DE1667209C - Process for the production of oxidation catalysts. Eliminated from: 1268609 - Google Patents

Description

i 667

The present invention relates to new improved catalysts for the oxidation of olefins which the empirical formula

where ti a number from 0 to 20, b a number from 0 to 15, ti and / i together a number from 2 to 20, c a number s mi 0.1 to 7, ti a number from 0, L bi? 4, e is a number from (1.1 to 2, / "about 12 and ι; a number from 35 to 85, correspond.

The catalysts according to the invention can be used in all known processes for catalytic oxidation of olefins with air or molecular oxygen with formation of the known end products such as unsaturated Aldehydes and acids are used. Here in a catalytic dip phase oxidation reaction used catalysts according to the invention increase the overall conversion to some of the desired end products such as unsaturated aldehydes and acids without excessive oxidation of the olefin used to undesirably higher levels Oxidation products of carbon, such as carbon monoxide and carbon dioxide.

Catalysts for the oxidation of olefins by means of I.uft or molecular oxygen, which oxides of Bismuth, molybdenum and phosphorus are described in Tier LISA. Patent 2,941,007. Other catalysts for the oxidation of olefins, which oxides of iron. Wi-.inuts, phosphorus and Molybdenum are contained in the German patent I 125 901. In British patents S78 803 and 893 077 are catalysts Oxidation of olefins using I.uft or molecular Oxygen described, the cobalt b / w. Nitrile molybdate as a catalytically active HestanJicil ent, 15 echo. None of these previously known catalysts contain a combination of nickel oxide and cobalt oxide lint ile oxides of fish, bismuth, phosphorus and Molybdenum, which is why the found-type catalysts differ from the previously known catalysts.

I) Mixing of nickel oxide or cobalt is necessary <\) d or mixtures thereof to achieve the result The catalyst has a very high yield .111 dem Desired oil oxidation product, /. K. a: i Aerolein starting from propylene.

(ieiiiiUl of the USA.-Patent 2,941007 are SIt. ') (irwiclitspro / cnt of the reactor / produced ■ propylene consumed in a single passage over the catalyst and 71.8 "/ _{n of} the consumed propylene unconverted into v> acrolein, while the largest part the remainder of the propylene consumed is converted into carbon monoxide and carbon dioxide. The highest yield from acrolein in a single pass 125 901 70 "/ ,, de ·, / !! guided propylene Ik consumes 1 single passage over the catalyst, and to this are 8l ⁿ / ₀ AuoLui. the Gcsnmliiiuw.iudlung of propylene ß» in acrolein hei single pass is therefore 59 "/ ,,

The catalytic vapor phase reaction is generally observed, but with an increase in the Conversion of the aclionic component a decrease the selectivity occurs, which is why in the previously known processes there is no dipphase oxidation von / H. Propylen in Acrolein the Uni vandlting in Acrolein is usually not very high in a single pass. Such as U. in the procedures according to German Auslegeschrift I 137 427, British Patent 893 077 or French Patent I 315 258 is there to increase profitability the process is necessary on an industrial scale, the olefin from the end product mixture to be separated again and fed back to the starting products. Such procedural measures but these procedural measures are expensive and cumbersome are not required with the catalysts according to the invention.

In contrast to the prior art methods is the erlindungsgemälien catalysts 95 ° / ₀ converted the zugefülirten propylene at a single passage over the catalyst and in this case 75 "'converted ,, the converted propylene to acrolein. Accordingly, with the catalysts of this invention in a single pass a Overall conversion of propylene to acrolein of 71% achieved This result is in fact not obvious and surprising in view of the prior art.

With the catalysts of the invention, the formation of carbon monoxide and carbon dioxide is minimal; in general only about 2% of the olefin in carbon monoxide and only about 5% in carbon dioxide is converted, while the overall conversion of propylene el · ·· 95'V a is _0.

The catalysts according to the invention may provide homogeneous mixtures, homogeneous products or complexes of unknown physical or chemical nature. those made up of a combination of the oxides of iron, bismuth. Phosphorus, molybdenum and continue to consist of nickel and / or cobalt. The catalyst principle is simplicity halher characterized by the following empirical formula:

ΝίΧΌί, ΚγΠι, / Ρ, Μο / Ο ,,

where 11 a / 1I1I son (I to 20, b a number from 0 to I 5. ti plus / 1 2 to 20, ι eir.c number from 0.1 to 7, i / a number from 0.1 to 4, e is a number from 0.1 to 2, / about 12 and t; is a number from 35 to 85.

Because of its especial ^1, favorable catalytic properties cilindungsgcmäßcn those catalysts are preferred, which are represented by the following three empirical Eormeln:

where α is a number from 3 to 14, b is a number from 1 to 3, ι a / aiii from 1 to .1, (/ about 1, ρ 12 and / a / aiii from 45 to / 0;

Γο ,, Κ-ι, Μι, .Ρ ,, Μο, Ο ,,

where ti is a number of ?. to 7, h is a number from I to J, c is a number from I to 3, r / clwa I ₁ e 12 and / is a number from 45 to 70; such as

where (/ is a number less than 14, b is a number less than 1, 11 plus b = - ■ 1 to 14, α and b are both not 0 »γ a / aiii from 1 to 3, il a number from i to 3, e is about I, f 12 and r is a range from 45 to 70.
The /uer.t i'iianulc preferred catalyst can

I 667

can also be described as a product that contains the following components:

Nickel phosphomolybdate 20 to 99.8 mole percent
Lisenphosphomolybdate 0.1 to 40 mole percent

Bismuth phosphomolybdate 0.1 to 40 mole percent

Of these, a very particularly preferred catalyst has the following composition:

Nickel phosphomolybdate. 80 to 90 mole percent
Lisenphosphonmlybdate ... 5 to 10 mole percent
W ismutphosphiunolyhdate 5 to H) mole percent

The catalysts according to the invention are common manufactured in the following way:

Phosphoric acid is added to an aqueous solution of a suitable molar compound, such as I). Ammonium molybdate, added, after which an aqueous solution of a water-soluble iron salt and a water-soluble bismuth salt and also a water-soluble nucleus salt, cobalt salt or a mixture thereof / u is added to the solution of the phosphomolyb- "liiii-iäiir'j. However, this order can also be changed. For example, a woody solution of a suitable molecular compound is added to an aqueous solution of the water-soluble Si!. P ι resulting slurry is then, if erumischt, heated together with i'liciii carrier material / u remove water and dry the solid cake lim / <i formed. The solid cake is then calcined in air at an elevated temperature. ! This (is iliihcn w> rlcilhaft. To the specific Qbertlii. '' Height of the eigentll ·. Iien catalyst to produce and leigern seme Selektisität / <<.

(Iceignete water-soluble salts for the production of the K: ital>sali> rs geni.'i! · of the invention are for example 'mtrat, f ^; .iron (III) -mtrat [Fe ₂ (NO ;,) ,, ie / iellen F ^: All agents can form these water-soluble salts -i) of the metal and acid oiler of an acid, these mixtures being an

Nickel nitrate. Kolvl
and llydrate |. '.ns
μΐ '-.'.- t / t become, youlike /. II. Miichuui- '.
Metalloxvds and

15th

30th

• to

15th

Place the water, borrowed salts are used be able. Molybdenum, molybdic acid or phosphomolybdenum acid can e.g. B. can be used instead of ammonium molybilate.

1 "> ic er'indungs) 'i MAESSEN catalysts siiul particularly effective who... Are .ic iiicleryeschlagen on a carrier appropriated Triigerstoffe are / Π Sili / iiimdiotyd, silicon carbide and aluminum oxide f) cr rräi'.erstoff \ mi. .ds sol or as Ge! / u dem l'hosphoiiiiolybdal hlamm before drying the catalyst / n; '- ■ ('11;'. t. The catalysts can be in many fi in forms, e.g. as grain oiler in Tablcttenforiii are used.They can be used both in the lest bed arrangement and in a vortex classifier.

The crrimliiiig.sgcin.iHen catalysts are used under customary for such Oxyd.itlonsreaktioncn process conditions, ie at a temperature in the range of D ¹ to 45O C and a pressure in the range of 0.5 bi> 10 atmospheres (absolute) and preferably at a Temperature in the range from .KHl to 4 SO ⁰ C at atmospheric pressure, llei the Ox, -

65 dation of olefins, such as? .. B. propylene, with the inventive catalysts, the contact time of the mixture of propylene and air with the catalyst is generally 0.1 to 12 seconds and preferably 0.5 to 8 seconds for a Pressure win 1 atmosphere. The feed gas generally contains 0.5 to 5 moles of oxygen per mil of propylene. To put it somewhat differently, the preferred molar ratio of the constituents in the gaseous starting mixture is 4 to 10 mol of air per MnI of rupylene. It is preferred that water be fed to the reactor in the form of steam along with the gaseous mixture of propylene and air. The large volume of water in the outlet mixture causes a dilution and removal of my heat of reaction; However, there is no need to turn one's eyes to water if the heat of reaction can be effectively dissipated. The Moher Ratio of Water per Mo! Propylene can range from i in. 20, but a ratio of 5 to in is preferred. The output ^ gasgemi .ch used can be saturated hydrocarbons such as Athaii. Propane, etc., because they are inert and do not affect the oxidation of the olefins. In the production of unsaturated nitriles such as acrylonitrile and nitrile nitrile, ammonia is still present in the starting gas mixture. In general, air is used as a source of molecular oxygen: it can contain either zero molecular oxygen as such or a mixture of oxygen with inert gases such as nitrogen. Carbon dioxide, etc. can be used.

The present invention is accomplished by du: fo'gendi-p Examples further explained:

B e 1 s (l i e i 1

A. 163 g of nickel nitrate are dissolved in HOmI distilled water; 21.wy 1 isenoxydnitral become 1 · ¹ . 12 ml of distilled water are dissolved, 25 og of bismn nitrate are dissolved in 18 ml of distilled water. the 2.4ml konzeuiricite nitric acid contains: all mentioned solutions are combined.

B. 113.6 g Ammoniunimolybdat m IKi ml of distilled water are dissolved, and to the solution f> .. 12 u added a 85 ⁿ / "strength Phosphnrsäiiie.

Solution H. which is pale yellow in color. winch / 11 Given solution Λ, and / u the resulting Λ111 Schlärnmung were U. 2 g of silica in lorin one, aqueous sol. The sludge obtained was dried and heated to 400 C ap of the air. chilled product was ground to powder, and d, i, powder was formed into TableMen and here, n.h Annealed (Calcinienuii ·) for 6 hours. Ii became found ilaH tier catalyst ilie following unpi ri'clic formula has:

Ni ₁₁ ^ ₁ Fc ₁ Bi ₁ P ₁ Mo ₁₃ O ₁ ,

Examples 2 to IO

Table 1 below gives some modifications of the composition of the catalyst of Example I. again, and the procedure was the same as in Example I.

table

iici- N icki! | - cobalt Iron! IID- Bismuth- Animu-
niurn- phosphorus
acid Carrier-
siolT Empirical formula -pic'l iiiinit
(K) nilrat
Iy) nitrate
(B) nitral
(B) molybdenum
(G) (HS "/ ,,)
(G) SiO ₂
(B) of the catalyst 155.0 4.6 21.6 25.0 113.6 1.26 40.0 Ni ₁₀ Co ₀₁₃ Fe, Bi ₁ P ₀₁₂ Mo ₁₂ O ₅₃ 3 155.0 4.6 21.6 25.0 113.6 6.3 40.0 Ni ₁₀ Cu ₀₃ Fe ₁ Hi ₁ P ₁ Mo ₁₂ O ₅₇ 4th i 55.0 4.6 21.6 25.0 113.6 3.15 40.0 Ni ₁₀ Co ₀₁₃ Fe ₁ Ri ₁ P ₀₁₅ Mo ₁₂ O _6n 5 105.0 96.8 32.4 37.6 170.0 9.0 60.0 Ni ₄₁₅ COjFe ₁ BiJP ₁ Mo ₁ OO ₅ J (l I (.3.0 12.2 64.8 75.2 170.0 9.0 60.0 Ni ₇ Co ₀ 5Fe ₂ Bi ₂ P ₁ Mo ₁₂ O ₅ J 7th 163.0 48.4 32.6 37.6 170.0 9.0 60.0 Ni ₇ Co ₂ FcBi ₁ P ₁ Mo ₁₂ O ₅₄ 163.0 21.6 25.0 113.6 3.16 34.2 Ni ₁₀₁₅ Fe ₁ Bi ₁ P ₀₁₅ Mo ₁₂ O ₅₆ ^l ) 163.0 21.6 25.0 113.6 9.48 34.2 Ni ₁₀₁₅ Fe ₁ Bi ₁ P ₁₁₅ Mo ₁₂ O ₅₈ H) 106.0 43.2 50.0 113.6 6.32 40.0 Ni ₇₁₅ Fe ₂ Bi ₂ P ₁ Mo ₁₂ O ₅₅ Il 70.0 65.8 75.0 113.6 5.10 60.0 Ni _4i5 Fe ₃ Bi ₃ P _0iS Mo ₁₂ 0 ₅₃ 12th 186.0 28.0 17.4 113.6 6.32 60.0 Ni ₁₂ Fe ₁₁₃ Bi ₀₁₇ P ₁ Mo ₁₂ O ₅₈ 13th 190.0 21.6 25.0 113.6 6.32 40.0 Ni ₁₄ Fe ₁ Bi ₁ P ₁ Mo ₁₂ O ₆₀ 14th 163.0 10.8 37.5 113.6 6.32 40.0 Ni ₁₀₁₅ Fe ₀₁₅ Bi ₁₁ J ₁ P ₁ Mo ₁₂ O ₅₇ I? 145.0 3 "\ 4 37.6 170.0 9.00 60.0 Co ₆ FeIBi ₁ P ₁ Mo ₁₂ O ₅₀ IΛ - 108.7 48.6 56.4 170.0 9.00 60.0 Co ₄₁₅ Fe ₁₁₅ Bi ₁₁₅ P ₁ Mo ₁₂ O ₄₉

A catalyst was produced according to the example of the German Palentschrift 1 125 901 with the inclusion that instead of 173 g MoO ₃ 212 g (NH ₄ ) _fi Mo ₇ O ₂₄ -4H ₂ O was used. The received. 5 mm measured in diameter and 2.5 mm thick iCalalysatortabletten were preheated for 5 hours at 230 C and sintered then 5 hours at 450 ⁰ C in .iiiem airflow. The catalyst obtained corresponded to the empirical formula,

Fe. ,, ₅ Bi _4i5 P, Mo ₁₂ O ₅₂ .

A catalyst of the empirical formula was used as the catalyst according to the application

Ni ₁₀₁₅ Fe ₁ Bi ₁ P ₁ Mo ₁₂ O ₅₇ are used.

60 ml of the above catalysts were placed in a Pyrex glass tube 20 mm in diameter and 350 mm in length, which was placed in an Al ₂ O ₃ fluidized bed bath. The composition of the starting gas mixture was propylene: air: water vapor = 1:10:12. The other reaction conditions and results are given in Table 2 below.

table

German patent 1125 901

No. No. 2

No. 3

According to registration

Reaction conditions Uadtomperatur (° C) .. Contact time (sec.) ..

result

Conversion (mole percent)

Selectivity for acrolein

Single pass yield of acrolein (mole percent)

By-products (mole percent)

Acrylic acid

acetic acid

Carbon dioxide

Carbon monoxide ....

Other

298 2.5

14.0 89.5

12.5 418
2.1

80.8
48.7

35.2

380
2.2

66.3
57.0

37.8

0.1 4.2 3.3 0.1 0.3 0.3 0.8 18.9 11.0 0.5 19.2 10.9 3.0 3.0

298
2.5

94.7
74.3

70.3

10.5
0.8
7.9
2.2
3.0

Remarks:

Trials No. 2 and No. 3 were carried out at higher temperatures! carried out as Experiment No. 1 to increase the conversion.

The contact time given in the table was calculated from the reaction temperature and the reaction pressure. The result of the standard temperature and the contact time calculating the standard pressure was 12 for all batches of Table I

Claims (1)

Claim: Process for the preparation of catalysts for the oxidation of olefins with air, thereby characterized in that phosphoric acid and aqueous solutions of a molybdenum, iron and bismuth compound as well as a nickel and / or cobalt compound in such amounts, that the ratio of the elements mentioned to each other of the general formula corresponds to where α is a number from 0 to 20, b is a number from 0 to 15, α plus b together is a number from 2 to 20, c is a number from 0.1 to 7, d is a number from 0.1 to 4, e is a number from 0.1 to 2, / about Yi and g is a number from 35 to 85, from the resulting mixture, optionally after adding a suitable carrier, the water evaporates and the dry product obtained in a known manner on the Air glows and, if necessary, crushed and deformed.