DE2746134A1 - METHOD FOR PRODUCING MALEIC ACID ANHYDRIDE - Google Patents

Description

JlO

27A6134

51 148-BR

Applicant: The Standard Oil Company
Midland Building
Cleveland, Ohio 44115, USA

Process for the preparation of maleic anhydride

The invention relates to the production of maleic anhydride from hydrocarbons having four carbon atoms; in particular a process for the preparation of maleic anhydride by oxidation of η-butane, n-butenes, 1,3-butadiene or a mixture thereof with molecular oxygen in the gas phase at a reaction temperature of about 250 to about 600 C in the presence of a catalyst.

In the Belgian patent specification 828 074 is the use of a catalyst, the phosphorus, molybdenum, bismuth, copper, at least one element from the group Fe, Ni, Co and K and optionally
Contains Li, Na, Rb, Cs, Be, Mg, Ca, Sr or Ba, in the production of maleic anhydride from 1-butene, 2-butene, butadiene, pentane,
Pentadiene, cyclopentadiene and benzene are described. Comparative example 4 on pages 20 and 21 of this patent specifies

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that when using a catalyst of the formula P- λλ ^ ιο "

Bi ₀ . _Λ , 0υ _{Λ CJ} O-rt . in the oxidation of butene-1 maleic acid-Ο, 36 U, M or, ο

anhydride is obtained in a yield of 27.9 %, based on the amount of butene-1 fed.

In the French patent 1 601 955 is the use

of a catalyst with the composition ΑΟ ,, - ΒλΟ, .- ΜλΟ, .- Ν 0-R „0

described, in which A Cr, Mo, W or U, B V or Nb, M P,

As, Sb or Bi, N Cu, Ag, Fe, Co or Ni, R Li, Na, K, Cs or Rb mean. A preferred composition consists of 15

up to 55 atoms * A, 30 to 70 atoms * B, O to 15 atoms * M, 0.1 to 20 atoms * N and O to 15 atoms * R.

The aim of the invention is to find new, more effective catalysts for the oxidation of η-butane, n-butenes and 1,3-butadiene can be verwei det and deliver maleic anhydride in higher yields.

After extensive research it has now been found that this goal can be achieved by using maleic anhydride produced by the oxidation of η-butane, n-butenes, 1,3-butadiene with molecular oxygen in the gas phase in the presence of catalysts containing molybdenum, phosphorus, oxygen and the in the following groups I to IV specified components contain: (i) bismuth, copper and a halogen selected from the group chlorine, bromine and iodine, or (2) arsenic and at least one element selected from the group Sn, the rare earth metals, Zr, Rh, Mn, Re, Ru, Cu, Pb, Zn, Ti, Cr, Nb, Al, Ga or the alkaline earth metals, or (ill) at least one element,

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selected from the group As, Rb, Pd, Cd, Cs, Tl and In, or (IV) Rubidium and at least one element which is selected from the group Sn, the rare earths, Ni, Cr, Ba, Fe, Rh, Mn, Re, Ru, Co and Cu.

The catalysts used according to the invention are more effective catalysts for use in the oxidation of n-butane, n-butenes and 1,3-butadiene and they have the surprising Advantage that they provide maleic anhydride in higher yield. Particularly advantageous yields are with the catalysts of the invention for 1,3-butadiene and n-butenes obtain.

The invention relates to a process for the preparation of maleic anhydride by oxidation of η-butane, n-butenes, 1,3-butadiene or a mixture thereof with molecular oxygen in the gas phase at a reaction temperature of about up to about 600 C in the presence of a catalyst and optionally in the presence of steam, which is characterized by that a catalyst of the general formula is used as the catalyst:

where mean:

X is a halogen selected from the group consisting of chlorine, bromine and iodine,

a, b and c numbers from 0.001 to 10,

d is a number from 0.001 to 5 and

f is a positive number that stands for the oxygen atoms that are used

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./te

Saturation of the valence states of the remaining elements present required are;

X Mon ₁₀ P. As 0 II

a 12 b ex

where mean:

X at least one element selected from the group Sn, the Rare earth metals, Zr, Rh, Mn, Re, Ru, Cu, Pb, Zn, Ti, Cr, Nb, Al, Ga and the alkaline earth metals,

α is a positive number less than about 20, b and c numbers from 0.001 to 10 and

χ the number of oxygen atoms necessary for the saturation of the

Valence states of the remaining elements required X _Q Mo ₃ P _b O _x III

where mean:

X at least one element selected from the group As, Rb, Pd, Cd, Cs, Tl and In,

α is a positive number less than about 10, b is a positive number less than about 3, and

χ the number of oxygen atoms necessary for the saturation of the

Valence states of the remaining elements required

X Mon ₁₀ P. Rb 0 IV

a 12 b ex

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where mean:

X at least one element selected from the group Sn, the rare earths, Ni, Cr, Ba, Fe, Rh, Mn, Re, Ru, Co and Cu, α is a positive number less than about 20, b and c numbers from 0.001 to 10 and

χ the number of oxygen atoms that saturate the valence states the other existing elements are required.

In particular, hydrocarbons with 4 carbon atoms are made from high yields and selectivities in an effective, convenient and economical manner at a relatively low temperature achieved in maleic anhydride. The exothermic of the reaction is small, so that the reaction can be easily controlled can.

The most important aspect of the present invention is that used Catalyst. The catalyst can be any of the above-indicated catalysts of formulas I to IV Act. The catalysts used according to the invention have preferred limitations on their composition.

If catalysts of the formula I are used, preferred catalysts are those in which a, b and c numbers from 0.01 to 5 and d represent a number from 0.001 to 1.0. Preference is also given to catalysts in which α is a number from 0.5 to 1.5, Catalysts in which b is a number from 0.1 to 1.0, catalysts in which c is a number from 0.1 to 1.0, and catalysts in which d is a number from 0.0 1 to 0.5. Catalysts that are particularly advantageous are those

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^ 27A6134

in which d is a number from 0.005 to 0.1. Particularly preferred catalysts are those in which X is chlorine.

When catalysts of Formula II are used, they are preferred Catalysts those in which α is a positive number of less than about 20, catalysts in which b is a number of 0.01 to 5 denotes catalysts in which c denotes a number from 0.01 to 5. Very beneficial results are obtained with catalysts in which b is a number from 0.5 to 1.5 and c is a number from 0.1 to 1.0. Preferred catalysts are those in which each element X is incorporated separately into the catalyst. Particularly preferred catalysts are those in which X copper in combination with at least one of the other elements, which are also denoted by X, is.

When catalysts of Formula III are used, preferred catalysts are those in which α is a positive number less than about 7 and catalysts in which b is a positive number less than about 2. Very advantageous results are obtained with catalysts in which α is a number from 0.01 to 3 and b is a number from 0.01 to 1.0. Particularly advantageous catalysts are selected those in which X represents at least one element from the group _f rubidium cesium, thallium and indium. Excellent results are obtained with catalysts in which each element X in the catalyst formula is separately incorporated into the catalyst.

When catalysts of Formula IV are used, they are preferred Catalysts those in which α is a positive number less than

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about 12 means catalysts in which b is a number from 0.01 to 5, and catalysts in which c is a number from 0.01 to 5 means. Particularly preferred catalysts are those in which b is a number from 0.5 to 1.5 and c is a Number from 0.1 to 1.0. Very advantageous catalysts are those in which X is at least one element that is selected from the group Ni, Cu, Sn and the rare earths.

The processes for preparing the catalysts used in accordance with the invention can vary widely. A number of procedures are known to those skilled in the art. Various processes for the production of the catalysts, like z.ß. by coprecipitation, by evaporative drying or by oxide mixture and subsequent calcination of the obtained catalysts.

The preferred process for preparing catalysts of Formulas I to IV comprises preparing the catalysts in an aqueous slurry or solution of compounds containing molybdenum and phosphorus, to which the remaining components are added and the subsequent evaporation of this aqueous mixture. However, when producing catalysts of formula II the preferred method involves preparing the catalysts in an aqueous slurry or solution of compounds containing molybdenum, arsenic and / or phosphorus, and the subsequent addition of the remaining compounds. To suitable Molybdenum compounds that can be used to prepare the catalysts of Formulas I to IV include molybdenum trioxide, Phosphomolybdic acid, molybdic acid and ammonium heptamolybdate.

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/ η-

Excellent results are obtained when using catalysts according to the invention in which at least a part of the molybdenum used to produce the catalysts is supplied in the form of molybdenum trioxide. To suitable phosphorus compounds, which can be used in making the catalysts include orthophosphoric acid, metaphosphoric acid, Triphosphoric acid, phosphorus halides or oxyhalides. The remaining components of the catalysts can be in the form of the oxide, Acetats, Formate, Sulphate, Nitrate, Carbonate, Halogenide and Ox / halides are added.

It is important to note that when preparing catalysts of Formula I, particularly preferred catalysts are those in which bismuth is in the form of a bismuth halide or Oxyhalide is supplied. It is not clear where the halogen atom is located in the catalytic structure. The infrared analysis shows that the catalysts for the most part based on phosphomolybdate and that the halogen is most likely is in the form of a molybdenum oxyhalide.

Excellent results are obtained when phosphoric acid and molybdenum trioxide are left in water for about 1.5 to about 3 hours heated to reflux, but a commercial phosphomolybdic acid can also be used with success, the rest Adding components to the aqueous slurry and boiling down to a thick paste, with at least one of the components in the form of a halide or oxyhalide is added, and air drying at 110 to 120 C. However, if catalysts Formula II will give the best results

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J »

obtained when the catalysts are calcined after drying
will. The catalysts of the formulas III and IV can also be prepared by mixing the catalytic components in an aqueous slurry or solution by heating the
aqueous mixture to dryness and by calcining the resulting catalysts.

With the exception of the catalysts of Formula II, is preferred According to the production process according to the invention, calcination is generally not necessary to achieve the desired catalysts. However, the calcination can be carried out by heating the dry catalytic components to a temperature of about 300 to about 700 C, with the preferred calcination at a Temperature of 325 to 450 C is carried out. The converted hydrocarbon can be η-butane, n-butenes, 1,3-butadiene or a mixture of these. The use of 1,3-butadiene, n-butenes or a mixture of hydrocarbons is preferred, formed in refinery streams. The molecular oxygen is most conveniently added in the form of air, but it is Synthetic streams containing molecular oxygen are also suitable. Except for the hydrocarbon and molecular oxygen other gases can also be added to the reactant feed. For example, the reactants can be water vapor or nitrogen can be added.

The ratio of reactants can vary widely and is not critical. The ratio of hydrocarbon to molecular Oxygen can be within the range of about 2 to about 30 moles of oxygen per mole of hydrocarbon. Preferred Oxygen ratios are from about 4 to about 20 moles of oxygen

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per hol hydrocarbon

The reaction temperature can vary widely and depends on the particular hydrocarbon used and the particular hydrocarbon used Catalyst off. Typically temperatures from about 250 to about 600 C are used, with temperatures of 250 to 450 C are preferred.

The catalyst can be used alone or a carrier can be used. Suitable supports include silica, alumina, alundum, silicon carbide, boron phosphate, zirconia, and titania. The catalysts are conveniently used in a fixed bed reactor in the form of tablets, pellets or the like, or in a fluidized bed reactor employing a catalyst which preferably has a particle size of less than about 300 microns. The contact time may be 20 seconds or more of a fraction of a second to z \ j. The reaction can be carried out at atmospheric pressure, at elevated pressure or at reduced pressure.

Excellent results have been obtained using a coated catalyst consisting essentially of one inert carrier material with a diameter of at least 20 microns and an outer surface and a continuous one Coating of the active catalyst on the inert support, which is firmly adhered to the outer surface of the support. By using of these coated catalysts in the reaction to produce maleic anhydride, a very low exotherm is achieved, which allows better control of the reaction.

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High yields are achieved in a single pass and undesirable by-products are eliminated. A special one Coated catalyst consists of an inner support material with an outer surface and a coating of the active catalytic material on this outer surface. These catalysts can be made by a number of different methods getting produced.

The carrier material for the catalyst forms the inner core of the catalyst. This is essentially one
inert carrier of essentially any particle size
and shape, with a diameter greater than 20 microns being preferred. For use in a commercial reaction vessel (reactor) according to the invention, those are particularly preferred
Carriers that are spherical and about 0.2 cm to about 2 cm in diameter. Suitable examples of essentially inert support materials include alundum, silicon dioxide, aluminum oxide, aluminum oxide-silicon dioxide, silicon carbide, titanium dioxide
and zirconia. Particularly preferred among these supports are alundum, silica, alumina and alumina-silica.

The catalysts can contain essentially any proportions of support and catalytically active material. The limits for this ratio (this relation) depend only on the relative ability of the catalyst and the support material, to match. Preferred catalysts contain about 10 to about 100 percent by weight of the catalytically active material, based on the weight of the wearer.

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These coated catalysts can be produced by various processes. The basic method of manufacture of these catalysts consists in partially wetting the carrier material with a liquid. The carrier should not be wetted (moist) on the outer surface of the total mass. It should feel dry to the touch. When the wearer is wet, then the active catalytic material can agglomerate into separate aggregates when attempting to coat the support therewith. These partially moist supports are then brought into contact with a powder of the catalytically active material and the mixture is gently agitated until the catalyst has formed. Careful movement is most expedient in the V / eise, that wan the partially moist (wetted) carrier in a rotating Drum or in a rotating piston and adds the active catalytic material. This can be very economical be performed.

When using the catalysts of the invention for the production of maleic anhydride, excellent yields with small amounts of by-products are obtained as part of an advantageous reaction obtain.

The invention is illustrated by the following examples in which preferred embodiments of the invention are described in more detail explained, but without being limited thereto.

Examples T -60

Production of maleic anhydride using various catalysts according to the invention

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Oil

Examples 1-5

Production of maleic anhydride using catalysts of the formula I.

example 1 A catalyst of the formula Mo ₁₀ P _{1 oo} Bi _A -0υ _Λ "-C1. _ΛΖ 0, became

IZ 1.32 0.5 0.25 0.06 τ

prepared as follows: a slurry was prepared from 86.4 g (0.60 mol Mo) molybdenum trioxide and 7.6 g (0.067 mol P) 85% phosphoric acid in 500 ml distilled water and this was boiled for 3 hours with stirring Production of phosphomolybdic acid, which was yellowish green in color. To this slurry, 2.5 g (0.0125 mole Cu) of copper acetate was added with no change in color, then 7.9 g (0.025 mole Bi) bismuth chloride dissolved in 4.0 ml of concentrated hydrochloric acid was added. The mixture was evaporated to dryness and air dried at 110 ° C. overnight. The catalyst was ground and sieved to recover the fraction having a particle size of 1.65 to 0.55 mm (10/30 mesh).

A portion of the catalyst particles was placed in a 20 cc fixed bed reactor (-Reaction vessel) equipped with a stainless steel tube with an inner diameter of 1.02 cm was. The reactor was brought to reaction temperature under a stream of air heated and the 1,3-butadiene / air feed listed below was added with an apparent contact time passed over the catalyst for 3 to 4 seconds and that

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The pleasure of performing was achieved by studying and analyzing the products emit te It.

The results of these tests are given in Table I below specified · To determine the number of carbon atoms in the Charge and in the product the following definitions have been applied:

Yield in one mole of maleic anhydride obtained .__ single pass ^) = moles of hydrocarbon fed in

_. ,. Moles of converted hydrocarbon .__

Total conversion = r—: τττΐ '- "7 χ 100

° moles of hydrocarbon in the

feed

e ι ix · «An. ·. Yield in one pass _{1 / v} ^

Selectivity = rr y: ^B - * χ 100 Total conversion Examples 2 to 5

Tobelle I

Production of maleic anhydride from 1,3-butadiene using the catalyst Mo ^ £ ^ 32 ^Bi 0 5 ^ 0 25 ^C1 0 06 ° f

Teaio. Loading
kungsver
ratio 310 23 Results {%) 6.97 selectivity Example! , ⁰ C. L air /
Bad exothermic toilet 329 41 Total acid maleic acid
anhydride 44.09 83.9 2 301 351 34 8.31 47.88 91.7 3 317 379 27 48.10 47.07 89.6 4th 333 53.47 89.4 5 349 52.67

HC = hydrocarbon 809817/0736

27Λ613Α

In the same way, were catalysts that different Amounts of phosphorus, bismuth, copper and chlorine contained, used to make maleic anhydride from 1,3-butadiene. In the same manner as well, various of the present invention were made Catalysts with elements such as Mn, Rh, Ru, Ti, Zn, Re, Pb, a rare earth element, In, Sn, Zr, Cr, Pd or a mixture thereof activated to achieve the desired yields of maleic anhydride from η-butane, n-butene, 1,3-butadiene and a mixture of it «

Examples 6-23

Production of maleic anhydride using catalysts of the formula II

Examples 6-8

Various catalysts of Formula II were prepared as follows:

Example 6

25 ° x

A slurry consisting of 317.8 g of ammonium heptamolybdate (NH ₄ ) ^ Mo ₇ O ₂₄ .4H ₂ O and 1500 ml of distilled water was boiled with stirring. 11.91 g of ammonium arsenate NH ₄ H ₅ AsO were added to this slurry. added and heating was extended for 20 minutes

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274613 /,

continued for a long time, the color was white. After the addition of 7.5 g of copper acetate, the color changed to light blue. To this mixture, 22.8 g of phosphoric acid H ₃ PO ₄ (as an 85 # solution) were added and 10 minutes later 7.5 g of hydrazine were added to give a dark blue solution which evaporated to a thick paste overnight 100 to 120 ° C was dried and ground and sieved to a particle size of less than 0.28 mm (<50 mesh). The catalyst obtained was for 1 hour at 371 ° C in 40 ml / min. Air calcined.

Example 7 ^Mo 12 ^P 1.32 ^As 0.5 ^Cu 0.20 ^Cr 4 ° x

A slurry was prepared which consisted of 105.9 g of ammonium heptamolybdate, 700 ml of distilled water at 60 ° C. and 3.97 g of ammonium arsenate in the form of a solution in 25 ml of water; on boiling for 45 minutes, a white precipitate formed. 15.2 g of chromium oxide were added to this mixture, 2.4 g of copper acetate were added 15 minutes later and 7.6 g of 85% phosphoric acid were added 1/2 hour later. The solution was boiled down to a thick paste, dried in an oven overnight at 110-120 ° C, and ground and sieved to a particle size of less than 0.28 mm (£ 0 mesh). The calcination was the same as given in Example 2.

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Example 8

25 % Moj2 ^P i 32 ^As o 5 ⁰⁰ O 20 ^Cr 4 ° x ^{+ 75} ^ Alundum (coated)

This catalyst was prepared in the same manner as in Example 3, but this time using the dry catalyst particles in the form of a layer on 0.32 cm (1/8 inch) -SA5223 alundum spheres were applied by using 50 g of alundum, partially wetting the alundum with 1.8 g of water and adding of 16.7 g of the active catalyst prepared above in five equal portions. During and after every encore the alundum rolled in a glass flask. The powder was evenly distributed on the alundum surface and the end product was dried. The hard uniformly coated catalyst that was obtained consisted of the alundum support and the continuous, firmly adhering coating made of the active catalyst. The catalyst was then poured into 40 ml at 371 ° C. for 2 hours Air / min, calcined.

Examples 9-23

Production of maleic anhydride from 1,3-butadiene

Some of the catalyst particles prepared according to Examples 6 to 8 was introduced into a 20 cc fixed bed reactor fitted with a stainless steel tube with an inner diameter 1.02 cm. The reactor was heated to reaction temperature under a stream of air and a 1,3-butadiene / air feed, as indicated below, with a

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apparent contact time of 3 to 4 seconds over the catalyst and the performance was determined by collecting and analyzing the products. The results of these experiments are given in Table II below.

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Tobelle II

Production of maleic anhydride from 1,3-butadiene using catalysts from

Formula II

Example catalyst feed ^ Temp. ⁰ C. Results (%)

No. Luf-fc / ΗΓ Bad- Exothermic Total Acid Maleic Anhydride-Selective! «

9 Mo ₁ , P ₁ ,, As _n -Cu _n , _0 25.20 263 270 6.41 4.56 71.11

XZ X JZ U j U ZJ X

10 'Mo ₁₀ P ₁ ,, As _n .Cu _n , .O 26.30 280 306 38.33 32.09 83.73

XZ X «JZ \) m D U · Jj X

11 IiO ₁₁ P ₁ ,, Ae _n .Cu _n , .O 26.58 294 389 60.19 50.16 83.33

XZ X JZ U 3 U Z3 X

a, 12 ^Mo i2 ^P l 32 ^As 0 5 ^Cu 0 25 ° x ²⁹ * ^{28 308 343 5} ° * " ⁴³ " ^{12 84} * ⁵⁷

^{13 Mo} 12 ^P 1.32 ^Ae 0.5 ^Cu 0.2 ^Cr 4 ° x ^{24 '55 251 256 17} " ^{19 4} ' ^{13. 24} '° *>

^ 14 Mo ₁₂ P _{3 32} As _{n 5} Cu _{Q 2} Cr ₄ 0 _x 26.19 269 355 50.93 43.25 84.93 * °

O 15 Mo ₁₉ P ₁ ,, Ae _n ,. Cu _n , Cr, O 24.56 286 369 52.51 43.82 83.44

^ ^ XZ X * JZ U * JW · Z 4 X

ω 16 ^Mo i2 ^P i 32 ^ 0 5 ^Cu O 2 ^Cr 4 ° x ²⁵ * ^{06 303 367 55} * ^{74 47} * ^{41 85 '06}

17 ^Mo i2 ^P l 32 ^As 0 5 ^Cu O 2 ^Cr 4 ° x ^{25 '26 316 371 51} * ^{05 44} ' ^{58 87} " ³²

18 257 Mo "Ρ," Αβ _{Λ r} Cu _no Cr, 0 + 23.77 303 320 · 50.71 44.23 87.22 75% Ali

19 25ZMo ₁₀ P ₁ ,, As _n .Cu _n , Cr, O + 21.74 321 348 51.90 45.91 88.47 ^ |

75% Alan Auft- ² (b2-layered) ^X S

20 257 Mo, P As _n. Cu _n CrO ibeschi ^{25 05 336 388 46 98 39 36} 83.78 co

Ii L.ii 0.5 u. L 4 χ ν cntet) ^

21 25JMo ₁₁ P ₁ ,, Ae _n .Cu _n , Cr, 0 (») 25.86 371 406 47.31 41.28 87.26

XZ X jL U j U Z HX

22 25JMo ₁ -P. , .As _n .Cu _n , Cr, 0 ( “ ) 24.84 386 413 46.30 42.55 91.89

XZ XaJZ \ J J l) 4 HX

23 25% Mo, P Ae _n .Cu _n , Cr.0 (· ") 22.74 418 446 47.11 40.74 86.48

XZ X jZ U 3 U Z H X

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Examples 24-50

Production of maleic anhydride using catalysts of the formula III

Examples 24-27

Various catalysts of the formula III were prepared as follows:

Example 24

^Rb 0.5 ^Mo 3 ^P 0.33 ° x

An aqueous slurry was prepared by adding 55.3 g of molybdenum trioxide to 1 liter of boiling distilled water with stirring, the slurry was boiled for about 2 hours. To this aqueous slurry was added 4.9 g of a 85 / Sigen phosphoric acid solution was added, whereby the color of the Slurry changed to red. About 200 ml of distilled water was added to maintain a solution level of about 800 ml. 7.5 g of rubidium carbonate were added to this aqueous mixture added, the color of the slurry turned light yellow, and after about 30 minutes, 25 ml of distilled Water added. The catalyst was heated with stirring, evaporated to dryness and air dried at about 110 ° C. The catalyst was ground and sieved to obtain a fraction with a particle size of 1.65 to 0.55 mm

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(10/30 mesh).
Examples 25-27

Various catalysts according to the invention were prepared. These catalysts had the general formula X- _K Mo ,, P _{n oo} 0.

U, O «3 U, JJ X

These catalysts were prepared according to the method of Example 1, but this time 86.2 g of MoO and 7.7 g of 85% H “PO. were used. After the phosphoric acid was added, the element represented by X was added. The following compounds and quantities were used to prepare the catalysts:

example
No. Element X = link Amount (g; 25th Cs Cesium acetate 19.2 26th Tl Thallium (l) acetate 26.3 27 In Indium acetate 29.2

After the addition of Element X, the catalysts were evaporated to dryness, air dried, ground and sieved as indicated in Example 1.

Examples 28-46

Production of maleic anhydride from butene-2

Some of the catalyst particles prepared according to Examples 25-27 was introduced into a 20 cc fixed bed reactor fitted with a stainless steel tube with an inner diameter

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1.02 cm. The reactor was under a Air stream heated to reaction temperature and an air / butene - ^ / hLO feed was as indicated below with an apparent contact time of 1.0 to 1.5 seconds Passed over the catalyst and the performance was assessed by collecting and analyzing the products. The results these tests are given in Table III below.

Examples 47-50

Production of lialeinic anhydride from butene-2 using supported catalysts

There are various catalysts prepared using the catalyst of Example 2 of the formula Cs _{n K} Mo _o P _{n oo} 0, diluted with 30 wt -.% Of carrier having a small surface size

2 (i.e. from ^ - 20 m / g). These catalysts were based on the Reacted above with butene-2 and air. The results of these tests are in the table below IV stated.

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example Manufacturing Tabel III Temp ("C.) Butene-2 89 HC "H keep up. Events (K) Maleic acid an No. from maleic anhydride .) Bath 60 1 , 0 Total acid * hydride
46.9 28 - 410 60 1 0 57.9 41.1 29 catalyst Operational
time (hrs 416 36 1 21 57.4 46.4 30th ^Rb 0.5 ^Mo 3 ^P 0.33 ° x 31.0 438 Loading «μ 42 1 10 61.9 47.3 31 ^Rb 0.5 ^Mo 3 ^P 0.33 ° x 55.0 438 Exothermic ie Lnf + 81 1 6th 58.9 38.4 Λ » 32 ^Rb 0.5 ^Mo 3 ^P 0.33 ° x 76.0 442 423 81 1 0 47.9 30.0 OO 33 ^Rb 0.5 ^M ° 3 ^P 0.33 ° x 79.0 384 427 80 1 0 41.7 37.4, iw
CO
OO 34 "Os ^ o.ss ⁰ " 83.0 403 451 79 1 0 51.1 36 «^
i ^ a 35 ^C8 0.5 ^Mo 3 ^P 0.33 ° x 1.8 415 455 79 1 0 51.4 37.4 / 07 36 ^C8 0.5 ^M ° 3 ^P 0.33 ° x 3.5 415 457 74 1 0 54.1 cn 37 ^Cs 0.5 ^M ° 3 ^P 0.33 ° x 19.4 421 398 74 1 0 56.5 JP- * 38 ^C8 0.5 ^Mo 3 ^P 0.33 ° x 334.1 325 418 72 1 0 35.7 KJJ
CO 39 ^C8 0.5 ^M ° 3 ^P 0.33 ° x 337.0 339 431 1 0 A3.8 -P ^ 40 ^T1 0.5 ^Mo 3 ^P 0.33 ° x 4.0 353 430 0 44.4 ^T1 0.5 ^Mo 3 ^P 0.33 ° x 5 440 ^T1 0.5 ^Mo 3 ^P 0.33 ° x 25th 342 359 372

Continuation from Table III

41 42 43 44 45 46

ⁿ 0.5 ^Mo 3 ^P 0.33 ° x ^T1 0.5 ^Mo 3 ^P 0.33 ° x ^T1 0.5 ^Mo 3 ^P 0.33 ° x ^In 0.5 ^Mo 3 ^P 0.33 ° x ^In 0.5 ^Mo 3 ^P 0.33 ° x ^In 0.5 ^Mo 3 ^P 0.33 ° x

27 363 386 29 377 402 46 386 413 3.0 386 401 23 399 421 27 396 414

69 1 O 69 1 O 69 1 O 76 1 O 74 1 O 74 1 O

46.6 43.2 51.0 40.6 39.5 41.7

* measured as total acid

.p cn

Table IV

Performance of the supported catalysts in the manufacture of Maleic anhydride from butene-2

• Example no.

catalyst

Operating Charging Temp £ ° C> Results [%) ~ Time (hrs.) Yerhü, ltn. Bad Exothermic Total Acid * Maleic Acid

oo 47 J 48 7OZ

+ 3 OZ TiO

ο 50 7OZCs ₀₅ Mo ₃ P ₀₃₃ O _{x + 3} OZ

• measured as total sturgeon

45

44

71

T-JUT t / HCT
85

₃₃ 2
₃ 95
430
383

346
418
446
396

40.1
49.4
56.0
41.3 *

18.7 36.0 41.9

hydride

N>

CD CO

ar

Examples 51-60

Production of maleic anhydride using catalysts of the formula IV

Example 51

Produced a catalyst of the formula Ni _ß o ^ O ^ ° 1 9 ^{^>} '\ 19 ^ 9 ^ ^WUR de as follows:

A slurry was made from 86.4 grams (0.6 moles) of molybdenum trioxide and 7.7 grams (0.067 moles) of 85% phosphoric acid in 800 ml of distilled water, this was boiled for 2 hours with stirring, whereby a yellow-green color was obtained. to 0.74 g (0.01 mole) of nickel oxide was added to the slurry with no change in color, after which 2.49 g (0.0125 mole) Copper acetate hydrate added, again no change in color was observed. Boiling was continued for an additional 1.5 hours, heating was discontinued, it was distilled Water was added to the mixture to bring the volume to 800 ml and the slurry was stirred overnight. The next day, 14.4 g (θ, 1 mol) rubidium acetate were added and a heavy yellow precipitate immediately formed. This mixture was boiled down to a thick paste and over Dried overnight in an oven at 110 to 120 ° C. The catalyst was ground and sieved to a particle size of 0.33 up to 0.55 mm (20/30 mesh).

The reactor consisted of a stainless steel tube with an internal diameter of 1.02 cm x part of the catalyst fraction

809817/0738

was filled into the 20 cc reaction zone of the reactor. The reactor was heated to reaction temperature and with an apparent. Contact time of 1.0 to 1.5 seconds became one Air / ßuten - ^ - feed, as indicated below, via the Catalyst passed and performance was determined by collecting and analyzing the products. The results of the Experiments are given in Table V in Examples 53 to 60.

Example 52 Production of maleic anhydride from 1,3-butadiene

In the same way as indicated above, the catalyst Ni ₀ “Cu. 25 ^Mo 12 ^P l 32 ^Rb 2 ° implemented ^{with Luit and 1} Z ³ - ⁶ "* ⁰⁰ " * ⁶¹¹ . An air / 1,3-butadiene (84/1) feed was passed over the catalyst with an apparent contact time of 1.5 seconds at a reaction temperature of 285 ° C. The results of this experiment gave a yield of 17.8 % total acid in a single run *

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Tobelle V

Capacity of the catalyst Ni _{Q 2} Cu _{0 2} 5 ^M ° 12 ^P 1 32 ^Rb 2 ° x ^{in the manufacture} 9 ^v © n
Maleic anhydride from butene-2

example of operational loading temples; Results [%) ~~~

No. time (hrs.) _{Ratio Bqd} exothermic total acid maleic anhydride

Air / HC

53 0.7 92 375 418 39.3 35.8

ο 54 3.3 96 340 386 43.8 39.5

⁰⁰ 55 5.0 96 299 322 44.5 32.5

Air / HC 375 92 340 96 299 96 315 91 308 91 304 120 317
302 106
93

^. 56 24.0 91 315 343 Γ) 0.3 34.2

-J 57 26.5 91 308 337 48.9 32.6

° * 58 28.0 120 304 331 45.2 35.1

59 46.0 106 317 366 49.1 37.3

60 46.0 93 302 319 48.1 43.6

CD Ca?

Claims (41)

Claims 1. Process for the preparation of maleic anhydride by oxidation of η-butane, n-butenes, 1,3-butadiene or a Mixture thereof with molecular oxygen in the gas phase at a reaction temperature of about 250 to about 600 C in the presence of a catalyst, characterized in that a catalyst of the general formula is used as the catalyst is used where mean: X is a halogen selected from the group consisting of chlorine, bromine and iodine, a, b and c numbers from 0.001 to 10, d a number from 0.001 to 5 and f a positive number of oxygen atoms that contribute to the desolation of the valence states of the remaining elements present 809817/0736 ORIGINAL INSPECTED ~ ² "27A6134 where mean: X at least one element selected from the group Sn, the rare Earth metals, Zr, Rh, Mn, Re, Ru, Cu, Pb, Zn, Ti, Cr, Nb, Al, Ga and the alkaline earth metals, α a positive number less than about 20, b and c numbers from 0.001 to 10 and χ the number of oxygen atoms that saturate the valence states the other existing elements are required; ¹ Wb ⁰ X < ^ΙΠ) where mean: X at least one element selected from the group As, Rb, Pd, Cd, Cs, Tl and In, α is a positive number less than about 10, b is a positive number less than about 3, and χ the number of oxygen atoms required to saturate the valence states of the remaining elements. where mean: X At least one element selected from the group Sn, the Rare earths, Ni, Zr, Ba, Fe, Rh, Mn, Re, Ru, Co and Cu, α is a positive number less than about 20, b and c numbers from 0.001 to 10 and χ the number of oxygen atoms that are needed to saturate the valence 809817/0736 states of the other existing elements are required. 2. The method according to claim 1, characterized in that a catalyst of the general formula is used as the catalyst where mean: X is a halogen selected from the group consisting of chlorine, bromine and iodine, a, b and c numbers from 0.001 to 10, d a number from 0.001 to 5 and f is a positive number of oxygen atoms responsible for saturation of the valence states of the remaining elements present are. 3 «Method according to claim 2, characterized in that a, b and c numbers from 0.01 to 5 and d a number from 0.001 to 1.0 mean. 4. The method according to claim 2, characterized in that a is a number from 0.5 to 1.5. 5. The method according to claim 2, characterized in that b is a number from 0.1 to 1.0. 6. The method according to claim 2, characterized in that c is a number from 0.1 to 1.0. 809817/0736 7. The method according to claim 2, characterized in that d is a number from 0.005 to 0.1. 8. Method according to Claim 2, characterized in that d is a number from 0.01 to 0.5. 9. The method according to claim 2, characterized in that X is chlorine. 10 * Method according to claim 2> characterized in that as Catalyst the catalyst ^Mo 12 ^Bi 0.5 ^P 1.32 ^Cü 0.25 ^Cl 0.06 ° f is used. 11. The method according to claim 2, characterized in that 1,3-butadiene is used for the reaction. 12. The method according to claim 1, characterized in that a catalyst of the general formula is used as the catalyst will where mean: X at least one element selected from the group Sn, the Rare earth metals, Zr, Rh, Mn, Re, Ru, Cu, Pb, Zn, Ti, Cr, Nb, Al, Ga and the alkaline earth metals, α is a positive number less than about 20, 809817/0736 b and c numbers from 0.001 to 10 and χ the number of oxygen atoms that make up the valence states the other existing elements are required. 13. The method according to claim 12, characterized in that
α means a positive number less than about 12. 14. The method according to claim 12, characterized in that b is a number from 0.01 to 5. 15. The method according to claim 12, characterized in that c is a number from 0.01 to 5. 16. The method according to claim 12, characterized in that b is a number from 0.5 to 1.5 and c is a number from 0.1 to 1.0. 17. The method according to claim 12, characterized in that X is copper. 18. The method according to claim 12, characterized in that X is copper and chromium 19. The method according to claim 12, characterized in that fur the reaction 1,3-butadiene is used. 20. The method according to claim 12-19, characterized in that the catalyst in the form of a layer on an inert support
is applied. 809817/0736 Process according to Claim 20, characterized in that the catalyst consists essentially of an inert one Carrier material with a diameter of at least 20 microns and an outer surface and a continuous coating the active catalyst that adheres firmly to the outer surface of the carrier. 22. The method according to claim 21, characterized in that the active catalyst is about 10 to about 100 wt .- JJ of the inert The carrier. 23. The method according to claim 21 or 22, characterized in that that the inert carrier is selected from the group consisting of silicon dioxide, aluminum oxide, aluminum oxide-silicon dioxide, silicon carbide, Titanium dioxide and zirconium dioxide. 24. The method according to claims 21 to 23, characterized in that that the particle size of the inert carrier is 0.2 to 2 cm. 25. The method according to claim 1, characterized in that a catalyst of the formula is used as the catalyst X Mon ₀ P.0
a 3 b χ where mean: X at least one element selected from the group As, Rb, Pd, Cd, Cs, Tl and In, α is a positive number less than about 10, 809817/0736 b is a positive number less than about 3 and χ the number of oxygen atoms that are used to saturate the VaIeηz- the remaining elements are required. 26. The method according to claim 25, characterized in that α means a positive number of less than about 7. 27. The method according to claim 25, characterized in that b is a positive number less than about 2. 28. The method according to claim 25, characterized in that a is a number from 0.01 to 3 and b is a number from 0.01 to 1. 29. The method according to claim 25, characterized in that X means at least one element from the group Rb, Cs, Tl and In. 30. The method according to claim 25, characterized in that X is rubidium. 31. The method according to claim 25, characterized in that X is cesium. 32. The method according to claim 25, characterized in that X is indium. 33. The method according to claim 25, characterized in that X is thallium. 34. The method according to claims 25 to 33, characterized in that 809817/0736 that the active catalytic material is supported on a titanium dioxide support, Zirconia, alumina or silica is applied. 35. The method according to claim 25, characterized in that n-butenes can be used for the reaction. 36. The method according to claim 1, characterized in that as Catalyst a catalyst of the general formula is used X Mon ₁₀ P. Rb O
a 12 b ex where mean: X at least one element selected from the group Sn, the rare Earths, Ni, Zr, Ba, Fe, Rh, Mn, Re, Ru, Co, and Cu, α a positive number less than about 20, b and c numbers from 0.001 to 10 and χ the number of oxygen atoms that saturate the valence states the other existing elements are required. 37. The method according to claim 36, characterized in that α means a positive number of less than about 12. 38. The method according to claim 36, characterized in that b is a number from 0.01 to 5. 39. The method according to claim 36, characterized in that c is a number from 0.01 to 5. 809817/0736 40 «The method according to claim 36, characterized in that that b is a number from 0.5 to 1.5 and c is a number from 0.1 to 1.0 mean. 41. The method according to claim 36, characterized in that X has at least one element selected from the group Ni, Cu, Sn and the rare earths, means. 809817/0736