DE2337315C3 - Process for the production of acrylonitrile or methacrylonitrile from propylene or isobutylene - Google Patents

Description

the use of Co - Fe - Bi - W - Mo - Si - nitric acid and a solution of a fixed one

Alkali Metal Catalysts for the Oxidation of Amount of Ammonium Molybdate in Aqueous Am-

monia dropwise to the above solution in The Methods for Preparing the Catalyst

Stirring added, causing a precipitate to form, is not critical. The catalyst can also

will. After standing overnight, the lowering is achieved by methods other than those explained above.

blow washed by repeated decanting, put. Likewise are the starting materials that

filtered, dried and finally calcined. The 5 used for the production of the catalyst,

Calcined product is pulverized and not crucial to pellets.

or particles of desired shape and size. The catalyst can be used alone or in combination shaped. Similarly, any known carrier can also be used. Catalysts are produced, the barium, zinc As a carrier, those can be used for or other metals of group II of the period io the reaction in question beneficial host system, instead of calcium. have effects, such as B. silica, alumina, Bi_Mo-W-II-X-O-Kata! Ysaior (l) alumina-silica, silicate diatomaceous earth, etc.,

which are deactivated, for example, by a heat treatment

A fixed amount of ammonium parawolf-four have been given. These carriers can for example

Rarnat is dissolved in hot water, followed by 15 in an amount of 10 to 90 percent by weight of the

the addition of niobium pentoxide. In this solution catalyst will be used

a fixed amount of calcium nitrate dissolved The catalyst can either be in a fluidized bed

and thereafter applying a solution of a fixed amount or in a fixed bed, though

of bismuth nitrate in nitric acid and a solution of the bed arrangement with greater advantages

a fixed amount of ammonium molybdate 20, since the life of the catalyst is extreme

long in aqueous ammonia dropwise with stirring.

added, whereby a precipitate is formed. The dimensions and the arrangement of the cataly- The precipitation is treated as in the previous satorkörner is not decisive, but depends in the example. After a corresponding decision, it primarily depends on whether the catalyst can be used in one drive, as well as other catalysts, a fluidized bed or a fixed bed. The instead of calcium barium, zinc or other catalyst can also be shaped or granulated by means of suitable known metals of group II of the periodic table and processes in order to create the required mechanical strength other metals that stand for X in place of niobium,
can contain, made willows. The indicated in the method according to the invention

n; \ Ar. w 11 ν nv.t-, ι. "". , ^ 3 ° turned propylene or isobutylene charge must

lsi-ivio-w-Ii-λ-vj-r ».uiaiysaior i -ϊ. ,,,. . , · · * ■ j ι

not necessarily be highly purified, but it can

A solution of ammonium mcilybdate in aqueous also a mixture of propylene or isobutylene

Ammonia is used to produce a jointly with saturated hydrocarbons, such as. B. with

precipitated precipitate can be used with a solution of propane and butane. However, should

Calcium nitrate is treated in nitric acid, the 35 being any gases that cause ammoxidation among the

Amounts of Mo and Ca are equimolar. The common special reaction conditions in any one

The precipitate which has precipitated out is washed, significantly influencing a noticeable degree, such as, for example, B.

filtered, dried and then calcined. The acetylene, n-ButyW: n and the like, preferably in the for

Product is calcium molybdate with egg formula CaMoO ₄ . does not contain the feed used in the reaction

It will be an aqueous solution of tungstic acid 4 ° as it forms undesirable by-products

with a solution of bismuth nitrate in nitric acid can.

treated, with the molar ratio of tungstic acid. Likewise, other diluents,

to bismuth nitrate is 1: 2. The treated which do not affect the ammoxidation in the

Solution is heated to dryness until the formation of reaction mixture occurs without any adverse effect

Ammonium nitrate and nitric oxide stops. The one to be 45. Such diluents include, for example

Solid obtained in this way is used to produce steam, nitrogen and carbon dioxide. the

of bismuth tungstate of formula Bi ₂ O ₃ · WO ₃ calci- amount of diluent in the feed

ned. for the reaction is preferably more than

A solution of iron nitrate in nitric acid will be 0.5 moles per mole of propylene or isobutylene. steam

with a solution of bismuth nitrate in nitric acid 5 <> acts in the reaction mixture not only as

treated, taking the amounts of Fe and Bi equi-diluent, but he also shows a the

are molar. The mixed solution is up to the selectivity of the catalyst for the formation of

Heat dry until the generation of nitric oxide acrylonitrile or methacrylonitrile-enhancing effect

stops. The solid obtained becomes the manufacture and also makes the activity of the catalyst

Provision of bismuth ferric acid of the formula BiFeO ₃ kai- 55 permanently. Accordingly, it becomes ordinary

ziniert. preferably, the feed has at least 0.5 moles of steam

Add calcium molybdate (CaMoO ₄ ), bismuth per mole of propylene, or isobutylene,

tungstate (Bi ₂ O ₃ · WO ₃ ) and the bismuth ferrate As a source for the oxygen, which in the invention

(BiFeO ₃ ) are kneaded with water, dried. Used in accordance with ammoxidation can be purer

calcined and then into pellets or larger 60 oxygen or any oxygen containing gas

Particle deformed. can be used. In particular, it can be advantageous

Similarly, other air-wise catalysts can be used. A corresponding one

be prepared by mixing and kneading, such as the proportion of oxygen in the reaction charge

for example calcium molybdate (CaMoO ₄ ) and Wis- is suitably 0.8 to 4 mol, and preferably

Mung tungstate (Bi ₈ O ₃ · WO ₃ ) with bismuth vanadai 65 wise about 1.0 to about 2.5 Mo! per Mon! Propylene

(BiVO ₄ ), bismuth titanate (Bi ₂ Ti ₂ O ₇ ), bismuth tantalate or isobutylene. A feed of oxygen in the

(BiTaO ₄ ), bismuth niobate _{(Bi 2 NbO 5} , BiNbO ₄ ) and excess beyond the limit given above

Bismuth zirconate [Bi ₂ (Zr0 ₃ ) ₃ ]. inevitably leads to the formation of by-products,

such as carbon monoxide and carbon dioxide. In contrast to this, a feed of Oxygen in an amount below the above range to reduce the selectivity of the End product.

An appropriate proportion of ammonia in the feed to the reaction mixture is suitable in the range from 0.5 to 3 mol, and preferably in the range from about 0.8 to 1.2 mol per mol of propylene or isobutylene.

The ammoxidation is usually carried out under atmospheric pressure, although optionally can work even with a slight overpressure or slightly reduced pressure.

The reaction is carried out at a temperature in the range between 300 and 550 ^° C., preferably between 350 and 500 ° C. Reaction temperatures which are higher than the upper limit lead to the decomposition of propylene or isobutylene, reduce the selectivity and promote it Side reactions: The ammoxidation is particularly advantageously carried out at a temperature of approximately 400.degree.

A contact time of 0.3 to 20 seconds, in particular 0.5 to 15 seconds, is preferred. One

ίο contact time that exceeds the upper limit value, causes the decomposition of the reaction product and other undesirable side reactions.

The following examples are given to illustrate the invention. In the examples they are The terms "% conversion" and "% selectivity" are defined as follows:

% Conversion =

Used moles of propylene or isobutylene. Added moles of propylene or isobutylene 100

Moles of propylene or isobutylene converted to acrylonitrile or methacrylonitrile Moles of propylene or isobutylene consumed

• 100

The term "%" also means percent by weight.

Examples 1 to 6

Bi-Mo-W-Ca catalyst

H) WOO ₄ , ·

90.6 grams of ammonium paratungstate
5 H ₂ O] and 245.6 g of calcium nitrate [Ca (NO _3)., 4 ■ H ₂ O] were dissolved in 1 1 water which was maintained at 60 ⁰ C, dissolved unjter stirring. A solution of 168.2 g of bismuth nitrate iBi (NO ₃ ) ₃ · 5 H ₂ O] in 202 ml of 10% nitric acid and a solution of 122.6 g of ammonium molybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4 H ₂ O] in 267 ml of 10% aqueous ammonia was added. Then 10% aqueous ammonia was added to the reaction mixture in order to adjust the pH to 4.0 and to precipitate a precipitate. After standing overnight, the precipitate was washed by decanting four times, filtered off and dried. The product was made into tablets with a diameter of 5 mm and then calcined at 600 ° C. for 16 hours.

Using the catalyst thus prepared, ammoxidation was carried out according to the following Working methods carried out.

45 In Example 1, 20 ml of the catalyst prepared in this way were introduced into a U-type reaction tube made of glass with an internal diameter of 10 mm. A gaseous mixture of propylene, ammonia, air and steam with a molar ratio of the four components of 27: 27: 300: 106 was passed through the reaction tube filled with the catalyst, which was kept at 420 ° C., at a flow rate of 460 ml / Min. The contact time was 2.6 seconds.

In Example 2, the procedure of Example 1 was used, the amount of catalyst introduced into the reaction tube being 30 ml, the reaction ^{temperature 400 °} C. and the contact time being 3.9 seconds, and the other conditions being the same.

In Example 3, the procedure of Example 1 was used, but instead of propylene Isobutylene was used and all other conditions were the same.

In Examples 4, 5 and 6 the procedure of Example 1 was used, but with the catalysts the four metal components contained in varied atomic proportions, and all other conditions were the same.

The results are shown in Table I.

table I. product catalyst Atomic ratio Around
Wall
lung Selek
activity example
No. Starting
material ON*)
ON
MAN *
ON
ON
ON Bi — Mon — W-
the same
*) the same
the same
the same
the same 1: 2-1: 3: 13.3
1 · 2 · 1 · 3 · 13 5 96.0
94.6
97.3
96.5
89.3
91.2 89.1
88.9
83.2
86.6
88.2
85.3 1
2
3
4th
5
6th
♦) ON Propylene
the same
Isobutylene
Propylene
the same
the same
: Acrylonitrile. 1: 2: 1: 3: 13.5
1: 2: 1: 6: 16.5
2: 1: 2: 4: 16
1: 2: 1: 1: 11.5 -Ca-O

*) MAN: methacrylonitrile.

Example 7
Bi - Mo - W - Ca catalyst

90.6 g of ammonium paratungstate [(NH ₄ ) ₁₀ W ₁₂ O _4I · 5 H ₂ O] and 122.8 g of calcium nitrate [Ca (NO ₃ ) ₂ · 4 H ₂ O] were dissolved in 1 liter of hot water. To this solution, 168.2 g of bismuth nitrate [Bi (NO ₃ ) ₃ · 5 H ₂ O] and 112.6 g of ammonium molybdate [(NH ₄ ) _e Mo ₇ O ₂ , · 4 H _a O] were added simultaneously with vigorous stirring. The resulting solution was heated to dryness in a sand bath until the formation of NO ₂ gas ceased. 1.5% graphite was added to the product. The mixture was then shaped into tablets with a diameter of 5 mm. The tablets were calcined at 600 ° C. for 10 hours.

Using the catalyst, ammoxidation of propylene was carried out in the same way Procedure as in Example 1 carried out. The results are given in Table II.

Examples
Bi-Mo-W-Ba catalyst

90.6 g of ammonium paratungstate [(NH _{4) Ifl W] 2} O ₄₁ · 5H ₂ O] and 146 g of barium [Ba (NO _{3) 2]} were in 11-water, which was maintained at 6O ⁰ C, with stirring, dissolved. A solution of 168.2 g of bismuth nitrate [Bi (NOg) ₃ · 5 H ₂ O] in 202 ml of 10% nitric acid and a solution of 112.6 g of ammonium molybdate [(NH ₄ ) _e Mo ₇ O ₂₄ · 4 H ₂ O] in 267 ml of 10% aqueous ammonia was added. Then 10% aqueous ammonia was added to the reaction mixture to adjust the pH to 4.0 and to form a precipitate. After standing overnight, the precipitate was washed by decanting four times, filtered off and dried. The dried product was shaped into tablets and then ^{calcined at 600 °} C. for 16 hours.

Using the catalyst thus prepared, the ammoxidation of propylene was carried out according to the the same procedure as in Example 1 carried out. The results are given in Table II.

Example 9
Bi — Mo — W — Zn catalyst * ⁵

The process for preparing the catalyst according to Example 8 was repeated, 153.5 g of zinc nitrate [Zn (NO ₃ ) ₂ · 6 H ₂ O] being used instead of 146 g of barium nitrate and all other conditions remaining.

Using the catalyst thus prepared, the ammoxidation of propylene was carried out according to the the same procedure as in Example 1 was carried out. The results are given in Table II.

Comparative experiment 1
Bi-Mo-Ca catalyst

245.6 g of calcium nitrate [Ca (NO ₃ V 4 HgO] were dissolved in 1 l of water, which was maintained at 6O ⁰ C, dissolved. To this solution were simultaneously added dropwise 168.2 g of bismuth nitrate [Bi (NO _{s) 3} · 5 H ₂ O] in 202 ml of a 10% nitric acid and a solution of 122.6 g of ammonium molybdate [(NH ₄₎ Mo ₇ O _{e M} · 4 H ₂ O] in 276 ml of 10% aqueous ammonia was added. Subsequently, aqueous Ammonia was added to the reaction mixture, thereby adjusting the pH to 4.0 to form a precipitate, and the precipitate thus formed was treated in the same manner as in Example 1.

Using the catalyst thus prepared, the ammoxidation of propylene was carried out according to the the same procedure as in Example 1 carried out. The results are given in Table II.

Comparative experiment 2
Bi-Mo-W catalyst

Bismuth oxide [Bi _g O _s ], molybdenum _{oxide [MoO 3} ] and tungsten oxide [WO ₃ ] were mixed in a molar ratio of BiO: MoO ₃ : WO ₃ = 2: 1: 2. The mixture was kneaded together with a small amount of water and then dried at 120 to 13O ⁰ C. The dried product was ^{calcined at 540 °} C. for 16 hours.

The ammoxidation of propylene was carried out using the catalyst thus prepared the same procedure as in Example 1 was carried out.

Table II

example Initial product catalyst Atomic ratio Around Selek No. material Wall activity lung (54) ( O / \
\/O)

7th Propylene ON Bt-Mo-W-Ca-O 1: 2: 1: 1.5: 12 93.5 87.1 8th the same ON Bi-Mo-W-Ba-O 1: 2: 1: 1.5: 12 97.2 85.3 9 the same ON Bi-Mo-W-Zn-O 1: 2: 1: 1.5: 12 97.2 85.3 Comparison
attempt 1 the same ON Bi - Mo - Ca - O 1: 2: 3: 10.5 70.3 73.8 Comparison
attempt 2 the same ON Bi - Mo - W - O 4: 1: 2:15 85.6 75.6

709 636/244

Examples 10 to 16 Bi-Mo-W-Ca-Nb catalyst

74.1 g ammonium parawolfiramate [(NH ₄ ) I ₀ W ₁₂ O ₄₁ · 5H ₂ O], 9.4 g niobium pentoxide (Nb ₂ O ₅ ) and 251.3 g calcium nitrate [Ca (NO ₃ ) ₂ · 4 H ₂ O] were dissolved in 1 1 water which was maintained at 6O ⁰ C with stirring. A solution of 172 g of bismuth nitrate [Bi (NOa) ₃ · 5 H ₄ O] in 207 ml of 10% nitric acid and a solution of 125.5 g of ammonium molybdate [(NH ₄ ) _e Mo, O] were simultaneously added dropwise to this solution ₂₄ · 4 H ₂ O] in 298 ml of 10% aqueous ammonia was added. Then 10% aqueous ammonia was added to the reaction mixture to adjust the pH to 4.0 and to precipitate a precipitate. The precipitate was treated in the same manner as in Example 1.

In Example 10, the ammoxidation of ao Propylene carried out by the same procedure as in Example 1.

In Examples 11 and 12 the procedure of Example 10 was followed using the process conditions as indicated below, and all other conditions the same stayed.

Example 11 Example 12

Amount of catalyst 30 ml 10 ml Reaction temperature 400 ° C 450 ° C Contact time 3.9 sec. 1.3 sec.

10

30 In Example 13, the ammoxidation of isobutylene by the same procedure was performed as in Example 10 with the exception that isobutylene was used in place of propylene.

In Examples 14, 15 and 16 the procedure of Example 10 was followed, using catalysts were used, which contained the five metal components in varying atomic ratios and all other conditions remained the same. The results of Examples 10-16 are recorded in Table III.

Example 17
Bi-Mo-W-Ca-Nb catalyst

74.1 g ammonium paratungstate [(NH ₄ ), ₀ W, ₂ O ₄₁ · 5H ₂ O], 9.4 g niobium pentoxide [Nb ₂ O ₅ ] and 125.7 g calcium nitrate [(Ca (NO ₃ ) ₂ · 4 H ₂ O] were dissolved in hot water. 172.2 g of bismuth nitrate [Bi (NO ₃ ) ₃ · 5 H ₂ O] and 125.5 g of ammonium molybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4 H ₂ O] was added simultaneously with vigorous stirring. The resulting slurry was heated to dryness in a sand bath until the formation of NO ₂ -Ga; was ceased. From this dried product a pelletized catalyst was produced in the same manner as prepared in Example 7.

Using the catalyst so prepared, the ammoxidation of propylene was after the same procedure as in Example 10 leads through. The results are given in Table III

Table III

Example output "
No. Material

Product catalyst

Atomic ratio

Conversion
lung

selectivity

10 Propylene ON Bi — Mo— 11th the same ON the same 12th the same ON the same 13th Isobutylene MAN the same 14th Propylene ON the same 15th the same ON the same 16 the same ON the same 17th the same ON the same B ε i s ■ game 18 until 24 Bi-Mo-W-Ca-Ti catalyst

Bi-Mo-W-Ca-Nb-O 1: 2: 0.8: 3: 0.2: 13.4

1: 2: 0.8: 3: 0.2: 13.4
1: 2: 0.8: 3: 0.2: 13.4
1: 2: 0.3: 3: 0.2: 13.4
1: 2: 0.5: 3: 0.5: 10.55
1: 1.8: 0.3: 6: 0.7: 14.55
1: 1.8: 0.9: 6: 0.1: 15.05
1: 2: 0.8: 1.5: 0.2: 11.9

? 6.5 90.0 95.0 89.8 94.0 88.5 98.0 84.3 96.3 89.6 95.5 87.5 96.5 88.5 94.0 90.2

75.1 g ammonium paratungstate [(NH ₄ ) J ₀ W ₁₂ O ₄₁ · 5 H ₁ O], 5.75 g titanium dioxide | tiO ₂ ] and 254.5 g calcium nitrate [Ca (NO ₃ ) g · 4 H ₂ O ^{] were dissolved in 1} liter of water, which was kept at 60 ° C., with stirring. A solution of 174.4 g of bismuth niirate [Bi (NOj) ₃ -5H ₁ O] in 210 ml of 10% nitric acid and a solution of ammonium molybdate [(ΝΗ ₄ ) _β Μο, Ο ₂₄ · 4H were added dropwise to this solution at the same time ₁ O] in 301ml of 10% aqueous ammonia was added. Then 10% aqueous ammonia was added to the reaction mixture and the pH was thereby adjusted to 4.0 for the precipitation of a precipitate. The precipitate was treated in the same manner as in Example 1.

In Example 18, using the si prepared catalyst, the ammoxidation of propylene by the same process as in Bei Game 1 performed.

In Examples 19 and 20, the procedure of Example 18 was used using the procedure conditions were varied as follows and all other conditions remained the same.

Example 19 Example 20

Amount of catalyst 30 ml 10 ml

Reaction temperature 400 ° C 450 "C

Contact time 3.9 sec. 1.3 sec.

In Example 21, the ammoxidation was voi Isobutylene by the same procedure as i

I 23

Example 18 was carried out, with the exception that isobutylene was used instead of propylene. In Examples 22, 23 and 24 the procedure of Example 18 was followed, using catalysts were used, which contained the five metal components in varying atomic proportions, and all other conditions remained the same. The results of Examples 18-24 are recorded in Table IV.

Example 2: 5

Bi-Mo-W-Ca-Ti catalyst

A catalyst was prepared from the following compounds by the same method as in Example 17 made.

Ammonium paratungstate 75.1 g [(NH ₄ ) _ie W _lt O "· 5 H ₂ O]

Titanium dioxide [TiO ₂ ] 5.75 g

Calcium nitrate [Ca (NO ₃ ) ₂ · 4 H ₂ O] 127.3 g

Bismuth nitrate [Bi (NO ₃ ) ₃ · 5 H ₂ O] 174.4 g "

Ammonium molybdate 127.1 g [(NH ₄ ) _e Mo ₇ O ₂₄ · 4 H ₂ O]

The ammoxidation of propylene was carried out using the catalyst thus prepared the same procedure was carried out as in Example 10, all other conditions being the same stayed. The results are given in Table IV.

Examples 26-29

Bi-Mo-W-Ca-Ta catalyst 315

72.6 grams of ammonium paratungstate
5H ₂ O]. 15.4 g of tantalum pentoxide [Ta ₂ O ₅ ] and 246.2 g of calcium nitrate [Ca (NO ₃ ) ₂ · 4 H ₂ ^{O] were dissolved in 1} liter of water, which was kept at 60 ° C., with stirring. A solution of 168.7 g of bismuth nitrate [Bi (NO ₃ ) ₃ · 5HgO] in 203 ml of 10% nitric acid and a solution of 122.9 g of ammonium molybdate [(ΝΗ ^ Μο, Ομ · 4 H ₂ O] in 291 ml of 10% aqueous ammonia was added, then 10% aqueous ammonia was added to the reaction mixture

Table IV

Adjustment of the pH to 4.0 and precipitation of a precipitate added. The precipitation was treated in the same manner as in Example 1.

In Examples 26 and 27, the ammoxidation was carried out using the catalyst thus prepared carried out by the same method as in Example 1 of propylene or isobutylene.

In Examples 28 and 29 the procedure of Example 26 was followed, using catalysts were used which contained the five metal components in varying atomic ratios, where all other conditions remained the same. The results of Examples 26-29 are in Table IV laid down.

Examples 30 to 33

Bi-Mo-W-Ca-Zr catalyst

74.3 g ammonium paratungstate [(NH ₄ ) ₁₀ W ₁₂ O ₄₁ · 5 H ₂ O], 19.0 g zirconium nitrate [ZrO (NO ₃ ) ₂ · 2 H ₂ O] and 251.9 g calcium nitrate [Ca (NO ₃ ) ₂ x 4 H ₂ O] were dissolved in 1 L of water kept at 60 ° C with stirring. A solution of 172.6 g of bismuth nitrate [Bi (NO ₃ ) ₃ · 5 H ₂ O] in 207 ml of 10% nitric acid and a solution of 125.8 g of ammonium molybdate [(N Η ₄ ) were added dropwise to this solution at the same time. _β Μο, Ο ₂₄ · 4 H ₂ O] in 10% aqueous ammonia was added. Then 10% aqueous ammonia was added to adjust the pH to 4.0 and to precipitate a precipitate. The precipitate was treated in the same manner as in Example 1.

Examples 30 and 31 employed ammoxidation of propylene and isobutylene, respectively of the catalyst prepared in this way by the same procedure as in Example 1 carried out.

In Examples 32 and 33 the procedure of Example 30 was followed, using catalysts were used which contained the five metal components in varying atomic ratios, where all other conditions were the same. The results of Examples 30 to 33 are presented in dei Table IV shown.

example

Source material

Product catalyst atomic ratio

Um- selectivity

18th Propylene ON Bi — Mon — W 19th the same ON the same 20th the same ON the same 21 Isobutylene MAN the same 22nd Propylene ON the same 23 Propylene ON Bi — Mon — W 24 the same ON the same 25th the same ON the same 26th the same ON Bi — Mon — W 27 Isobutylene MAN the same 28 Propylene ON the same 29 the same ON the same 30th the same ON Bi — Mon — W 31 Isobutylene MAN the same 32 Propylene ON the same 33 the same ON the same

-Ca-Ti-O 1: 2: 0.8: 3: 0.2: 13.3 96.0 89.5

the same 94.4 89.1

also 93.5 88.0

the same 97.5 83.8

1: 2: 0.5: 3: 0.5: 13 95.7 89.1

-Ca-Ti-O 1: 1.8: 0.3: 6: 0.7: 15.2 95.0 86.8

1: 1.8: 0.9: 6: 0.1: 15.8 95.9 88.1

1: 2: 0.8: 1.5: 0.2: 11.8 93.5 89.0

-Ca-Ta-0 1: 2: 0.8: 3: 0.2: 13.3 95.7 88.3

also 97.0 82.0

1: 2: 0.5: 3: 0.5: 13 95.4 87.9

1: 1.8: 0.9: 6: 0.1: 15.8 95.6 87.0

-Ca-Zr-O 1: 2: 0.8: 3: 0.2: 13.3 95.5 87.5

also 97.0 82.2

1: 2: 0.5: 3: 0.5: 13 95.3 87.0

1: 1.8: 0.9: 6: 0.1: 15.8 95.5 86.0

Examples 34 to 40
Bi-Mo-W-Ca-Fe catalyst

75.1 grams of ammonium paratungstate
5 H, OJ, 29.0 g of iron (III) nitrate [Fe (NO ₃ )., · 9 H ₂ O] and 254.5 g of calcium nitrate [Ca (NO ₃ ) ₂ · 4 H ₂ O] were in 1 l of water, which was kept at 60 ° C., dissolved with stirring. A solution of 174.4 g of wisinut nitrate [Bi (NO ₃ ) ₃ · 5 H ₂ O] in 210 ml of 10% strength nitric acid and a solution of 127.0 g of ammonium molybdate in 302 ml of 10% strength aqueous ammonia were added dropwise to this solution admitted. Then 10% aqueous ammonia was added to adjust the pH to 4.0 and to precipitate a precipitate. The precipitate was treated in the same manner as in Example 1.

In Examples 34 and 37, using the catalyst thus prepared, the Ammoxidation of propylene or isobutylene by the same method as in Example 1 carried out.

In Examples 35 and 36 the procedure of Example 10 was used with the process conditions varied as set forth below and all other conditions were the same.

Example 35 Example 36

Amount of catalyst 30th ml 10 ml Reaction temperature 400 ⁰ C 450 ^C C Contact time 3, 9 sec. 1 , 3 sec.

In Examples 38, 39 and 40 the procedure of Example 34 was followed using Catalysts containing the five metal components in varying atomic ratios, and all other conditions being the same.

The results of Examples 34-40 are shown in Table V.

B is ρ ie 1 41
Bi-Mo-W-Ca-Fe catalyst

49.6 g ammonium paratungstate [(NHi) ₁₀ W ₁₂ O ₄₁ · 5H ₂ O], 76.8 g iron (III) nitrate [Fe (NO ₃ ) ₃ ■ 9 H ₂ O] and 269.2 g calcium nitrate [ Ca (NO ₃ ) ₂ · 4 H ₂ O] were dissolved in 11% of hot water. 184.4 g of bismuth nitrate [Bi (NO ₃ )., · 5 H ₂ O] and 134.4 g of ammonium molybdate [(NH,) ₆ Mo _? Oj4 · 4H ₂ O] was added. The resulting slurry was heated to dryness in a sand bath until the formation of NO ₂ -GaS ceased. 1.5% graphite was added to the dried product. The mixture was then shaped into tablets with a diameter of 5 mm. The tablets were lOStd. calcined at 600 ⁰ C.

Using the catalyst thus prepared, the same procedure as in Example 34 carried out an ammoxidation of propylene. The results are given in Table V.

Eg 1c 42 to 45
Bi-Mo-W-Ca-cocatalyst

49.8 g ammonium paratungstate [(NH ₄ I ₁₀ W ₁ OO ₄₁ · 5 H ₂ O], 55.5 g cobalt nitrate [Co (NOg) ₂ · 6 H ₂ O] and 270.1 g calcium nitrate [Ca (NO ₃ ) _{2 -4H 2} O] were dissolved in 1 l of water which was kept at 60 ° C. A solution of 185.0 g of _{bismuth nitrate [Bi (NO 3} ) ₃ · 5 H ₂ O] in 222 ml of 10% nitric acid and a solution of 134.8 g of ammonium molybdate [<NH ₄ ) ₀ Mo ₇ O ₂₄ · 4 H ₂ O] in 320 ml of 10% aqueous ammonia were added. Then 10% aqueous ammonia was used to adjust the pH

ίο added to 4.0 and precipitation of a precipitate. The precipitate was treated in the same manner as in Example 1.

In Example 42, using the catalyst thus prepared, pine ammoxidation of Propylene carried out by the same procedure as in Example 1.

In Examples 43, 44 and 45 the procedure of Example 2 was followed using catalysts were used, which contained the five metal components in varying atomic proportions, and all other conditions were the same.

The results of Examples 42 to 45 are set out in Table V.

Examples 46 to 49
Bi - Mo - W - Ca - Ni catalyst

49.8 g ammonium paratungstate [(NH ₄ ) ₁₀ W ₁₂ O _4I · 5 H ₂ O], 270.1 g calcium nitrate [Ca (NO ₃ ) ₂ · 4 H ₂ O] and 55.5 g nickel nitrate [Ni (NO _{3) 2} · 6 H ₄ O] were dissolved in 1 1 water which was maintained at 6O ⁰ C under stirring. A solution of 185.1 g of bismuth nitrate [Bi (NO ₃ ) ₃ · 5 H ₂ O] in 222 ml of 10% nitric acid and a solution of 134.9 g of ammonium molybdate [(NHi) ₆ Mo ₇ O ₂₁ · 4 H ₂ O] in 320 ml of 10% aqueous ammonia was added. Then 10% aqueous ammonia was added to adjust the pH to 4 and to precipitate a precipitate. The precipitate was treated in the same manner as in Example 1.

In Example 46, an ammoxidation of Propylene carried out by the same procedure as in Example 1.

In Examples 47-49 the procedure of Example 46 was followed using catalysts containing the five metal components in varying atomic ratios, and all other conditions being the same. The results of Examples 46 to 49 are shown in Table V shown.

B e i s ρ i e 1 e 50 to 53

Bi - Mo - W - Ca - Cr catalyst

49.8 g ammonium paratungstate [(NH ₄ ) J ₀ W ₁₈ O ₄₁ · 5 H ₂ O], 76.3 g chromium _{nitrate [Cr (NO 3} ), · 9 H, O] and 269.9 g calcium nitrate [Ca ( NO ₃ ) ₂ · 4 H ₂ O] were dissolved in 1 l of water kept at 60 ° C. with stirring. A solution of 184.9 g of bismuth nitrate [Bi (NO ₃ ) ₃ · 5 H ₂ O] in 222 ml of a 10% strength was added dropwise at the same time to this solution

Nitric acid and a solution of 134.7 g of ammonium molybdate [(ΝΗ ₄ ) _β Μο, 0 ₂₄ · 4Η ₂ 0] in 319 ml of 10% aqueous ammonia were added. Then 10% aqueous ammonia was used

Adjustment of the pH value to 4 and precipitation: a precipitate added. The precipitation was treated in the same manner as in Example 1.

In Example 50, ammoxidation of propylene was carried out using the so prepared Catalyst carried out by the same procedure as in Example 1.

In Examples 51, 52 and 53 the procedure of Example 5 was followed using catalysts were used, which contained the five metal components in varying atomic proportions, and all other conditions were the same. The results of Examples 50 to 53 are set out in Table V.

Examples 54 to 57
Bi-Mo-W-Ca-Mn catalyst

49.9 g of ammonium paratungstate [(NH ₄ ) _{] 0} W ₁₂ O ₄ , · 5 H ₂ O], 90.0 g of manganese nitrate [Mn (NO ₃ ) ;, · 6 H ₂ O] and 270.8 g of calcium nitrate [ Ca (NO ₃ )., · 4 H ₂ O] were in

1 1 of water, which was kept at 6O ⁰ C, dissolved with stirring. A solution of 185.5 g of bismuth nitrate [Bi (NO ₃ J ₃ -SH ₂ O] in 223 ml of 10% nitric acid and a solution of 135.2 g of ammonium molybdate [(NH ₄ ) _e Mo ₇ O _M -4 H ₂ O] in 321 ml of 10% aqueous ammonia was then added, followed by 10% aqueous ammonia to adjust the pH to 4.0 and precipitate one

ίο Precipitation added. The precipitate was in treated in the same manner as in Example 1.

In Example 54, an ammoxidation of Propylene carried out by the same procedure as that of Example 1.

In the. Examples 55, 56 and 57 followed the procedure of Example 54 using catalysts containing the five metal components contained in varying atomic proportions and with all other conditions the same were.

The results of Examples 54 to 57 are never shown in Table V.

table V product catalyst Atomic ratio Around
Wall
lung
(%) Selek
activity
(%) example
No. Starting
maleria 1 ON Bi-Mo-W-Ca-Fe-O 1: 2: 0.8: 3: 0.2: 13.2 98.7 89.0 34 Propylene ON the same the same 96.6 88.6 35 the same ON the same the same 95.2 87.6 36 the same MAN drsgl. the same 99.0 81.6 37 Isobutylene ON the same 1: 1.5: 0.5: 3: 0.2: 10.8 97.4 87.0 38 Propylene ON the same 1: 1.8: 0.3: 6: 0.5: 14.65 98.8 86.3 39 the same ON the same 1: 1: 1: 6: 0.3: 13.95 94.2 88.1 40 the same ON the same 1: 2: 0.5: 3: 0.5: 12.75 96.9 85.6 41 the same ON Bi - Mo - W - Ca - Co - O 1: 2: 0.5: 3: 0.5: 12.5 98.6 85.0 42 Propylene ON the same 1: 1.5: 0.5: 3: 0.3: 10.2 97.8 88.0 43 the same ON the same 1: 2: 1: 3: 0.2: 14.1 97.6 88.5 44 the same ON the same 1: 2: 1: 6: 0.5: 16.0 99.0 86.2 45 the same ON Bi - Mo - W - Ca - Ni - O 1: 2: 0.5: 3: 0.5: 12.5 96.7 87.6 46 the same ON the same 1: 1.5: 0.2: 6: 0.2: 12.8 90.1 87.7 47 the same ON Bi-Mo-W-Ca-Ni-O 1: 1.8: 1: 4: 1: 14.9 91.7 87.6 48 Propylene ON the same 1: 2.0: 0.8: 3: 0.8: 13.7 97.9 85.5 49 the same ON Bi-Mo-W-Ca-Cr-O 1: 2: 0.5: 3: 0.5: 12.5 96.5 86.2 50 the same ON the same 1: 1: 0.5: 2: 0.8: 19.2 96.7 86.7 51 the same ON the same 1: 2: 0.2: 3: 1.0: 12.6 90.9 88.2 52 the same ON the same 1: 3: 1.0: 6: 0.2: 19.9 92.3 84.9 53 the same ON Bi - Mo - W - Ca - Mn - O 1: 2: 0.5: 3: 0.8: 12.8 94.3 89.2 54 the same ON Bi-Mo-W-Ca-Mn-O 1: 0.5: 1.0: 3: 0.5: 10.0 92.2 87.4 55 Propylene ON the same 1: 1: 0.5: 3: 0.2: 9.4 94.4 88.6 56 the same ON the same 1: 3: 0.8: 3: 0.8: 18.5 93.1 87.8 57 the same

Examples 58 to 61
Bi-Mo-W-Ca catalyst

236 g of calcium nitrate [Ca (NO ₃ ), · 4 H ₂ O] were dissolved in 1 liter of water. To the solution was added dropwise 214 ml of a solution of 378 g of ammonium molybdate [(NH ₄ ) _e Mo, O ₂₁ · 4 H ₂ O] in 9.3% aqueous ammonia (the concentration of ammonium molybdate: 0.307 mol / L). Immediately thereafter, 13.8% nitric acid was quickly added to the mixed solution, thereby adjusting the pH to 5 to 5.5, followed by stirring. After standing at room temperature overnight, the deposited, co-precipitated precipitate was removed. The coprecipitate was sufficiently washed and then at a temperature of 120 to 130 ⁰ C for 16 hours. Dried. Subsequently, the dried coprecipitate at 540 ⁰ C was 16 hours. In calcined in bubbles of air. Calcium molybdate [MCaMoO ₄ ] was thus produced. The calcium molybdate was identified from its X-ray diffraction diagram.

240 ml of a solution of 83.3 g of tungstic _{acid [Wo 3} ■ H ₂ O], dissolved in 9.3% aqueous ammonia (thus an ammonium tungstate solution with a concentration of 0.66 mol / l) and 320 ml of a solution 485.1 g of bismuth nitrate [Bi (NO ₃ ) ₃ · 5 H ₂ O] in 13.8% strength nitric acid (concentration of bismuth nitrate: 1.0 mol / l) were mixed with one another with stirring. The mixed solution was

Heated to dryness until the formation of ammonium nitrate and nitric oxide ceased. A small amount of water was added to the dried solid, followed by kneading for 2 hours. After drying for 16 hours at 120 to 130 ° C., the dried solid was calcined at 540 ° C. for 16 hours while passing air over it. In this way, bismuth tungstate [Bi ₂ O ₃ · WO ₃ ] was produced. The bismuth tungstate was identified from the X-ray diffraction diagram.

The calcium glybdate thus prepared and the bismuth tungstate were mixed and kneaded together with a small amount of water for 3 hours. The paste was calcined under Furthermore passing air at a temperature of 120 to 130 ~ ^J C for 16 h. And then dried 16 hrs. At 540 C ^c. The calcined solid was brought to a grain size corresponding to a mesh size of 1.168 to 0.833 mm and used as a catalyst.

4 ml of the catalyst was placed in a U-shaped stainless steel reaction tube with an inner diameter of 8 mm. A gaseous mixture of olefin (in Examples 58 and 60 propylene and in Examples 59 and 61 isobutylene), ammonia, steam and air in a molar ratio of the four components of 1: 1: 2: 7.5 by the with the reaction tube filled with the catalyst ^{and kept at 420 °} C. with a flow rate of 80.5 ml / min. The contact time was 3 seconds. The results are set out in Table VI.

table VI product catalyst Atomic ratio Around
Wall
lung
(%) Selek
activity
(/ 0) example
No. Starting
material ON
MAN
ON
MAN Bi-Mo — W-
the same
the same
the same 2: 3: 1: 3: 18
the same
2: 1: 1: 1: 10
the same 92.7
93.1
92.9
93.9 87.1
86.3
88.1
85.8 58
59
60
61 Propylene
Isobutylene
Propylene
Isobutylene -Ca-O

Examples 62 to 69

Bi-Mo-W-Ca-Nb, Ti, V, Fe, Zr
or Ta catalyst

In the production of bismuth tungstate, bismuth niobate [BiNbO ₄ ], bismuth titanate [Bi ₁ Ti ₁ O,], bismuth vanadate [BiVO ₄ ], bismuth ferrate [BiFeO ₈ ], bismuth zirconate [Bi ₁ (ZrO ₈ ) ,] and bismuth tantalate [BiTaO ₄ ], a solution of bismuth nitrate in nitric acid, Mliobpentoxid [Nb ₁ O ₆ ], titanium dioxide [TiO ₁ ], a solution of ammonium metavanadate [NH ₄ VO ₈ ] in oxalic acid, an aqueous solution of iron (III) nitrate [Fe (NOs) ₃ ^ H ₁ O], an aqueous solution of zirconium nitrate [ZrO (NO ₈ ) ₈ · 2 H ₁ O] and tantalum pentaoxide [Ta ₁ O ₅ ], respectively, were used. These six compounds were identified from their X-ray diffraction patterns.

From each of these six compounds and the calcium molybdate mentioned in Example 58 and the in Bismuth tungstate mentioned in Example 58 became a catalyst in the same manner as in Example 58 manufactured.

Using the catalyst thus prepared, the same procedure as in Example 58 carried out the ammoxidation of propylene or isobutylene. The results are in the Table VII laid down.

B e i s ρ i e 1 e 70 and 71

Bi-Mo-W-Ca-Ti-Nb-
or -Zr catalyst

There were from the calcium molybdate from Example 58, the bismuth tungstate from Example 58, the Bismuth titanate from Example 65, the bismuth niobate from Example 62 and the bismuth zirconate from Example 68 two catalysts were prepared in the same manner as in Example 58.

Using these catalysts, following the same procedure as in Example 58, the Ammoxidation of propylene carried out. The results are shown in Table VII.

19 r fo

Table VII

Example starting product catalyst atomic ratio Um- Selek-

No material flexibility

lung

62 propylene AN Ui-M ₀ -W-Ca-Nb-O 3: 2: 1: 2: 1: 18 93.2 88.8

63 isobutylene MAN like the same 93.4 87.3

64 propylene AN like 3: 1: 1: 1: 1: 14 93.0 89.3

65 the same. AN Eli — Mo — W — Ca — Ti —O 4: 1: 1: 1: 2: 18 92.9 89.4

66 the same. AN Bi-Mo - W - Ca - V - O 3: 1: 1: 1: 1: 14 93.1 86.9

67 the same. AN Bi-Mo-W-Ca-Fe-O 3: 1: 1: 1: 1: 13 93.1 90.7

68 the same. AN Bi-Mo-W-Ca-Zr-O 4: 1: 1: 1: 3: 19 93.3 90.4

69 desg !. AN Bi-Mo-W-Ca-Ta-O 3: 1: 1: 1: 1: 14.9 92.9 87.1

70 the same. AN Bi-Mo-W-Ca-Ti-5: 1: 1: 1: 2: 1: 21 94.0 87.3

Mb-O

71 the same. AN Bi-Mo-W-Ca-Ti-7: 1: 1: 1: 2: 3: 27.5 94.1 86.6

Zr-O

_R. . . became tablets with a diameter of 5 mm and

Examples / 2 to // » ₅ deformed approximately 5mm in height. The tablets

Bi-Mo-W-Ca - Cr-Ti catalyst were at 65O ⁰ C for 10 hours calcined (at.

Temperature rise of 20 ° C / hour).

32.4 g of ammonium paratungstate [(NH ₄ I ₁₀ W ₁₂ O ₄ , - 20 ml of the catalyst were in a U-shaped

5 H ₈ O], 49.7 g of chromium nitrate [Cr (NO ₃ J ₃ ■ 9 H ₂ O], 9.9 g of glass reaction tube with an inner diameter

Titanium dioxide [TiO ;,] and 220.0 g calcium nitrate 3c of 10 mm filled. With the catalyst

[Ca (NO ₃ ) g · 4 H ₂ ^{O] were dissolved in 1} liter of water, the reaction tube filled on the sator and kept at 420 ° C.

6O ⁰ C was held, dissolved with stirring. a gaseous mixture of olefin (in

To this solution were added dropwise the same - Example 72 propylene and in Example 73 isobutylene),

early a solution of 150.6 g of white nitrate [Bi (NO ₃ V ammonia, air and steam in a molar

5 H ₁ O] in 181ml of 10% nitric acid and a ratio of the four components of 27: 27: 300:

a solution of 109.7 g of ammonium molybdate with a flow rate of 460 ml / min, passed.

[(NH ₄ ^ Mo ₇ Oi ₄ · 4 H ₂ O] in 260 ml of 10% aqueous The contact time was 2.6 sec.

added ammonia. Immediately afterwards In Examples 74, 75, 76 and 77 the

was 10% aqueous ammonia to the solution ammoxidation of propylene according to the same

added to adjust the pH to 4.0 and 40 procedures as described above performed with

to precipitate a precipitate. After leaving the exception that catalysts were used,

of the overnight precipitate, this was due to the soft varying of the six metal components

washed repeated decanting, filtered off and contained atomic ratios. The results are

then dried. The dried solid is recorded in Table VIII.

Table VIII

Example starting product catalyst atomic ratio Um- Selek-

No material versatility

lung

72 Propylene AN Bi-Mo-W-Ca-Cr-1: 2.0: 0.4: 3: 0.4: 0.4: 13.1 95.3 87.1

Ti-O

73 isobutylene MAN like the same 95.7 87.1

74 propylene AM like 1: 2: 0.2: 3: 0.4: 0.4: 12.5 92.8 85.3

75 same. AN same. 1: 2: 0.4: 3: 0.8: 0.4: 13.7 91.5 86.8

76 same. AN same. 1: 1.5: 0.8: 3: 0.2: 0.4: 12.5 95.2 84.4

77 same. AN same. 1: 2: 0.2: 3: 0.8: 0.8: 13.9 93.4 87.0

To evaluate the dimensional stability and mechanical properties of the catalysts used _; the compressive strength and the diameter of the pelletized catalysts were determined. The determination was made on a sample of the catalysts before and after use for conversion

from olefin to nitrile according to the following Procedure carried out.

65 Fs were put into a 10 ml of a catalyst cavity 5 mm in diameter and approximately 5 mm in height U-shaped glass reaction tube filled. Then a gaseous mixture of propylene, ammonia,

Air and steam in a molar ratio of the four components of 10: 10: 100: 10 by the reaction tube filled with the catalyst, which was kept at 500 ° C., with a diirchfiow performance of 130 ml / min over a period of 20 hours. The measurement of compressive strength and the diameter was recorded on approximately 50 pelletized catalyst samples and average values calculated.

The compressive strength was determined as follows: Each tablet sample was placed on a plate given with a diameter of 25 mm; thereafter was a cylindrical rod with a press end face with a diameter of 5 mm gradually pressed onto the sample until it broke. The pressure in kg when the sample was broken gave the compressive strength.

The results are given in Table IX.

table IX Compressive strength (kg)
Before the
use After
use Diameter (mm)
Before the
use After
use example
No. 15.3 15.5 4.77 4.77 72 13.7 13.9 4.79 4.78 74 13.6 13.3 4.78 4.78 75 15.8 15.6 4.75 4.74 76 16.5 16.7 4.80 4.81 77

Examples 78 and 79
Bi-Mo-W-Ca-Cr-Zr catalyst

75.1 g ammonium paratungstate [(NH ₄ I ₁₀ W ₁₀ O ₄₁ · 5 H ₂ O], 28.8 g chromium nitrate [Cr (NO ₃ ^ ₃ · 9 H ₂ O], 19.0 g zirconium nitrate [ZrO (NO ₃ )., · 2 H ₂ O] and 254.8 g of calcium nitrate [Ca (NO ₃ ) ₂ · 4 H ₂ O] were dissolved with stirring in 1 l of water which was kept at 60 ° C. To this solution a solution of 174.5 g of bismuth nitrate [Bi (NO ₃ ) ₃ · 5 H ₂ O] in 210 ml of 10% nitric acid and a solution of 127.2 g of ammonium molybdate [(ΝΗ ₄ ) _β ο, Ο ₂₄ x 4Η ₂ Ο] in 302 ml of 10% aqueous ammonia was added, and immediately thereafter, 10% aqueous ammonia was added to the mixed solution to adjust the pH to 4.0 and precipitate a precipitate treated in the same manner as in Example 72.

Ammoxidation of propylene was carried out using the catalyst thus prepared the procedure of Example 72 was followed.

In Example 79 the above procedure was followed using a catalyst containing the six metal components at varying atomic ratios, with all other conditions the same stayed. The results are set out in Tables X and XI.

Examples 80 to 83
48.0 g ammonium paratungstate [(NH ₄ ) ₁₀ W, ₂ O ₄₁ ·

5 H ₂ O]. 28 g of chromium nitrate [Cr (NO ₃ ) ₃ · 9 H ₂ O], 9.4 g of niobium pentoxide [Nb ₂ O ₅ ] and 251.3 g of calcium nitrate [Ca (NO ₃ ) ₂ · 4 H ₂ O] were used in FIG 1 water, which was kept at 60 ⁰ C, dissolved with stirring. A solution of 172.2 g of bismuth nitrate [Bi (NO ₃ ) ₃ · 5 H ₂ O] in 207 ml of 10% nitric acid and a solution of 125.5 g of ammonium molybdate [(NH ₄ ) _{6 were added dropwise to this solution at the same time} Mo ₇ O ₂₄ -4 H ₂ O] in 298 ml of 10% aqueous ammonia was added. Immediately thereafter, 10% aqueous ammonia was added to the mixed solution to adjust the pH to 4.0 and precipitate a sediment. The precipitate was treated in the same manner as in Example 72.

Using the catalyst thus prepared, following the procedure of Example 72 carried out the ammoxidation of propylene.

In Examples 81, 82 and 83 the above procedure was followed using catalysts were used which contained the six metal constituents in varying atomic proportions, all other conditions being the same.

The results are set out in Tables X and XI.

Table X example

Source material

Product catalyst

Atomic ratio

Um- Selekwandtivilät
lung

78 Propylene ON Bi-Mo-W-Ca-Cr-
Zr-O 79 the same ON the same 80 the same ON Bi-Mo-W-Ca-Cr-
Nb-O 81 the same ON the same 82 the same ON the same 83 the same ON the same

1: 2: 0.8: 3: 0.2: 0.2: 13.5 94.4 85.6

1: 2: 0.5: 3: 0.5: 0.5: 13.75 97.2 86.1

1: 2: 0.5: 3: 0.2: 0.2: 12.7 95.7 85.7

1: 2: 0.8: 3: 0.2: 0.6: 14.7 93.2 86.3

1: 1.5: 0.2: 2: 0.8: 0.4: 10.8 92.8 87.2

1: 1: 0.4: 6: 0.4: 0.4: 13.3 96.2 83.8

IJ

78 17.0 16.3 79 16.3 15.4 80 15.9 15.1 81 13.2 13.6 82 10.9 16.1 83 14.3 14.0 Example 84

23 24

Table XI

Example compressive strength (kg) diameter (mm)

No. Before the After the Before the After the

Use use use use

4.80 4.79

4.79 4.78

4.80 4.80

4.76 4.75

4.77 4.77 4.76 4.76

the reaction tube with a flow rate of 460 ml / min, conducted while keeping the internal temperature

It was held at 42O ⁰ C 161.0 g of zinc nitrate [Zn (NO _{3) 2} · 6H ₂ O], and the reaction tube. The contact time of 141.5 g of ammonium paratungstate [(NH ₄ ) I ₀ Wi ₂ O _41-20 was 2.6 seconds.

5H, O] dissolved in 500 ml of warm water, the conversion of propylene being 55.6% uno

was stirred. To this solution added dropwise, the selectivity for acrylonitrile was 89.6%.
at the same time a solution of 525.5 g bismuth nitrate ... . ,

[Bi (NO _s ) _a · 5 H ₄ O] in 310 ml of a 10% saltpeter comparison test 4

acid and a solution of 955 g Ammoniummolyb- 25 It was prepared according to Chem. Abstracts 1972, Vol. 76, dat [(ΝΗ ") _{β Μο 7 Ο} ί4 · 4 H ₂ O] dissolved in 200 ml of 10% 58 A catalyst was prepared 98Oe and given under watery ammonia. Thereafter, the ammoxidation of a silicon dioxide sol containing 30% propylene to acrylonitrile was carried out using this catalyst.
Silica added; after that the Mi- _v . . _x , ^ "

Schung adjusted to a pH value of 1.0 and ₅ o catalyst production

stirred for an hour. The 70.0 g cobalt nitrate, 24.3 g iron (III) nitrate and

slurry was introduced with a spraying 29.2 g of bismuth nitrate were dissolved separately in 20 ml destiltrockner dried at 20O ⁰ C and then liertem at 65O ° C water, 20 ml of distilled water and 30 ml 10 h calcined.. The catalyst had an average acidic aqueous solution produced by an average particle size of about 60 microns and an addition of 6 ml of concentrated nitric acid to an atomic ratio of Zn: Mo: Bi: W: Si: O = 1: 1: 2: 1: distilled Water, dissolved. A mixture of these 15.3: 44.6. The silica content was 50%. three aqueous solutions became one dropwise

150 ml (155 g) of the catalyst in a solution of 106.2 g of ammonium molybdate and 32.4 g were added to a fluidized bed reactor with an internal diameter of ammonium paratungstate in distilled water of 36 mm and a length of 420 mm. 40 given. A solution of a gas mixture of propylene, ammonia, 24.4 g of 20% strength silicon dioxide sol and 0.202 g of potassium and air (the molar ratio of the three component hydroxide in 15 ml of distilled water being added, components 1: 1.1: 12) through the catalyst The suspension obtained was sent, with stirring, to the reactor charged with a reactor which, with gradual evaporation, was heated to dryness. Temperature of 440 ⁰ C at a flow rate 45 The solid product thus obtained was kept into pellets of from 1,922 mi / min. The contact time molded 5 mm in size and then in one was 4.68 seconds. Airflow calcined for 6 hours at 45O ⁰ C. The

The conversion of propylene was 95.6% by atomic ratio of that in the obtained catalyst and the selectivity to acrylonitrile was 84.9%. contained metals was found as follows:

λ / 1 · v. Ui ⁵ ° Co ₄ FeIBi ₁ WgMo ₁₀ Si _{1 Μ} Κ _{0 Μ}

Comparative experiment 3 4 1 1 s 10 i.ss 0.0 «

_ .. _A .J ₁ . τ »1»,. ·, Ammoxidation of Proovlen to acrylonitrile

The ammoxidation of propylene to acrylonitrile

was at a temperature of 420 ^° C. with 20 ml of the catalyst thus prepared were in

Turn of a U-type reaction tube with an inside diameter according to Example 1 of DT-OS 21 59 616 55

The catalyst produced was filled in according to the following procedure of 10 mm. A gaseous mixture of

drive carried out. Propylene, ammonia, air and steam all in one

In a U-shaped bent reaction tube from the molar ratio of the four components of

stainless steel with an inner diameter of 27: 27: 300: 106 was

10 mm were filled with ^{20 cm 3 of catalyst.} The 60 sator charged and kept at 420 ° C reaction

catalytic reaction was carried out by pipe with a flow rate of 460 ml / min,

a gaseous mixture of propylene, am- passed. The contact time was 2.6 seconds. the

monia, air and steam in a molar ratio conversion of propylene was 96.5% and the

of the four components of 27: 27: 300: 106 by selectivity to acrylonitrile was 46.0%.

709 636/244

Claims (1)

Propylene to acrolein and in Chem. Zentralblatt Claim: 196ö, 2772, the use of Bi-Mo - W-Kataly Sators for the ammoxidation of isobutylene zi Process for the production of acrylonitrile or methacrylonitrile described. This well known too Methacrylonitrile dua-h conversion of propylene 5 catalysts are not yet satisfactory. So mar or isobutylene with oxygen and ammonia, for example when using propylene, although one achieve a sufficient degree of conversion in the gas phase at temperatures of 300 to, but nui 550 ° C above a bismuth, molybdenum and an unsatisfactory selectivity for acrylonitrile. Metal of group II of the periodic table is primarily the task of the present holding calcined oxide catalyst, d a- io invention to provide a method that the Her characterized in that one has a position of acrylonitrile or methacrylonitrile at one Catalyst of the empirical formula relatively low reaction temperature in a relatively "■ ·. _{w lf} allows a short contact time, both mil BiMO ₀ . ₃ _, ₀ w ₀ , ₀₅ _3, ₀ ii ₀ ,, _ _e , ₀ Ä ₀ _ _s . ₀ U3. ₂ _ _egg . _{5 high conversion} | _and high selectivity. in the II at least one of the metals magnesium, 15 other subtasks and advantages are from the dei Calcium, strontium, barium, zinc and cadmium following description as well as the execution as well as X Titanium, zirconium, niobium, tantalum, vanadium, examples can be found. Chromium, manganese, iron. Cobalt and / or Nickel The invention now relates to a method for zui is used. Manufacture of acrylonitrile or methacrylonitrile by ao conversion of propylene or isobutylene with acid substance and ammonia in the gas phase at temperatures of 300 to 550 ° C above a bismuth, molybdenum and a calcined oxide catalyst containing a metal from Group II of the Periodic Table, There are already numerous catalysts for the 25 which is characterized in that there is a catalytic ammoxidation of olefins in the catalyst of the empirical formula
Gas phase for the production of the corresponding unge- n; Mn w 11 YO .... ..... ·, · J al ■ L * ι ti j öllV10 _0l 3_j ₀ W ₀ , ₀ 5_3, ollo, le, 0 ^A 0-5.0 ^> -'3.2-61.5 saturated nitriles has been recommended with the intention of the selectivity for a desired unsaturated in II at least one of the metals magnesium, Increase nitrile without converting the olefin- 30 calcium, strontium, barium, zinc and cadmium reduce loading. The well-known oxide as well as X titanium, zirconium, 'niobium, tantalum, vanadium, Ammoxidation catalysts include all chromium, manganese, iron, cobalt and / or nickel, generally a combination of oxides of two or more is used. several metals, for example a Mo-Bi- (P) - The catalyst defined above provides in comparison the system described in Japanese Patent Application 35 with a conventional catalyst for registration 5870/1961, a Sn-Sb system, described in oxidation a low reaction temperature, in Japanese Patent Application 13 966/1962, such as approximately 400 ° C, in a kür-U-Sb system described in Japanese Patent Zeren contact time taking into account the prior application 24 367/1965 and an Fe -Sb system, the process conditions unexpectedly described in Japanese Patent Application 40 good yield of 80% or more.
19 111/1963. Of the metals of group II of the period - however, it was generally difficult, both systems calcium, barium and zinc are particularly preferred a high selectivity for the desired unsaturated. Nitrile as well as a high conversion of the olefin to Preferably the catalyst - removed achieve, d. that is, there was a need to look at the oxygen content - the formula Regulation of conversion to ensure high selectivity n; iur. w e Y to reach. With these known catalysts B> Mo ₀ , _s _ ₃ .oW _a , ₁ _ ₁ , ₅ II ₀ , ₂ _ ₅ . ₀ X ₀ . ₁ - _(I , ₀ . If the catalyst contains so much chromium that Nitrile of approximately 70%. Generally speaking, this is the atomic ratio of chromium to bismuth within The catalyst shows that the yield of unsaturated nitrile per catalyst is in the range from 0.1 to 3.0 low weight and the life of the catalyst excellent dimensional stability and mechanical short, since long contact time and high temperature, niche properties, compared to a catalyzer z. B. approximately 450 ⁰ C or above, required sator that does not contain chromium, and in particular are. compared to a conventional catalyst. The DT-OS 21 59 616 deals with the catalysis 55 The metal components can in the catalyst tables ammoxidation of propylene or isobutylene either as a mixture of metal oxides or in to acrylonitrile or methacrylonitrile, but they are in a bound state, Catalysts described there, the molybdenum, Typical process for the production of some Bismuth, antimony and a group II metal of the catalysts will now be explained. Periodic table contain, by no means a satisfactory 60 gj j ^ _Q ψ jj O catalyst Properties. In particular, they show at one lower reaction temperature an unsatisfactory A fixed amount of ammonium parawolf activity; They only work when the ramat is relatively high when it is dissolved in hot water. A solid reaction temperature Somewhat contented amount of calcium nitrate is used in the water. S5 rigcn solution resolved. Then there is a solution In Chem. Abstracts, 1972, Volume 76, 58 98Oe, a fixed amount of bismuth nitrate in