperatures, the catalyst compositions and the results are given in Table I.

Comparison examples 1 to 4

It was presented in Example 1 of the JA patent publication No. 32044/72 (Comparative Example 1) described in Example 1 of JA Patent Publication No. 32043/72 (Comparative Example 2) described in Example 3 of JA Patent Publication No. 42813/72 (Comparative Example 3) and that described in Example 1 of JA Patent Publication No. 1753/73 (Comparative Example 4) Catalyst [the catalyst particle sizes were 2.4 to 4.8 mm (4 to 8 mesh)] according to those described in these patent publications methods described. Using these catalysts, the reaction was carried out in a continuous manner 1st and 2nd stage carried out as in Example 1. The results are given in Table II.

Comparative examples 5 and 6

The same catalysts were prepared as in Examples 2 and 5, with the exception that they did not contain Be, and carried out the same reactions in a continuous 1st and 2nd stage using these catalysts as in Examples 2 and 5. The results are given in Table II.

The results in Tables I and II show that the presence of Be gives good results not only in the implementation in the 1st oxidation stage, but also in the implementation in the 2nd oxidation stage.

Comparative Examples 7 to 16

The catalysts shown in Table II (comparative examples 7 to 10) were prepared by the same procedure as described in Example 1, with the exception that 76.9 g of magnesium nitrate, 70.8 g of calcium nitrate, 63.5 g of Stron

709886/0989

^ 2735AU

tium nitrate or 78.4 g barium nitrate instead of 56.1 g beryllium nitrate used. Comparative catalysts (comparative examples 11 and 12) were prepared in an analogous manner the catalyst according to the invention used in Example 8 and comparative catalysts (Comparative Examples 13 to 16) according to the catalyst according to the invention used in Example 11. The same implementation was carried out as in Example 1, using these catalysts in the oxidation catalyst of the 1st stage. The received Results are given in Table II.

A comparison of these comparative catalysts with the catalysts of the invention shows that the Catalysts which contain Mg, Ca, Sr and Ba (which are alkaline earth metals) instead of Be give very poor reaction results when used as catalysts for the 1st oxidation stage be used. Furthermore, if they are used as catalysts for the 1st oxidation stage in the process the continuous 1st and 2nd stage are used, the amount of both unreacted isobutene and as By-product formed unsaturated hydrocarbons large. Hence, the 2nd stage oxidation reaction proceeds out of control, and the catalyst for the 2nd oxidation stage loses its activity within a very short time.

709886/0989

Table I.

ο co οο

■ O

co co co

Results of the Bi (Atomic ratio: Co Ni I.
Be I. P. K 1 1st oxidation stage i_ B-Um Share of ge TIMES Selek
tivi
activity at . Catalyst composition 1 Pe 4th 1 3 0.5 1 Reacti Wall
lung formed unge
satiated Koh
len v; ass er
fabrics (%) Stress
te in
one ,.
emmaU
genDurci "
corridor (%} 79.9 game . 1 12th 4th 1 3 0.5 1 onstem
temperature
( ⁰ C) 97.6 2.9 78.0 78.1 1 Pb 1 6th 4th 1 3 0.5 1 340 97.0 4.0 75.8 81.4 CVl 12th 1 18th 4th 1 3 0.5 1 370 97.3 3.3 79.2 80.8 3 12th 1 30th 4th 1 3 0.5 0.75 345 96.7 ^ l 78.1 78.3 4th 12th 3 4th 4th 1 3 - 0.75 360 96 _t 5 4.2 75.6 81.0 5 12th 6th 12th 4th 1 10 0.5 0.75 365 97.5 3.0 79.0 80.1 6th 12th 3 12th - 5 5 0.5 1 340 97.2 3.2 77.9 81.0 7th 12th 1 12th 4th 1 1 0.5 1.5 340 97.0 3.3 78.6 81.1 8th 12th 1 12th 4th 1 20th 2 0.2 335 97.0 3.6 78.7 80 _; 7th 9 12th 1 12th 5 - 3 0.5 2.0 340 96.8 3.7 78.1 82.3 10 12th 1 12th 4th 1 3 0.5 342 96.4 3.9 79.3 80.4 11 12th 12th 325 96.6 4 _f 0 77.7 12th 12th 370 12th

OJ cn

Table I (continued)

CD OO OO

(D CD CD

Reaction
temperature MAL- At
change Results 'the 2nd oxidation stage Converting the
unsaturated MAA yield
in one go at
game (° C) (%) MAA
(based on TIMES) Hydrocarbon
fabrics (%) ligen passage
(based on
iB) (.%) 335 80.8 Carrion in
a one-time
lig.yurc ± ig. Selecti
vity (%) 100 47.2 1 335 75.8 60.5 74.9 100 43.3 2 335 77.0 57.1 75.3 100 46 _T 6 3 335 76.1 58.9 76.5 100 44.4 4th 335 76.4 56.8 74.6 100 43.0 5 335 77.3 56.9 74.5 100 47.1 6th 335 78.4 59.6 77.1 100 47.1 7th 335 77.2 60.4 77.0 100 46.6 8th 335 77.1 59.3 76.8 100 46.9 9 335 76.7 59.6 77.3 100 45.0 10 335 77.5 57 _T 6 75.1 100 46.4 11 335 76.2 58 _r 5 75.5 100 44.2 12th 56.9 74.7

Table II

(O OO OO

(O α » (O

Ver
as- composition Bi Fe (Atomic ratio) of the catalyst for the Ni P. K Ti Si 1st oxidation stage Approx Sr Ba ^ 4 «k ^^^ M vl * j ^ p ^^
example n> 1 1 Co o, i 0.4 _ Me - _ _ 1 12th 1 1 4th 8.5 0.1 - 0.4 - - - - - 2 12th 1 1 - - 0.08 - 1.5 - - - - 3 12th 1 3 4th ² ; 5 0.5 0.07 - - - - - - 4th 12th 1 6th % 5 1 0.5 1 - - - - - - 5 12th 1 4th 4th 1 0.5 1 - - - - - - 6th 12th 1 12th 4th 1 0.5 1 - - - - - - 7 ■ 12th 1 12th 4th 1 0.5 1 - 3 3 - - 8th .12 1 12th 4th 1 0.5 1 - - - 3 - 9 12th 1 12th 4th 1 0.5 1 - - - _ _ 3 10 12th 3 12th 4th 5 0.5 0.75 _ _ - - 11 12th 3 12th - 5 0.5 0.75 - - 5 - - 5 12th 12th 1 12th - - 0.5 0.2 - - - - - - 13th 12th 1 12th 5 - 0.5 0.2 -. - 3 3 _ _ 14th 12th 1 12th 5 - 0.5 0.2 - - - - 3 15th 12th 1 12th 5 ■ - 0.5 0.2 - - - - 3 16 12th 5 -

df

Table II (continued)

O CO OO CD

Reaction Results of the 1st oxidation stage Share of ge TIMES selectivity
(%) Comparison temDerature i-B - Um- formed un— 64 _r 6 example ( ⁰ O wandluna saturated
Hydrocarbon
fabrics (%) Yield in
one time
leagues through
corridor (%) 62.0 1 340 (%) 9.1 60.8 65.3 2 340 94 _r l 9.6 59.8 64.1 3 340 96.4 8.6 62.2 63.7 4th 340 95.3 13.0 57.7 67.2 5 370 90 _r 0 10.3 60.4 78.0 6th 365 9 ^, 9 14.6 59.5 79.5 7th 540 88.6 • 44.7 ^ 5.5 80.0- 8th 340 58.3 46.7 44.5 79.2 9 540 56.0 52.8 39.6 80.5 10 340 ^ 9.5 59.8 33.5 80.0 11 335 42.5 , 56.4 36.8 80.2 12th 535 45.7 62.0 52.0 79.5 13th 525 40.0 45.0 46.1 79.7 14th 325 57.5 47.1 45.8 81.1 15th 325 55.1 56.9 36.1 16 325 45.3 60.4 33.8 41.7

co co cn

Reaction Table II (I. MAL - Um MAA selectivity V Converting the MAA yield in (%) K) temperature change (referring to MAL) unsatisfied a one-time 22.7 CO Localization} Yield in
an eirar, a- (%) Konxenwasser—
fabrics gen passage
(based on 22.2 cn Ver Ugen through 63 ₇ 5 i-B) 23.3 equal
example ( ⁰ O Results of the 2nd oxidation stage (%) corridor (%) 63.3 (%) 17.6 335 58.4 37.1 61.9 100 '23.7 335 58.3 36.9 59.9 100 19.2 1 335 60.4 37.4 64 _y 0 100 2 335 50.4 50.2 61.2 100 5 • 335 61.4 59.3 100 4 " 535 52.6 52.2 100 5 555 6th 355 7th 555 8th 355 9 355
355 > Implementation is getting out of hand, and 10 555 MAA is hardly formed. 11
1 p 355 Lc 355 13th 355 14th 15th 16

Reference Examples 1 to 7

Investigations were made with respect to that used in Example 1 Catalyst for the 2nd oxidation stage the effect that in the feed gas for the reaction in the 2nd oxidation stage contained hydrocarbons with regard to the reaction results

Instead of the gas reacted in the 1 × oxidation stage, a gas mixture obtained by adding isobutylene or xylene in the concentrations shown in Table III to MAL (purity 99.5% by weight) was used according to the method described in Example 1 at a space velocity of 2000 hours " ¹ µm while maintaining the MAL (a mixture containing isobutylene or xylene): O ₂ : N ₂ : H ₂ O molar ratio at 1: 1.5: 13.0: 17.5 The results are given in Table III.

From Table III it can be seen that in the reaction of the 2nd oxidation stage, unsaturated hydrocarbons, such as Isobutylene or xylene, adversely affect the formation of MAA.

Table III

Reference
example Concentration on un
saturated coals
hydrogen in the
supplied MAL (%.
based on carbon) Xylene Reacti
onstem
temperature
( ⁰ C) Conversion
lung
by MAL MAA (related
on MAL) Selek
tivi Isobutylene 0 335 Training in
one activity 1 0 0 335 81.1 By-
⁹ W. 77.4 CVi 5 0 335 77.4 62.8 76.4 3 10 ο 335 63.6 .59.1 68.9 4th 15th ι 335 54.4 43.8 62.0 VJl 0 4th 335 76.9 33.7 75.3 6th 0 7th 335 66.7 57.9 63.1 7th 0 56.3 42.1 61.3 34.5

709886/0989

Use the same procedure as in Example 1
Catalysts made by adding another ingredient
(Component Z) (Ce, Ti, Zn, Cr, La, Al, Cd, Pb, Ag and Cu) in the catalyst prepared in Example 1 introduced.
The continuous 1st and 2nd stage reaction was carried out in the same manner as in Example 1 using these catalysts. The results
are shown in Table IV.

Examples 23 to 31

The same procedure as in Example 1 was used to prepare catalysts by adding the phosphorus component in the catalysts used, prepared in Example 1, partially or completely replaced by arsenic or boron or by partially or completely by the potassium component of the catalysts prepared in Example 1 Replaced rubidium, cesium or thallium. The same direct reaction was carried out in a continuous 1st and 2nd stage as in Example 1 using these catalysts. The results are given in Table V.

709886/0989

Table IV

CO OO 00

O CO 0 »CO

at
game Mon 1 Fe Co Ni Be P. K Z Reacti
on s tem
temperature
C ⁰ O i-B-
Edging
lung Share of ge
formed un-
saturate
Hydrocarbon
fabrics TIMES Selek
activity 13th 12th Results of the 1st oxidation stage 12th 4th 1 3 0.5 1 l (Ce) 340 97.7 • 2.8 Yield in
one a
malign
Passage 80.9 14th 12th Catalyst composition
(Atomic ratio) 12th 4th 1 5 0.5 1 3 (Ti) 340 97.7 2.7 79.0 82.5 15th 12th Bi 12th 4th 1 3 0.5 1 2 (Zn) 340 97.5 3.4 80.6 81.7 16 12th 1 12th 4th 1 5 0.5 1 2 (Cr) 540 98.2 2.6 79.7 80.5 17th 12th 1 12th .4 1 3 0.5. 1 1 (La) 340 97.4 3.1 78.9 83.4 18th 12th 1 12th 4th 1 3 0.5 1 ^ (AX) 540 97.1 3.3 81.2 85.8 19th 12th 1' 12th 4th 1 3 0.5 1 2 (Cd) 340 97.8 3.1 81.4 ■ 81.5 20th 12th 1 12th 4th 1 3 0.5 1 1 (Pb) 340 98.0 S ¹ 79.7 61.8 21 12th 1 12th 4th 1 3 0.5 1 2 (AS) 540 97.7 2.7 80.2 81.4 22nd 12th 1 12th 4th 1" 3 0.5 1 KOi) 340 97.5 3.2 79.5 82.2 1 80.1 1 1

Table XV (continued)

Reaction
tempeiratijur Results of the 2nd oxidation stage ! MM
(based on MAL) selectivity Converting the!
unsaturated
Hydrocarbons— ■ MAA yield in
a one-time
Byaana ibezo— at
game ! NAL Um-
change c%) i Yield in Gi) fabrics i
I. gen on i-B) (° C) 81.2 gear {%) 76.1 06)! {%) 335 7β, 3 61.8 76.0 100; 48.8 13th 335 79.6 59.5 75.3 100 ! 48 _; 0 14th 335 79.0 59.9 77.3 100 47.7 15th 335 80.1 61.1 77.5 100 48.2 16 ' 335 77.8 62.1 76.9 100 50.4 17th 335 78.0 59.8 76.9 100 48.7 18th 335 77.3 60.0 76.8 100 47.8 19th 335 79.0 59.4 76.5 100 . - 47.6 20th 335 77.9 60.4 76.9 100 48.0 21 335 59.9 100 48.0 22nd

Table V

at Composition (atomic ratio Mon Bi Fe .Co Ni Be > of the catalytic converter for the 1st As B. K Oxidation level Cs I. TX game 12th 1 12th 4th 1 3 P. - ■ - 1 Rb - - 23 12th 1 12th 4th 1 3 - 0.5 1 - - - 24 ·. 12th 1 12th 4th 1 3 - - 0.5 1 - - - 25th 12th 1 12th 4th 1 3 - - - - ■ ■ - o, i - 26th 12th 1 12th 4th • ι 3 0.5 - - - - - 1 27 12th ,1 12th 4th 1 3 0.5 - - - - - - 28 12th 1 12th 4th 1 3 0.5 0.5 0.75 0.75 - - 29 12th 1 12th 4th 1 3 0.5 0.5 - - - - 0.75 30th 12th 1 12th 4th 1 3 - - - 0.5 -. - 31 0.5 0.5

Table V (port setting)

ο u> ca ct> σ>

at
game Reaction
temperature
( ⁰ O Results of the 1st oxidation stage Share of educated
unsaturated coals
hydrogen
(%) TIMES Selecti
vity
(%) 23 340 iB - Um
change
(%) 3.7 Yield in
a unique one
Passage (.%) 81.7 24 340 96.5 3.3 78.8 82, .7 25th 340 97.0 5.1 80.2 81.3 26th 340 97.1 V 78.9 80.3 27 340 96.7 3.4 77.6 82.0 28 340 96.9 2.9 79.5 81 _; 4th 29 340 97.4 3.2 79.3 81.7 30th 540 97.0 h ¹ 79.2 82.2 31 340 97.2 3; 2 79 ₇ 9 82.1 97.1 79; 7th

Table V (port setting)

<o QP OO

Results of the 2nd oxidation stage Reaction
temperature
( ⁰ O MAL conversion
lung
(%) MAA
(based on MAL) selectivity
(%) Converting the
unsaturated
Coal water
fabrics
(%) MAA yield
in a one
times through
corridor
(%) at
game 335 78.0 Yield in
one time
leagues through
corridor (%) 77.2 100 47.4 23 335 77.2 60 _t 2 76.9 100 47.6 24 335 77.4 59.4 76.7 100 46.9 25th 335 76.0 59.4 75.3 ^ 100 44.4 26th 335. 77.2 57.2 75.7 100 46.4 27 335 78.0 58.4 77.3 100 47.8 28 335 77.7 6O _y 3 76.5 100 47.0 29 335 77.3 59.4 76.5 100 47.2 30th 335 77.2 59.1 76.9 100 47.3 59.4

- 2S--

EXAMPLES 32 to 34

The reactions in the 1st and 2nd stage were continued in the examples 1, 2 and 13 ICX) O hours under the same reaction conditions. The changes in the reaction results were determined

During the reaction, the temperatures of the metal baths in the oxidation zones of the 1st and 2nd stage were kept constant. The results are given in Table VI. As can be seen from Table VI, even after a time lapse of 1000 hours no significant degradation of the reaction results in the 1st oxidation stage and in the 2nd oxidation stage.

Comparative example 17

As a comparison to Example 33, those in the comparative example were used 5 carried out reaction in the 1st and 2nd stage for 1000 hours under the same reaction conditions. One determined the changes in the reaction results.

During the reaction, the temperatures of the metal baths in the 1st oxidation stage and the 2nd oxidation stage became constant held. The results are given in Table VI.

It can be seen from Table VI that no significant degradation of the reaction results of the 1st oxidation stage was observed. however, that in the course of time the reaction results of the 2nd oxidation stage became very poor. This degradation seems mainly on the effects of those contained in the converted gas which was formed in the 1st oxidation stage to be attributed to unsaturated hydrocarbons.

709886/0989

Table VI

\ 1
32 Verstri
chene
Time
(Hours.) Results of the 1 x oxidation stage Reaction
temperature
( ⁰ O iB - Um
change
(%) Share of ge
formed un
saturated
Coal water
fabrics (%) TIMES Selecti
vity
(%) 2
53 0 *
1000 340
340 97.6
97.5 2.9.
2.8 Yield in
one time
leagues through
gear (.%) 79.9
80.5 \ 15th
'54 0 *
1000 370
370 97.0
97.5 4.0
3.6 78.0
78.5 78.1
78.1 at
game 5
17th 0 *
1000 340
340 98.0
98.1 2.5 75.8
76 _r l 80.4
8O _; 3 Ver
equal
example 0 *
1000 370
370 9% 9
9 ^, 0 10.3 78.8
78.8 63; 7th
63.9 60.4 '
60.1

The symbol (*) means the early stage of the reaction.

Table VI (continued)

(O OQ OO

1
32. Results of the 2nd oxidation stage Reacti
onstem
temperature
( ⁰ C) MAL- At
change
(%) MAA
(based on MAL) selectivity
(%) Converting the
unsaturated
Hydrocarbon
fabrics
. (90 MAA yield in
a unique one
Passage (be
moved to iB)
( ⁰ Zo) \ 2
33 335
335 80.0
81.1 Training in
one a
times »Through
corridor (%) 74.9
75.2 100
100 47.2
47.9 \ 13th
34- 535
335 75.8
77.2 60.5
61.0 75.3
74.9 100
100 43.3
44 _; 0 example 5
17th 335
535 80.5
80.4 57.1
57.8 75.8
75.5 100
100 48.1
47.8 Ver
equal
example 335
335 61.4
49.7 61.0
60.7 64.0
58.4 100
100 23.7
17.4 39.3
29.0

27354U

Examples 35 to 37

The same reaction of a continuous 1st and 2nd stage as in Example 1 was carried out using the same reaction at a 1st oxidation stage as used in Examples 1, 2 and 13, and below Use of propylene instead of isobutylene. The reaction results are given in Table VII.

709886/0989

Table VII

at
game Results of the 1st oxidation stage Mon Bi Fe Co Ni Be P. K Ce Reacti
onstem
temperature
( ⁰ O Propylene
conversion Share of
educated
unsaturated
Hydrocarbon
fabrics Acrolein Selek
tivi
activity 55
36
37 Catalyst composition
(Atomic ratio) 12th
12th
12th 1
1
1 12th
6th
12th 4th
4th
4th 1
1
1 I VN VN VN 0.5
0.5
0.5 1
1
1 1 555
555
555 98.2
97.5
98 ₇ 6 2.0
2.9
1.8 yield
in one
unique.
Passage 86.5
85.9
87.5 84.9
85.6
86.1

CO CTJ

Table VII (Port setting)

at
game Results of the 2nd oxidation stage Reaction
temperature
( ⁰ C) Acrolein
conversion
<*) * Acrylic acid
(based on acrolein) Selectivi
activity
(%) Conversion to
unsaturated
Hydrocarbon
fabrics
(%) Acrylic acid
Yield in
one time
leagues through
gang (rel
gen on Pro
pylene) (%) 55
56
37 560
360
560 88.7
87.9
90.0 Au sb. in
one a
times .by
corridor (%) 90.5
90.1
91.2 100
100
100 68.2
66.2 "
70.7 . 80.3
79.2
82 _T 1

2735AH

Reference example 8

As a reference example for Examples 35 to 37, the reaction was carried out under the same conditions as in the reaction the 2nd stage carried out in Example 1, but acrolein with a purity of 99.6% by weight at a Space velocity of 2000 hrs. ~ Was used and the acrolein: Op: N ~ iH-O molar ratio in the starting gas mixture was held at 1: 1.5: 13.0: 17.5. The results are shown in Table VIII.

Table VIII

Reaction ^{temperature (0} C) 360

Acrolein Conversion (%) 91.0

Acrylic acid yield in
a single pass (based on acrolein) (%) 82.5

Selectivity (%) of acrylic acid

(based on acrolein) 90.7

Examples 38 to 42

48.5 g of bismuth nitrate, 116.5 g of cobalt nitrate, 29.1 g of nickel nitrate, 484.8 g of ferric nitrate and 10.1 g of potassium nitrate were added to 150 ml of water and dissolved by heating to form a solution (solution A).

Separately, 212 g of ammonium molybdate were dissolved in 400 ml of water by heating and 5.76 g of 85% phosphoric acid to form
a solution (solution B) added. Furthermore, 41.2 g of gold tetrachloride (III) acid were dissolved in 200 ml of water with heating to form a solution (solution C).

One mixed the solution B with 'the solution A, which at increased Temperature was stirred. After thorough mixing, solution C was added. With careful stirring, the Mixture evaporated to dryness and then dried at 120 ° C for 8 hours. The dried product was at 600 ° C

709886/0989

2735AU

Calcined in a muffle furnace for 16 hours. The obtained solid was formed into particles having a particle size pulverized from 2.4 to 4.8 mm (4 to 8 mesh).

The composition of the inventive catalyst prepared in this way was Mo ₁₂ Bi ₁ Fe ₁₂ Co ₄ Ni ₁ Au ₁ P ₀ ^ K ^.

Using the same procedure as above, various catalysts with various compositions, as indicated in Table IX.

The same reaction of a continuous 1st and 2nd stage as in Example 1 was carried out, this being the case Catalysts used for the 1st oxidation stage. The results are given in Table IX.

The results in Table IX show that the catalysts of the present invention containing Au give effects which are equivalent to those of the catalysts according to the invention which contain Be.

709886/0989

Table IX

Results of the 1st oxidation stage 12th Catalyst composition (Atomic ratio) C ₀ Ni Au P. κ 1 Reacti i-B- Share of ge MAYf Selek
activity
(%) 12th Fe 4th 1 1 0.5 1 onstem
temperature
( ⁰ C) Conversion
lung
00 formed un
saturated
Hydrocarbon
fabrics (%) Au sb .in
one
once
By
corridor &) 79.0 at
game .12 Bi 12th 4th 1 1 0.5 1 340 96.8 3.9 76.5 77.4 38 12th 1 4th 4th 1 1 0.5 1.5 365 96.5 4, ⁵ - 74.7 78.6 39 12th 1 30th 4th 1" 2 0.5 0.5 378 97.1 ³ , ⁷ 76.3 80.1 40 ■ 1 12th 4th 1 0.5 1 360 97.3 3.8 77.9 78.6 41 1 12th 342 97.2 3.6 76.4 42 1

Table IX (continued)

ο co OO

ο co α »

Bel-
game Results of the 2nd oxidation stage Reaction
temperature
C ⁰ C) TIMES-
Urawandlüng
(%) MAA
(based on MAL) selectivity
(%) Converting the
unsaturated
Hydrocarbon
fabrics
(%) MAA yield in
a one-time
gen passage
(based on iB)
(%) 38
39
40
41
42 335
335
335
335
335 76.2
75.8
77.1
76.4
76.5 Yield in
one a
malign
Passage 75.1
74.3
75.6
74.9
75.4 100
100
100
100
100 43.8
42.1
44.5
44.6
44.1 57.2
56.3
58.3
57.2
57.7

(M

cn

27354U

Examples 43 to 54

A catalyst of the composition Mo ₁₉ Bi _-1 Fe ₁₁₀ Co ₄ Ni ₁ Nd ₁ P- ^ K _{1 was} prepared in the same way as in Example T, with the exception that 43.8 g of neodymium nitrate instead of 56.1 g g beryllium nitrate used. Various catalysts having various compositions as shown in Table X were prepared by the same procedure.

The performances of these catalysts were determined in the same manner as in Example 1. The results are given in Table X.

709866/0989

Table X

12th Results of the 1st oxidation stage (Atomic ratio s Co Ni Nd ) P. K 1 Reacti i-3- Share of ge MAY Se-
lek-
& «T
(X) at 12th Catalyst Composition Fe 4th 1 1 0.5 1 onstem
temperature
( ⁰ C) Conversion
lung
(%) formed un
saturated
Hydrocarbon
fabrics (%) yield
in a
unique.
By-
qanq (%) 78.9 game 12th 12th 4th 1 1 0.5 1 340 96.7 3.9 76.3 78.1 43 12th Bi 6th 4th 1 1 0.5 1 370 96.5 4.2 75.4 80.5 44. 12th 1 18th 4th 1 1 0.5 1 360 97, o 3.7 78.1 80.1 45 12th 1 30th 4th 1 1 0.5 0.75 375 96.5 4.0 77.3 73.0 46 12th 1 4th 4th 1 1 - 0.75 365 96.3 4.1 75.1 8.0.5 47 12th 1 12th 4th 1 0.5 0.5 O ₇ 75 344 97.2 3.7 78.2 79.3 48 12th 1 12th - 5 3 0.5 1 345 96.8 3.8 76.8 78.6 49 12th 3 12th 4th 1 0.2 0.5 2 33o 98.2 2.8 77.2 80.7 50 12th 6th 12th 4th 1 6th 2 1.5 350 96.4 4.0 77.8 80, 1 51 12th 3 12th 5 - 2 0.5 0.5 338 98.0 3.9 78.5 81.0 52 1 12th 4th 1 0.7 0.5 330 98.5 2.6 79.8 79.0 53 1 12th 345 97.1 3.7 76.7 54 1 1

Reaction
temperature
C ⁰ C) Table X (Port setting) selectivity
(%) Converting the
unsaturated
Hydrocarbon
fabrics
(%) MAA yield
in a one
times through
gang (related
on iB)
(%) 335 Results of the 75.0 100 43.6 at
game 335 TIMES-
Transformation
(%) 2nd oxidation stage 75.3 100 42.9 43 335 76.1 WAA
(based on MAL) 75.8 100 45.5 44 335 75.6 Yield in
one a
malign
Continuous (%) 75.0 100 44.2 45 335 76.9 57.1 76.1 100 43.0 46 335 76.3 56.9 76.4 100 45.7 47 ' 335 75.3 58.3 76.3 100 44.5 ■■ 48 335 76.4. 57.2 76.8 100 47.7 49 335 76.0 57.3. 74.8 100 44.2 50 335 80.5 58.4 74.7 100 45.1 51 335 75.9 58.0 76.0 100 47.8 52 335 77.0 61.8 75.5 100 44.4 53 78.8 56.8 54 76.7. 57.5 59.9 57.9

te 2735AU

Examples 55 to 67

Catalysts were prepared in the same way as in Examples 38 and 43, with the exception that Ce ₁ Ti, Zn ₁ Cr ₁ La ₁ Al ₁ Cd ₁ Pb or Cu were additionally added to the catalysts prepared in Examples 38 and 43 Using these catalysts, the reaction was carried out in a continuous 1st and 2nd stage as in Example 1. The results are given in Table XI.

709886/0989

Table XI

Mon Bi ] . (Atomic ratio; Ni Au Nd P. K Z . Oxidation level? i-B-Um- Share of TIMES ! SE-
ti vi-
tabßfc) at 12th 1 Results of the l Co 1 1 - 0.5 1 3 (Ti) React Wall- educated Yield in 79.9 game 12th 1 Catalyst composition 4th 1 1 - 0.5 1 1 (La) functional lung
(%) unsaturated
ten coals
water. (%) one a
malign
Continuous (%) 79.5 12th 1 4th 1 1 - 0.5 1 1 (Pd) tempe-
rature
( ⁰ C) 98.1 3.0 78.4 80.6 55 12th " 1 Fe 4th 1 1 - 0.5 1 1 (Cu) 340 98.3 2.9 78.1 79.7 56 12th 1 12th 4th 1 - 1 0.5 1 1 (Ce) 340 97.4 3.3 78.5 79.1 57 12th 1 12th 4th 1 - 1 0.5 1 3 (Ti) 340 98.2 3.1 78.3 79.0 58 12th 1 12th 4th 1 - 1 0.5 1 2 (Zn) 340 97.1 3.4 76.8 79.5 59 12th 1 12th 4th 1 - 1 0.5 1 2 (Cr) 340 97.5 2.9 77.0 78.8 60 12th 1 12th 4th - - 1 0.5 1 1 (La) 340 97.0 3.6 77.1 80.4 61 12th 1 12th 4th 1 - 1 0.5 1 4 (Al) 340 97.5 3.0 76.8 79.4 62 12th 1 12th 4th 1 - 1 0.5 1 2 (Cd) 340 96.8 3.9 77.8 79.7 63 12th 1 12th 4th 1 - 1 0.5 1 1 (Pb) 340 97.0 3.6 77.0 79.7 64 12th 1 12th 4th 1 - 1 0.5 1 1 (Cu) 340 97.2 3.4 77.5 80.0 65 12th 4th 340 97.4 3.1 77.6 66 12th 340 96.9 3.7 77.5 67 12th 340 12th

Table XI (port setting)

at
game Results of the 2nd oxidation stage Reaction
temperature
C ⁰ O TIMES-
conversion
(%) HAA
(based on MAL) Selecti
vity
(%) Converting the
unsaturated
Hydrocarbon
fabrics
(%) MAA yield in
a one-time
gen passage
(based on
iB)
(%) 55 335 78.3 Yield
one a
malign
Passage
V / o / 75.7 100 46.5 56 335 77.2 59.3 75.8 100 45.7 57 335 77.1 58.5 75.7 100 45.8 58 335 78.0 58.4 76.2 100 46.5 59 335 77.4. 59.4 75.8 100 45.1 60 335 79.6 58.7 76.4 100 46.8 61 335 77.0 · 60.8 75.5 100 44.8 62. 335 78.1 58.1 75.8 100 45.5 63 335 76.2 59.2 75.1 100 44.5 64 335 77.2 57.2 76.3 100 45.4 65 .335 77.5 58.9 76.5 100 46.0 66 335 77.8 59.3 75.6 100 45.6 67 335 77.1 58.8 75.4 100 45.0 58.1

Examples 68 to 80

- 44--

2735AU

Catalysts were prepared in the same manner as in Examples and 43, using the X component of the Catalysts of Examples 38 and 43 by arsenic or boron and the R component of the catalysts by rubidium, Replaced cesium or thallium. A reaction was carried out in a continuous 1st and 2nd stage after the same Procedure as in Example 1 using these catalysts. The results are shown in Table XII specified.

709886/0989

Table XII

oo oo σ>

composition Bi Fe (Atomic ratio) of the catalyst Ni AU Nd _ As for the s 1st oxidation stage Rb Cs Tl example 1 12th Co 1 1 _ 0.5 B. K _ _ 68 12th 1 12th 4th 1 1 - 0.5 - 0.5 1 - 0.1 - 69 12th 1 12th 4th 1 1 - - - - - 0.75 - - 70 12th 1 12th 4th 1 1 - - 0.5 - - - 0.75 71 12th 1 12th 4th 1 - 1 - - - _ _ _ 72 12th 1 12th 4th 1 - 1 - 0.5 - 1 - _ 73 12th 1 12th 4th 1 - 1 0.5 - - 1 - - - 74 12th 1 12th 4th 1 - 1 0.5 - 0.5 1 - 0.1 _ 75 12th 1 12th 4th 1 - 1 0.5 7th - '-. - 1 76 12th 1 12th 4th 1 - 1 0.5 _ _ _ .0.75 - 77 12th 1 12th 4th 1 - 1 _ _ 78 12th 1 12th 4th 1 - 1 0.5 0.5 0.5 0.75 0.75 79 12th . 1 12th 4th 1 1 _ _ 0.5 80 12th 4th 0.5

TableXH (port setting)

example Reaction
temperature
( ⁰ C). Results of the 1st oxidation stage Share of ge
formed un
saturated
Hydrocarbon
fabrics (%) TIMES selectivity
(%) 68 340 iB - Um-.
Change
(%) ³ , ⁵ Yield in
one time
leagues IXarch-
corridor (%) 78 _T 6 69 340 97.5 3.9 76.6 79.1 70 340 . 96.8 76.6 78.4 71 340 97.7 • v 76.6 79.5 72 "' 340 96.9 4.0 77.0 79 ^ 3 73 340 96.4 3.6 76.4 78.8 74 340 97.0 V 76.4 78.8 75 340 97.2 V 76.6 79, o 76 340 97.0 V 76.6 77.7 77 340 96 _? 8th V 75.2 78.5 78 340 97.1 3.6 76.2 78.1 79 340 97.1 ³ , ⁶ 75.8 78 6 80 340 96, 7 V 76.0 78 ^ 8 96.9 76.4

■ ν «O CO

Reaction
temperature
C ⁰ C) TIMES-
Transformation.
<%) Table XII (Continuation) Converting the
unsaturated
Hydrocarbon
fabrics
(%) MAA yield in
a one-time
gen passage.
(based on
iB)
(%) “Si at
game ' 335 76.9 Results of the 2nd oxidation stage 100 44.2 ■ ■ ^^ J
CaJ
cn 68 335 76.2 MAA
(based on TIMES) 100 43.4 69 335 76.7 Yield in
a one-time
gen passage
(%) Selek
tivi
activity
(%) .100 44.3 70 335 77.3 57.7 75.0 100 44.6 71 335 75.5 56.6 74.3 100 42.9 72 ' 335 75.9 - 57.8 75.4 100 43.3 73 "335 76.2 57.9 74.9 100 43.9 74 335 76.5 56.1. 74.3 100 44.3 . 75 335 76.0 56.7 74.7 100 42.9 76 335 76.3 57.3 75.2 100 44.2 77 335 76.3 57.8 75.5 100 43.6 78 335 76.6 57.1 75.1 100 43.6 79 335 76.4 58.0 76.0 100 43.9 80 57.5 75.4 57.4 74.9 57.5 75.3

⁵⁰ 27354U

Examples 81 to 84

The reaction was continued in a continuous 1st and 2nd stage in Examples 38, 43, 44 and 59 for 1000 hours continued under the same reaction conditions. The changes in the reaction results were determined. The results are given in Table XIII.

The results in Table XIII show that the catalysts of the invention, which contain Au or Nd, for the Processes in a continuous 1st and 2nd stage are suitable because they have high conversions and high selectivity result in the 1st oxidation stage and to a high degree reduce the formation of unsaturated hydrocarbons as by-products. In contrast, the catalyst has which does not contain the aforesaid ingredient (Comparative Example 17) has poor performance in the 1st oxidation stage and gives large amounts of unsaturated hydrocarbons as by-products, as in Table VI shown. For this reason, if such a catalyst is used as a catalyst for the 1st oxidation stage in the process of a continuous 1st and 2nd stage is used, the life of the catalyst for the 2nd oxidation stage is reduced.

709886/0989

Table XIII

Bel-
game Composition (atomic ratio) of the catalyst for the 1st oxidation stage Bi Fe Co Ni Au Nd P. K Ce Verstri
chene
current time
(StS.7 81 Mon 1 12th 4th 1 1 - 0.5 1 - 0 * '
1000 82 12th 1 12th 4th 1 - 1 0.5 1 - ο * '
1000 83 12th 1 6th 4th 1 - 1 0.5 1 - o '^;
1000 84 IZ 1 12th 4th 1 - 1 0.5 1 1 1000 12th

*) The symbol (*) indicates the early stage of the reaction.

Table XIII (porting)

00 a>

<O € »

at
game Results of the 1st oxidation stage Reaction
temperature
<° C) iB -
conversion
(%) Share of educated
unsaturated coals
hydrogen
(%) TIMES Selecti
vity
(%) 81 340
340 96.8
96.9 3.9
3.8 Yield in one
one-time through
corridor (%) 79.0
79.1 82 ¹ 340
340 96.7
97.0 3.9
3.7 76.5
76.6 78.9
79.5 83 370
370 96.5
96.5 4.2
4.2 76.3
77.1 78.1
77.7 84 340
340 97.1
97.3 3.4
3.3 75.4
75.0 79.1
79.3 76.8
77.2

Or

CO cn

Table XIII (continued)

at
game Results of the 2nd oxidation stage Reaction
temperature
(° C) MAL-Um-
change
(%) MAA
(based on MAL) Selek
activity
(%) Converting the
unsaturated
Hydrocarbon
fabrics
(%) MAA yield in
a one-time
gen passage
(based on iB)
(%) 81 335
335 76.2
76.3 Yield in one
one-time through
corridor
(%) 75.1
75.1 100
100 43.8
43.9 82 335
335 76.1
76.5 57.2
57.3 75.0
75.3 100
100 43.6
44.4 83 335
335 75.6
75.8 57.1
57.6 75.3
74.9 100
100 42.9
42.6 84 335
335 77.4
78.0 56.9
56.8 75.8
75.5 100
100 45.1
45.5 58.7
58.9

2735AU

Examples 85 to 88

By using the catalysts for the 1st oxidation stage used in Examples 81 to 84,
one carried out an implementation in a continuous 1. and
2nd stage in the same manner as in Example 1, with the exception that propylene was used as the starting gas instead of isobutylene. The reaction results are given in Table XIV.

709886/0989

Table XIV

at
game Results of the 1st oxidation stage Mon Bi Fe Co Ni AU Nd P. K Ce React
functional
temp
( ⁰ C) Propy
len-um-
change
(%) Share of ge
forms, uns.
Hydrocarbon
fabrics (%) Acrolein Seleto
üvi-
rate (%) 85
86
87
88 Catalyst composition
(Atomic ratio) 12th
12th
12th
12th 1
1
' 1
1 12th
12th
6th
12th 4th
4th
4th
4th 1
1
1
1 1 1
1
1 0.5
0.5
0.5
0.5 1
1
1
1 1 360
360
360
360 98.1
98.6
98.2
98.7 2.3
1.9
2.1
1.8 Au sb. in a.
unique
Continuous (%) 85.4
85.8
84.2
86.0 83.8
84.6
82.7
84.9

Table XIV (continued)

CO OO OO

ο co α »co

at
game Results of the 2nd oxidation stage rteakti-
onstem-
temperature
( ⁰ C) AeroIein
conversion
(%) Acrylic acid
(based on acrolein) Selek
tivi-
rate (%) Converting the
unsaturated
Hydrocarbon
fabrics
(%) Acrylic acid yield
in a one-off
Passage (related
on propylene)
(%; 85
86
87
88 360
360
360
360 88.4
88.9
88.4
89.3 Yield in one
one-time through
corridor (%) 89.8
90.0
90.0
90.5 100
100
100
100 66.5
67.7
65.8
68.6 79.4
80.0
79.6
80.8

cn he »

Claims (14)

Claims Q is at least one element selected from Au and Nd; R is at least one element selected from K, Rb, Cs and Tl; X is at least one element selected from P, As and B; Z at least one element selected from Ce, Ti, Te, Zn, Ge, Sn, Cr, Ga, La, In, Al, Cd, Pd, Mn, V, Pb, Nb, Ag, Zr, Cu and U, represents; a, b, c, d, e, f, g, h, i and j, respectively, mean the number of atoms of Mo, Bi, Fe, Co, Ni, Be, Q, R, X and Z, and when a is 12, b is 0.1 to 10, c is 0.5 to 40, d is O to 12, e is O to 12 with the proviso that the sum of d and e is 0.5 to 15, f is 0 to 35, g is 0 to 8 with the proviso that the The sum of f and g is 0.1 or more, h is 0.01 to 5, i is O to 5, j is O to 12 and k means the number of oxygen atoms, which are the atomic valences saturate the other elements. 2. The catalyst of claim 1 wherein when a is 12, b is 0.5 to 7, c is 1 to 35, d is 0 to 10, e is 0 to 10 provided that the sum of d and e is 0.5 to, f is O to 30, g is O to 6, provided that that the sum of f and g is 0.1 or more, h is from 0.01 to 4, i is from 0 to 4, and j is from 0 to 8. 709886/0989 1 "27354H 3. A catalyst according to claim 1, wherein when a is 12, b is 0.5 to 7, c is 8 to 30, d is 0 to 10, e is 0 to 10 provided that the sum of d and e is 0.5 to 12, f is 0 to 20, g is 0.1 to 4, provided that that the sum of f and g is 0.1 or more, h is 0.01 to 3, i is O to 3, and j is O to 8. 4. The catalyst of claim 1 wherein when a is 12, f is 0.1-35. 5. The catalyst of claim 1 wherein when a is 12, f is O is. 6. Catalyst according to claim 1, wherein R is K. 7. A catalyst according to claim 1, wherein R is Rb. 8. A catalyst according to claim 1, wherein R is Cs. 9. Catalyst according to claim 1, wherein R is Tl. 10. A catalyst according to claim 1, wherein Q is Au. 11. A catalyst according to claim 1, wherein Q is Nd. 12. A process for the preparation of unsaturated aldehydes, characterized in that there are 3 carbon atoms in a straight line Chain-containing olefins in the gas phase in the presence of a catalyst according to claim 1 at a Temperatuj oxidized. Temperature from 250 to 700 ° C, preferably 250 to 550 ° C, 13. The method according to claim 12, characterized in that air is used as the oxygen source. 14. The method according to claim 12, characterized in that the reaction is carried out in the presence of an inert gas will. 709886/0989