DE1203757B - Process for the production of acrylic acid nitrile and methacrylic acid nitrile by reacting propylene or isobutene with oxygen and ammonia - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

Number:
File number:
Registration date:
Display day:

C07c

German class: 12 ο - 21

1203 757
D33663IVb / 12o
June 29, 1960
October 28, 1965

The invention relates to a process for the production of acrylonitrile or methacrylonitrile by reacting propylene or isobutene with molecular oxygen and ammonia in the gas state, the amount of olefin between 1 and 20 percent by volume, that of oxygen between 1 and 20 percent by volume and that of ammonia between 2 and 10 percent by volume is, in each case based on the amount of the total feed, in the presence of an inert gaseous diluent and eiifes tin, optionally applied to a support catalyst at temperatures of 300 to 55O ⁰ C, which is characterized in that the reaction in the presence of a mixture of the oxides of antimony and tin, advantageously in an atomic ratio of 1: 0.1 to 10, and / or a compound of antimony, tin and oxygen as a catalyst, which is heated to temperatures of 540 to 1100 ° C. before the reaction has been. ao

The catalysts used in this process must be antimony, oxygen and tin and can either be made from mixtures of antimony oxides with tin oxides or as oxygen-containing There are compounds of antimony and tin, such as tin antimonate; under the reaction conditions the catalyst can be in one or both forms. The catalyst can be in in any suitable manner, e.g. B. from the oxides of antimony and tin, or from the compounds of tin or antimony, e.g. B. the hydroxides, have been produced when heated in the presence an oxygen-containing gas, e.g. B. air, are converted into the oxides. For the production of the catalyst can be any oxide of antimony and tin or oxides can be used, such as antimony trioxide, antimony tetroxide, antimony pentoxide or mixtures of these Oxides, stannous oxide, stannous oxide, metazinic acid or mixtures of these oxides. It can also contain water Forms of these oxides can be used, e.g. B. those caused by the action of aqueous nitric acid on metallic antimony or tin or mixtures of these metals. as Particularly good catalysts have proven to be those in which the antimony tetroxide is used as a mixture or as a compound with stannous oxide.

The atomic ratio of tin to antimony in the catalyst can vary within fairly wide limits, e.g. B. between 0.1: 1 and 10: 1. The catalyst mixture must be in the presence of an oxygen-containing gas, e.g. B. air, at a temperature process for the production of acrylonitrile
and methacrylonitrile by reacting
Propylene or isobutene with oxygen and
ammonia

Applicant:

The Distillers Company Limited,

Edinburgh (Great Britain)

Representative:

Dr. W. Schalk, Dipl.-Ing. P. Wirth,

Dipl.-Ing. G. E. M. Dannenberg

and Dr. V. Schmied-Kowarzik, patent attorneys,

Frankfurt / M., Große Eschenheimer Str. 39

Named as inventor:

John Bernard Bream, Redbourn, Hertfordshire;

John Lynn Barclay, Tadworth, Surrey;

David James Hadley, Epsom Downs, Surrey;

David Gordon Stewart,

Epsom, Surrey (UK)

Claimed priority:

Great Britain July 1, 1959 (22 509),

dated October 3, 1959

(33 592.33 593)

between 550 and HOO ⁰ C, the best temperature for this treatment is related to the ratio of antimony to tin in the catalyst. For example, with a catalyst composed of 2 tin atoms per antimony atom, good results are obtained when it has ^{been heated to about 950 °} C .; a catalyst having tin atom per 1 4 antimony atoms gives, when heated to about 700 ⁰ C good results.

A particularly preferred process for preparing the catalyst is that stannous oxide or the hydrous oxide obtained by the action of aqueous nitric acid on metallic tin is intimately mixed with antimony pentoxide, antimony tetroxide or the hydrous oxide obtained by the action of aqueous nitric acid on metallic antimony and the resulting mixture is mixed 550 to HOO ⁰ C is heated.

509 719/409

Another preferred method of making the residence time is given by:

of the catalyst is that of cationic salts

of tin and antimony, for example chloride, with catalyst volume

Water hydrolyzes, the resulting precipitate flow rate of the gas per second

is separated and heated. The complete Hydro 5

lysis is done by adding a volatile base, such as (calculated at room temperature and normal Ammonia. A particularly suitable catalyst pressure); it is preferably 1 to 30 seconds, The reaction can take place at atmospheric pressure

and antimony pentachloride can be prepared by or by means of a pressure above or below the atmospheric pressure Mixture of the two in water with ammonia can be carried out. It is preferred to use pressures of up to a pH value of over 5.0, the 1 to 5 atmospheres apply.

Separated precipitate and at a temperature The unsaturated nitrile can be in any suitable

between 550 and 1100 ⁰ C is heated. Neten way obtained from the reaction gases

Are the tin and antimony compounds in the, e.g. B. by washing with water, preferential mixture in the form of their low valence 15 wise at an acidic pH, and then present, z. B. as divalent tin or three-fractionated distillation of the aqueous solution. According to valuable antimony compounds, the mixture must be a process, the hot reaction gases in an atmosphere of oxygen and an inert first with a cold, dilute aqueous acid gas, such as nitrogen, carbon dioxide or steam, washed solution, whereby the excess ammoerheated, whereby the ratio of oxygen 20 niak is neutralized and a part of the nitrile is washed out and the total supply of the gas is regulated; from the treated gas is then washed with cold that no portion of the catalyst during the pre-water the residual nitrile washed janschließend heating to a temperature of about 65O ⁰ C, the nitrile from the aqueous solutions is exceeded by proceeds. After this preheating, the mixture is obtained by fractional distillation,
then still in the air to a temperature of 25. The method of the invention provides a further 550 to 1100 ° C heated. The production of the catalyst way for the production of acrylonitrile and methsator is not bean acrylonitrile in even better yields in one language within the scope of the invention. one-step process from the corresponding olefins

The catalyst used in the process is. Compared to a known copper and molybdenum, optionally on a support, for. B. silica 30 Danish-containing catalyst (see. The French patent acid. Regardless of how the Oxyde script 1 098 400) and against a known or water-containing oxides of tin and antimony bismuth phosphomolybdate catalyst (see. Which were produced, the mechanical Resistance gische patent specification 571 200) are according to the invention catalyst is obtained by longer washing with manure better yields.
Water increased before drying. 35 The in French patent specification 1 098 400

The conversion of propylene or isobutene with indicated yields of acrylonitrile were Oxygen and ammonia cannot be reached in the presence of the catalyst, as the following experiments show sators can be made in any suitable manner, it has been made one containing copper and molybdenum

z. B. in the presence of a fixed catalyst catalyst as in Example 3 of the French sators in the form of granules or tablets or 40 patent specification 1098 400 and manufactured according to the in the form of a fluidized bed or a shaking Example 5 tested for its effect, at 500 ° C and beds. 90% of the propylene was dwelled for 2.9 seconds

The amount of propylene or isobutene in the carbon dioxide, and in the presence of all gaseous feed is 1 to from 2 percent added chlorine, the yield of 20 percent by volume, suitably about 2 to 10 percent by volume of carbon dioxide was even higher. Even at 300 ⁰ C percent; an amount between 4 is preferred and the amount of carbon dioxide was 67%
6 percent by volume. 47.5 parts by weight of alumina grains, particle size:

Also, the amount of oxygen is from 1 to DIN sieve 4-10, 20 Ge-volume percent at 100 ⁰ C with 3.75, preferably 2 to 15 Volum- weight parts of a solution of cupric nitrate in 20 Geprozent. The oxygen can be impregnated with inert gases 5 ° by weight of water. The mixture would be diluted and e.g. B. be supplied as air. Stirred for 15 minutes at 100 ⁰ C, 16 hours at 16O ⁰ C

The reaction is dried in the presence of an inert and for 4 hours in a stream of air on gas as a diluent, e.g. B. nitrogen, propane, 475 ° C heated. The grains were then carried out at 100 ^° C. butane, isobutane, carbon dioxide and steam with a solution of 2.1 parts by weight of ammonium, preferably soaked in 20 parts by weight of water in the presence of water molybdate; the steam or mixtures of steam and mixture were dried as before.
Nitrogen. The amount of water vapor can, for. B. between A gaseous mixture of 2% propylene,

20 and 60 volume percent of the total charge 3% ammonia and 95% air was at 500 ° C and be. 2.9 seconds residence time, calculated at normal pressure

The amount of ammonia is 2 to 10 volume and temperature, in a glass tube with 5 mm internal percent of the total charge. The highest diameter, which was immersed in a bath of molten beuten of acrylonitrile in the presence of tin, obtained excess ammonia over this catalyst, so that, for. B. headed. Of the propylene charge, 90% of the gas mixture leaving the reaction vessel was converted into carbon dioxide, 2% in acrylonitrile, 6% in at least 1 mol of ammonia per 10 mol of acrylic acid-65 acrolein and 2% in hydrocyanic acid,
contains nitrile. The preferred amount of ammonia is In a further experiment, 2% chlorine,

about 6 percent by volume of the charge, if this is based on the total charge, the gas-5 % Contains propylene. added shaped mixture. At 500 ° C, 90%

5 6

of propylene in carbon dioxide, 5% ^m acrylic acid gaseous mixture of 5 percent by volume propylene,

nitrile and 1% ^m hydrogen cyanide. 6 percent by volume ammonia, 55 percent air by volume

Lowering the reaction temperature to and 34 percent by volume of water vapor passed, wherein

410 ° C. without the addition of chlorine resulted in the following residence time being 4 seconds.

Yields: 1% acrylonitrile, no acrolein, 5–63.9% of the propylene was in acrylonitrile

0.5% hydrogen cyanide and 87% carbon dioxide. Converted at 300 ^{° C.} The yield of acrylonitrile,

the yield, based on the amount of propylene based on propylene consumed, was 67.4% × 1% acrylonitrile, 0.2% acrolein, 0.4% hydrocyanic acid
and 76% carbon dioxide.

The method of the invention is described in Examples to Example 3
explains in which parts by weight and parts by volume

have the same ratio to each other as 190 parts by weight of powdered tin were in grams

to cubic centimeters. '' small parts into a boiling nitric acid solution

Example 1 ^from ^ parts by volume of concentrated nitric acid

given i5 and 3200 parts by weight of water. 97.6 Ge

153.4 parts by weight of stannous chloride, SnCl ₈ · H ₂ O, weight parts of powdered antimony was added in small been% strength hydrochloric acid dissolved ^he parts to 400 parts by volume of warm concentrated in 150 parts by weight of l; this solution was added to nitric acid with vigorous stirring. Both mixtures were slowly added to 1500 parts by weight of water. Heated to the boil until no nitrous gases were formed. At the same time, 67.75 parts by weight of antimony gases were evolved. The pentachloride, SbCl ₅ , was added dropwise with stirring. After the still hot antimony oxide suspension for tin addition, the temperature of the mixture was given oxide for 5 minutes, the precipitate was filtered off, raised to 95 ° C with water, the mixture was then washed to the room, dried, through a DIN No. 12 sieve cooled temperature, sieved with 500 parts by weight of water and the larger particles removed, tableted, diluted and the pH by adding 25 and in the air for 16 hours to 700 ⁰ C and then dilute aqueous ammonia solution to 5 to 5.5 16 hours heated to 1000 ^{0 C.} The catalyst set. The resulting precipitate was filtered off with an atomic ratio of tin to antimony, which was equal to 2: 1 by reslurrying in water.

washed and filtered again. The precipitate The catalyst was held in a 4SI ° C

was dried at 100 ⁰ C and first given 30 reaction vessel in the air and through this one

3 hours to 380 ⁰ C and then a further 16 hours gaseous mixture of 5 percent by volume propylene,

heated to 540 ⁰ C; the catalyst obtained was 54 percent by volume air, 35 percent by volume water

then granulated. steam and 6 percent by volume ammonia passed,

19.6 parts by weight of this catalyst were used, the residence time being 3.6 seconds.

added to a reaction vessel maintained at 411 ° C. 35 58.5% of the propylene was in acrylonitrile

A gas mixture of 2 volumes was converted through this. The yield of acrylonitrile was

share propylene, 4 parts by volume ammonia and 63.7%. based on the propylene consumed. That

94 parts by volume of air with a flow rate of acrylonitrile contained less than 1% acetonitrile, of 25,000 parts by volume per hour, measured at

Room temperature and normal pressure. 40 Example4

47.4% of the propylene was in acrylonitrile

and 17.4% ^m carbon dioxide converted; the 492 parts by weight of antimony tetroxide were with

The yield was 65.1%, based on the amount consumed by adding 95 parts by weight of tin powder

Propylene. to 400 parts by volume of concentrated nitric acid in

η · · ι «45 1600 parts by volume of water obtained, precipitated

P tin oxide intimately mixed. The mix was

48.7 parts by weight of powdered tin were heated for 16 hours 650 ⁰ C and tableted,
slowly with good stirring to a solution of the catalyst nitric acid was added with the density of 1.42 in the reaction vessel and passed through this a 1000 parts by weight water in a bath maintained at 481 ⁰ C 250 parts by volume, where the 5 ° gaseous mixture of 5 volume percent propylene, Acid during the addition was kept at its boiling point 55 percent by volume air, 34 percent by volume water. Then 200 parts by weight of steam and 6 percent by volume of ammonia were passed, pulverized antimony to 850 volumes with stirring, the residence time being 4 seconds.

divide given nitric acid with a density of 1.42. 65.6% of the propylene was in acrylonitrile

Both acid mixtures were converted in this way with stirring. The yield of acrylonitrile was

Heated to the boil for a long time until there is no nitrous 71.5%, based on the propylene consumed.
Gases more evolved. Then the tin oxide

slurry to antimony oxide slurry Example 5
give and stirred for a few minutes. The mixture

was filtered, washed with distilled water, 60 85.7 parts by weight of commercially available antimony pent-

dried and the resulting powder with 2 weight 8 hours to 725 ⁰ C were heated oxide, by

percent graphite mixed and pelletized. Then a DIN sieve No. 80 sieved and the grains in water

the catalyst was ^{slurried at 700 °} C. and on for 16 hours. 16.5 parts by weight of tin powder were used

finally heated to 1000 ° C for 16 hours. The ca to a boiling nitric acid solution of 70 vol-

catalyst had an atomic ratio of tin to anti-65 parts of concentrated nitric acid in 280 parts by weight

mon equals 1: 4. share water given; the precipitated tin oxide

The catalyst was in a kept at 471 ⁰ C was filtered off, washed and dissolved in water.

Given reaction vessel and slurried through this one. The two slurries were

mixed together, filtered and the filter cake dried at 10O ⁰ C. The catalyst obtained was sieved through a No. 7 DIN sieve, heated to 725 ° C. for 16 hours, then sieved through a No. 10 DIN sieve and pressed into tablets.

The catalyst was placed in a reaction vessel maintained at 492 ° C. and through this one Gaseous mixture of 5 percent by volume propylene, 54.5 percent by volume air, 34.3 percent by volume water vapor and 6.2 percent by volume ammonia passed, the residence time being 4.1 seconds.

62.0% of the propylene was converted to acrylonitrile. The yield of acrylonitrile was 65.7%, based on the propylene consumed.

Example 6

Following the procedure of Example 2, a catalyst of tin oxide and antimony oxide having an atomic ratio of tin to antimony is equal to 1: 4 was prepared, was heated to the first 16 hours 65O ⁰ C and then 16 hours at 725 ° C.

The catalyst was placed in a reaction vessel maintained at 420 ° C. and through this one Gaseous mixture of 5 percent by volume isobutene, 6 percent by volume ammonia, 34 percent by volume water vapor and 55 percent by volume of air passed, the residence time being 4 seconds.

41% of the propylene was converted to methacrylonitrile.

Example 7

Following the procedure of Example 3, a tin oxide and antimony oxide catalyst was used an atomic ratio of tin to antimony equal to 2: 1.

The catalyst was placed in a tubular reaction vessel maintained at 492 ° C with an inner Given a diameter of 25 mm. By introducing a gaseous mixture of 5 percent by volume Propylene, 6 percent by volume ammonia, 34 percent by volume water vapor and 55 percent by volume air the catalyst was whirled up, the flow rate of total gases being 9181 each Liters of catalyst per hour, measured at room temperature and normal pressure.

58.6% of the propylene was converted to acrylonitrile. The yield of acrylonitrile was 63.2%, based on the propylene consumed.

Example 8

Catalysts with various atomic ratios of tin to antimony were produced. In the table below shows the respective atomic ratio of tin to antimony and the heating treatment of the catalyst. About this Catalyst was measured at room temperature and at a rate of 251 per hour normal pressure, and a residence time of 4 seconds a gas mixture of 5% propylene, 55% air » 6% ammonia and 34% water vapor passed.

Heating the
Catalyst time in Reaction
temperature Yield in% based on propylene Acrolein Hydrocyanic acid Coals
dioxide Yield to Atomic ratio
from Sn: Sb on ( ⁰ C) O L Uli ViCIl ( ⁰ Q Acrylic acid
nitrile 6.4 7.6 5.3 Acrylic acid
nitrile, based
on in the catalytic converter 1000 16 480 48.2 6.8 8.8 8.3 consumed
Propylene 16: 1 1000 16 480 55.9 2.0 3.5 18.5 59.7 4: 1 750 16 440 52.1 1.6 7.8 17.5 62.9 2: 1 850 16 480 55.6 4.3 8.5 9.5 56.3 950 16 480 56.4 8.4 6.3 7.0 57.1 1000 16 480 49.1 3.9 2.2 17.7 58.7 725 16 420 47.3 3.4 7.3 15.8 59.0 2: 1 *) 900 16 481 60.1 4.7 7.7 9.8 53.3 950 16 480 56.0 7.2 5.3 8.3 60.1 1000 16 480 49.0 0.9 4.1 24.7 58.7 700 16 480 54.3 8.7 6.0 4.0 59.8 1: 1 1000 16 481 40.2 2.5 5.1 13.2 54.3 725 16 459 62.4 2.6 4.9 12.6 61.1 0.5: 1 800 16 472 61.3 6.0 7.4 8.1 - 900 16 479 60.5 6.8 7.6 6.6 - 950 16 479 54.1 2.5 5.5 12.7 - 650 16 462 58.7 2.8 6.1 11.8 63.0 0.25: 1 725 16 471 63.9 5.2 4.3 6.8 - 850 16 480 54.6 8.0 5.1 3.1 67.4 900 16 480 39.6 3.2 5.3 10.9 58.5 725 16 480 54.5 4.3 6.3 10.3 59.0 0.25: 1 *) 800 16 489 55.4 3.1 4.6 11.5 63.0 500 16 468 57.9 3.3 5.1 11.7 59.4 0.17: 1 600 16 469 56.3 3.7 5.1 12.5 - 675 16 484 55.3 0.6 4.7 11.0 - 650 16 479 56.1 3.8 5.2 10.8 - 0.125: 1 700 16 480 56.9 63.0 64.0

♦) Catalyst was heated in powder form.

Claims (8)

Patent claims: 1. A process for the production of acrylonitrile or methacrylonitrile by reacting propylene or isobutene with molecular oxygen and ammonia in the gas state, the amount of olefin between 1 and 20 percent by volume, that of oxygen between 1 and 20 percent by volume and that of ammonia between 2 and 10 Percent by volume, based in each case on the amount of the total charge, in the presence of an inert gaseous diluent and a tin-containing catalyst, optionally applied to a support, at temperatures of 300 to 550 ⁰ C, characterized in that the reaction is carried out in the presence of a mixture of the Oxides of antimony and tin, advantageously in an atomic ratio of 1: 0.1 to 10, and / or a compound of antimony, tin and oxygen is carried out as a catalyst, which has been heated ^{to temperatures of 540 to 1100 ° C. before the reaction,} 2. The method according to claim 1, characterized in that a mixture of antimony tetroxide and Stannioxyd or therefrom by carrying out the reaction in the presence by heating in an oxygen-containing gas to temperatures of 550-1100 ⁰ C entstandenem Zinnantimonat as a catalyst. 3. The method according to claim 1 and 2, characterized in that the reaction is carried out in the presence of a catalyst in which the atomic ratio of tin to antimony is about 2: 1 or 4: 1 and that of about 950 or 700 ^° C has been preheated. 4. The method according to claim 1 to 3, characterized in that the reaction is carried out in the presence of a catalyst which is obtained by mixing stannic oxide or the aqueous tin oxide obtained by the action of aqueous nitric acid on metallic tin with antimony pentoxide, antimony tetraoxide or the action of aqueous Nitric acid on metallic antimony obtained hydrous antimony oxide and subsequent heating of the mixture to temperatures of 550 to 1100 ⁰ C has been obtained. 5. The method according to claim 1 to 4, characterized in that the reaction is carried out in the presence of a catalyst which by preheating a mixture of divalent tin and or or trivalent antimony compounds in the presence of a mixture of oxygen and an inert gas to temperatures of at most about 650 ^° C. and subsequent heating in air to a temperature of 550 to 1100 ^° C. has been produced. 6. The method according to claim 1 to 5, characterized in that the reaction in Carries out the presence of a catalyst which has been applied to silica as a support. 7. The method according to claim 1 to 6, characterized in that the reaction in Presence of water vapor or mixtures of water vapor and nitrogen as inert carries out gaseous diluent. 8. The method according to claim 1, characterized in that the reaction is carried out with an ^{amount of propylene of about 5% and} an amount of ammonia of about 6%, in each case based on the amount of the total charge. Considered publications:
German Patent Nos. 897 560, 941 428;
Austrian Patent No. 180 257;
British Patent No. 774011;
French Patent No. 1,098,400;
U.S. Patent No. 2,481,826;
published documents of Belgian patent No. 571 200. A priority document was displayed at the time of the announcement. 509 719/409 10.65 © Bundesdruckerei Berlin