DE2644107A1 - PROCESS FOR THE CONVERSION OF AETHANE INTO AETHYLENE - Google Patents

Description

V / experienced for the conversion of ethane into ethylene

The present invention relates to gas phase catalytic dehydrogenation of ethane in ethylene in the presence of "oxygen, i.e. on the oxydehydrogenation of ethane in ethylene.

Ethylene was usually commercially produced by thermal cracking of ethane in an endothermic reaction at temperatures of about 600-1000 ⁰ C. (see., U.S. Patent No. 3,541,179). The response time of this process is very short, making effective heat recovery from the process stream difficult or impossible. Furthermore, the high temperatures used require the use of special alloys in the construction of the furnaces or reaction vessels for carrying out the reaction. The cracking reaction also causes the formation of relatively large amounts of low boiling by-products, such as hydrogen and methane, which make the recovery of ethylene from these by-products complicated and expensive.

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It is possible to make ethane using various oxyhalogenation catalyst systems to oxydehydrogenate in an exothermic reaction. However, these reactions are only at temperatures at least about 500-600 ° C. (see US Pat. No. 3,080,435). Further, the presence of the halogen atoms increases the Difficulty in obtaining all olefins formed. In addition, unusual and expensive construction materials are necessary, to prevent corrosion by the halogens and hydrogen halides in to withstand the reaction systems. Furthermore, the halogens themselves must also be recovered and recycled in order to achieve the To make the system economical.

The oxydehydrogenation of selected> C-j alkanes at relatively high Temperatures in an exothermic reaction i6t with selected Catalysts have been carried out containing vanadium (see US PSS 3,218,368, 3,541,179 and 3,856,881) and vanadium and molybdenum (U.S. Patent 3,320,331).

The use of molybdenum- and vanadium-containing catalyst systems for the gas phase oxidation of g ^ ß-unsaturated aliphatic Aldehydes, such as acrolein, to the corresponding $ (, ß-unsaturated Carboxylic acids such as acrylic acid are known. These catalyst systems comprise the elements Mo, V and X, where X is Nb, Ti or Ta (see Belgian patents 821 322, 821 324 and 821 325).

So far, however, it was not yet possible to use ethane easily at relatively oxydehydrogenate low temperatures with relatively high values for conversion, selectivity and productivity in ethylene.

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- y

As used herein, "percent conversion", "percent selectivity" and "productivity" are referred to defined on the present invention as follows:

I % Umandl. _ _{1GD y} , £

(v. ethane) ~ mole of athan in the lead to the catalyst bed Reaction mixture

Ia where A = molar ethane equivalent sum (carbon basis)

of all carbonaceous products excluding ethane in the outflow

manufactured * ® RoI Ethylene

II % select. (or effective = 1QD χ

for ethylene A.

(or acetic acid)

III product for ibs. Ethylene (or acetic acid), manufactured per ... ethylene (or = cuft. Catalyst (in. Catalyst bed) Acetic acid per hour of reaction time

Ethane is preferably oxydehydriert in a gas phase reaction at relatively high levels of conversion, selectivity and productivity and at temperatures below about 550 C, below 450 ⁰ C. with particular containing molybdenum and various other optional elements catalyst preparations to ethylene.

The aim of the present invention is to provide a method for the oxydehydrogenation of ethane in ethylene at relatively low temperatures with relatively high values of conversion, selectivity and productivity. Another aim is to create a process for the oxydehydrogenation of ethane in the presence of water at. Relatively low temperatures with formation of relatively high values for conversion, selectivity and productivity with respect to the Products ethylene and acetic acid. In the method according to the invention can ethane without the simultaneous formation of significant amounts of gas

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miger by-products, such as methane and hydrogen, which make the cryogenic Separation and purification of the ethylene were difficult and costly, oxydehydrogenated in ethylene and / or ground.

The present invention further provides new catalyst preparations for the vapor phase oxydehydrogenation of ethane in ethylene at relative low temperatures.

The objects of the invention are achieved by being in the exothermic Vapor phase oxydehydrogenation of ethane as a catalyst a preparation of the elements Mo, X and Y in a ratio

^Mo a ^X b ^Y c used, where

X for Cr, Mn, Wb, Ta, Ti, M and / or W, preferably for Mn, Nb,

V / and / or W, standsj

Y for Bi, Ce, Co, Cu, Fe, K, Mg, Ni, P, Pb, Sb, Si, Sn, Ti and /

or U, preferably Sb, Ce and / odsr U, stands; a has a value of 1; b has a value from 0 to 2, preferably 0.05-1.0? and c has a value from 0 to 2, preferably 0.05-1.0,

with the proviso that the total value of c for Co, Ni and / or

Fe <0.5.

The numerical values of a, b, and c represent the relative gram atom ratios of the elements Mo, X and Y, which are present in the catalyst preparation are present.

That used in the formation of the catalyst preparation shown above Si is different from that which is present in any support on which the catalyst can be used;

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This will be illustrated later.

The elements Mo, X and Y are in combination in the catalyst preparation with oxygen, presumably in the form of various oxides per se and possibly as chemical combinations of oxides, such as spinels and perovskites, present.

The catalyst is preferably made up of a solution of soluble compounds (salts, complexes or other compounds) each of the elements Mo, Y and X or, in the case of Si and Sb, also as a colloidal sol. The solution is preferably an aqueous one System with a pH of 1-7, preferably 2-6. The solution of the element-containing compounds is produced by

one dissolves sufficient amounts of the soluble compounds of each element to create the desired asbsc gram atom ratio of the elements Mo, X or Y. The selected compounds of the various elements should be mutually soluble as far as possible _D The Si compounds are usually added in the form of a colloidal silica sol. Where the selected compounds of the elements - apart from Si - are not mutually soluble with the other compounds, they can be added to the solution system last. The catalyst preparation is then produced by removing water or other solvent from the mixture of compounds in the solution system.

Water or other solvents can be obtained by evaporation of the combination of all compounds and solvents Mixture to be removed.

Where the catalyst is to be used on a carrier, the compounds of the desired elements are placed on a finely divided

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th porous carrier deposited, which among other things should have the following physical properties * surface area = about 0.1-500 m ² / g; apparent porosity = 30-60 %) where at least 90 % of the pores have a pore diameter between 20-1500 microns and the shape of the particles or tablets is about 3.2-8.0 mm in diameter. The separation takes place by immersing the carrier in the final mixture of all compounds, evaporation of the essential portion of the solvent and subsequent drying of the system at 80-220 ° C. for 2-60 hours. Then, the dried catalyst is calcined by 0.5-24 hours heating at about 220-550 ⁰ C. in air or oxygen

and delivers the desired preparation,

^Mo aVc

Usable carriers include silica, alumina, silicon carbide, Zirconia, titania and mixtures thereof.

When used on a support, the deposited catalyst usually comprises from about 10-50 wt -.% Of catalyst preparation, with the balance being the carrier.

The molybdenum is preferably in the form of ammonium salts, such as ammonium paramolybdate, and organic acid salts of Molybdenum, e.g. the acetates, oxalates, mandelates and glycolates, were introduced. Other suitable, water-soluble molybdenum compounds are partially water-soluble molybdenum oxides, molybdic acid and the chlorides of molybdenum.

When using vanadium, this is preferably in the form its ammonium salts, such as ammonium metavanadate and ammonium deca-

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vanadate, and organic acid salts of vanadium, such as the acetates, Oxalates and tartrates, introduced into the solution. Other suitable water-soluble vanadium compounds are partially water-soluble Vanadium oxides and the sulfates of vanadium.

When using niobium and tantalum, these are preferably introduced into the solution in the form of oxalates. Other suitable Sources of these metals in soluble form are compounds in which the metal is attached to a ß-diketonate, a carboxylic acid Amine, an alcohol or an alkanolamine are coordinated, bound or bound in complex form.

If titanium is used, this is preferably in the form of a water-soluble chelate coordinated with ammonium lactate in the Solution introduced. Other suitable soluble titanium compounds are those in which titanium is attached to a ß-diketonate, a carboxylic acid, an amine, an alcohol or an alkanolamine is coordinated, bound or bound in complex form.

If iron, nickel, cobalt, manganese, copper, chromium, bismuth, uranium, cerium, potassium, thallium, magnesium and lead are used, these are preferably introduced into the solution in the form of nitrates. Other suitable water-soluble compounds of these elements are the water-soluble chlorides and organic acid salts, such as the acetates, oxalates, tartrata, lactates, salicylates, formates and carbonates of these elements.

When using antimony and tin , these are preferably introduced into the catalyst system in the form of water-insoluble oxides. Suitable water-soluble compounds of these elements are

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Antimony trichloride, stannous chloride, stannous chloride, stannous sulphate and Stannous sulfate. Other suitable water-insoluble compounds of these elements are stannous hydroxide and stannous oxalate.

If tungsten is used, it is preferably introduced into the solution in the form of an ammonium salt, and / or ammonium paratungstate. Other suitable water-soluble tungsten compounds are the tungstic acids.

If silicon is used, it is preferably in the form of a aqueous colloidal silica (SiQ ^ sols in the catalyst system introduced.

When using phosphorus, this is preferably used as a phosphorus

acid or as 'water-soluble phosphate in' the catalyst system introduced.

To make the catalysts more effective, the Mo, X and Y metal components are believed to be reduced slightly below their highest possible oxidation state. This can be done during the Heat treatment of the catalyst in the presence of reducing agents, such as NHj or organic reducing agents, e.g. the organic complexing agents, which are introduced into the solvent systems from which the catalysts are made vuerden. The catalyst can also be used in the reactors Carrying out the oxidation can be reduced by using hydrogen or hydrocarbon reducing agents such as ethane, ethylene or propylene, passes through the catalyst bed.

The catalysts, whether or not deposited, can be used in a fixed or fluidized bed.

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The starting material used as a source of ethane should be a gas stream which contains at least 3 vol.-J $ ethane at atmospheric pressure. Furthermore, it can contain smaller amounts, that is to say 5 % by volume, of H2, CO and C _3. -Alkanes and alkenes. It can also substantial amounts, ie / '5 vol .- ^ b to N2 "CH ^, COo ^una" contain water as water vapor.

The catalysts of the invention seem to be their Ability to oxydehydrogenate ethane in ethylene to be specific as they do not oxydehydrogenate propane, η-butane and butene-1 but oxidized these materials into carbon dioxide and others,

Burn carbon containing products.

The components of the feed stream in the invention

Process used gaseous reaction mixture and the relative Ratios of the components in the mixture are as follows:

1 mole of ethane,

0.01-0.5 moles of molecular oxygen (as pure oxygen or

in the form of air) and

0-0.4 moles of water (in the form of water vapor).

Water or steam is used as a reaction diluent and a heat moderator for the reaction. Other materials that can be used as reaction diluents or heat moderators are inert gases such as nitrogen, helium, CO ₂ and methane.

In the normal course of the reaction in the absence of added water, 1 mole of water is formed per mole of oxydehydrogenated ethane. This Water formed during the reaction in turn causes the formation of some acetic acid, i.e. about 0.05-0.25 moles, per mole formed

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Ethylene. The water added to the feed stream causes the formation of additional amounts of acetic acid, i.e. up to about 0.25-0.95 Moles of acetic acid per mole of ethylene formed.

The components of the reaction mixture may be uniformly mixed prior to introduction into the reaction zone. The components uxerden preheated, individually or after mixing prior to their introduction into the reaction zone to a temperature of about 200-500 ⁰ C..

The preheated reaction mixture is brought into contact with the catalyst preparation in the reaction zone under the following conditions:
Pressure etu / a 1-30, preferably etu / a 1-20 at;

Temperature about 150-550 ⁰ C, preferably ^{about 200-400 0} C;

Contact time (reaction mixture on the catalyst) etu / a 0.1-100,

preferably about 1-10, seconds, and

-1 -1

Space velocity about 50-5000 hours, preferably 200-3000 hours. '

The contact time can also be expressed as a ratio between the obvious Volume of the catalyst bed and the volume of the gaseous reaction mixture can be defined, which are below the given Reaction conditions is passed to the catalyst bed in a unit of time.

The reaction pressure is initially determined by the feed of the gaseous Created reactants and diluents;

After the reaction has started, the pressure can preferably be used suitable back-pressure controllers which are on the side of the gaseous effluent of the catalyst bed are maintained.

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The reaction temperature is preferably established by puts the catalyst bed in a tubular converter, the walls of which are immersed in a suitable heat transfer medium, such as tetralin, molten salt mixtures or other suitable heat transfer medium, which are immersed to the desired reaction temperature be heated.

The process according to the invention can be carried out without added diluents with the exception of water for the selective oxydehydrogenation of ethane into ethylene and acetic acid are used to relate these end products deliver the following results:

End product ethane % effective. Productivity fo umwandl.

Ethylene (without added H ₂ O) * 2-7 60-85 4-7.5

Ethylene (with added H ₂ O) * 2-8 50-80 2-8.5

Acetic acid (without added H ₂ O) *

Acetic acid (with added water) *

2-7 15-25 1.5-4

2-8 15-45 2.5-5 * i.e. with or without water added to the ethane feed gas

The preferred catalysts for achieving the highest conversion and effectiveness with regard to ethylene and acetic acid are calcined preparations which _{contain the elements Mo, M, Nb. And Mn in the ratio Mo d} M _e Nb |> Mn} where M = V and / or W ;
d = 16

e = 1 to 16, preferably 1 to 8
f = 1 to 10, preferably 0.2 to 10
g = 0 to 32, preferably 0 to 5.

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The following examples illustrate the present invention, without restricting them.

The following examples show the production of various catalyst preparations and their use in the oxydehydrogenation of ethane in ethylene.

The activity of each test catalyst was determined either in a small U-shaped tubular reactor into which a pulsating flow of oxygen and ethane was introduced (test method A); or in a straight tube reactor into which ethane and oxygen were continuously introduced simultaneously (test method B); or in a backmix autoclave process (Test Method C). These test procedures were specifically as follows: Catalyst Test Procedure A

The catalysts were tested for their (oxy) dehydrogenation activity investigated by ethane in a pulsating microreactor system. The 50 cm reaction section containing the test catalyst Length and 8 mm diameter in the form of a silica U-tube was heated by immersion in a fluidized sand bath, its Temperature was controlled by a heating element. The heating elements for temperature control and measurement were swirled in the Submerged sand that extended at least 7.5 cm above the catalyst level in the U-tube. A previous investigation the temperature profile in the sand bath showed less than 3 ° change from head to bottom from that by the controller given fixed point.

The microreactor is attached to a gas chromatograph for analysis of the Product streams connected .. The helium carrier feed flowing through the microreactor was removed from the chromatograph by

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interrupted the helium supply line within the chromatograph at a point immediately after the flow control device, through a valve with 8 outlets and 2 positions ("8-port, 2-position value "; Union Carbide Corp., Special Instruments Division, Model C4-70) and from there through a manual operated sample injection valve with 6 outlets ("6 port manual sample injection valve"; Union Carbide model 2112-50-2) to the inlet arm of the U-tube reactor. The system was with an insertion opening provided, which had a rubber septum at the reactor inlet. The product gas from the reactor was passed through a cold trap, led back through the U-valve with 8 outlets, which the product flow to one of the two analysis systems of the chromatograph sent. Each valve was fitted with an adjustable bypass valve provided to compensate for the pressure drop in the chromatograph column in the analysis system.

The introduction of 2.0 ccm portions ("pulses) charge of 6.5 \ lol" -% oxygen, 8.0 \ lol .-% ethane and the rest of nitrogen took place through a gas-tight injection needle through the entrance immediately before The gas was diluted and passed over the catalyst (3.0 g) with the aid of the helium carrier gas, the carrier gas flowing through the reactor and the gas chromatograph for analysis at all times at 60 ccm / min.

The product mixture was analyzed on a stainless steel column filled with Poropak R with a diameter of 25 cm 3.2 mm. The column was starting at 3O ⁰ C, heated at 1O ⁰ C / min. Under these conditions the residence times were as follows / air 2.0 min / carbon dioxide 2.5 min; Ethylene 3.4 min; Ethane 4.0 min. The identity of the products was confirmed by chromatography

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BATH ORIGINAL

graph of known neat samples, with the severed tips being examined by mass spectrometry. "Poropak R" is a finely divided, spherical polystyrene resin crosslinked with divinylbenzene. Catalyst Test Procedure B

The catalysts were tested in a tubular reactor under the following conditions: Composition of the ethane gas charge: 9.0 \ lol _t -% C ₂ H ₆ , 6.0 vol .- ^ O ₂ and 85 vol .- ^ N ₂ ; Space velocity 340 hr j 1 at total reaction pressure. The catalyst efficiency was observed with increasing temperature. The reactor consisted of a 1.25 cm straight stainless steel tube, which was heated by a molten salt bath (using

HITEC ^ - 'heat transfer salt from DuPont) won about 30

3.2
cm depth. A 3.2 mm thermal element arm extended the full length of the center of the reactor tube and catalyst bed. The catalyst temperature profile was obtained by sliding the heating element through the arm. 26 cm of catalyst was introduced into the tube so that the top of the catalyst bed was 10 cm below the surface of the heat transfer salt. The catalyst bed was 12.5-13.75 cm long so it had a depth to cross section ratio of * M0. The zone above the catalyst bed was filled with glass beads in order to be used as a preheater. The gaseous effluent from the reactor was passed through a condenser and trap at 0 ° C. The gaseous and liquid products thus obtained were evaluated as described below.

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Catalyst Test Procedure C

In this high-pressure study, the reactor used was a bottom-agitated Magnedrive ^ir autoclave with a centrally mounted catalyst basket and a by-product outflow line. A fan operated magnetically at different speeds circulated the reaction mixture continuously over the catalyst bed. Such a reactor is shown in FIG. 1 of the study of Berty, Hambrick, Malone and Ullock with the title "Reactor for Vapor-Phase Catalytic Studies", reprinted 42E at the Symposium on Advances in High-Pressure Technology - Part II, Sixty-fourth National Meeting of the American Institute of Chemical Engineers ( AIChE) in New Orleans, Louis. On March 16-20, 1969, available from AIChE, 345 East 47th Street, New York, NY 10G17.

The backmix autoclave had a stainless steel catalyst canister above the blades of the fan; this thus blows the gas upwards and inwards in convection fashion through the catalyst bed. Two heat elements measure the temperatures of the incoming and outgoing gas. The oxygen was introduced into the reactor by a ratemeter at about 10.5 atm. Through a 0.63 cm line. The ethane-CO _x gaseous mixtures were introduced through a rotometer and then combined with the oxygen feed prior to introduction into the reactor. The liquids were pumped directly into the reactor through the same feed line as the gases, but the liquid inlet entered the line after the gases were mixed. The effluent gases were removed through an exit on the reactor side. Condensable liquid products were removed by a series of cold traps in two baths.

The first bath contained wet ice at ⁰ ° C. and had two in it

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submerged cold traps. The second bath of dry ice and ace-

ton at -78 ^ C. contained two cold traps. The non-condensable Components of the exit stream were measured at atmospheric pressure through a dry gas test meter to determine their total volume guided. A l / valve with 8 outlets allowed direct sampling of both product and feed gases through conduits that connect directly to the reactor feed and product streams were connected. No external recirculation was used.

The mass volume of the weighed catalyst sample was determined (approximately 150 ecm) and the sample was placed in the catalyst basket. The amount of catalyst introduced in each case was about 131.1 g. Stainless steel screens were placed above and below the catalyst bed to allow fluidization and circulation of the fine catalytic fiber particles to a minimum. To Introducing the catalyst basket into the reactor, this was sealed and the process lines were at ambient temperatures tested for a pressure about 7-14 atm above the expected maximum working pressure. Nitrogen became this test used.

After the reactor had Ieckfr8i shown ianer N ₉ was passed through the reactor and raising the temperature to 275-325 ⁰ C.. The composition of the gas feed was varied in the following ranges: 76-97 % C ₂ ^H 6 * ³ ~ ^{6 Vo1} · "^ ° 2>°" ¹⁰ % H ₂ O and 0-10 UoI . -% CO _x . After reaching the desired temperature, the oxygen and ethane-CO _x mixtures were adjusted to give the desired steady-state ratio at the desired total flow rate. The concentrations of the

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Components in the effluent gas were determined by the gas chromatographic analyzes described below. The reactor was allowed about 0.5-1 hour to reach steady-state conditions at the desired temperature. Then the traps of the liquid products were emptied, a dry gas test meter was read and the time was noted as the start of the experiment. In the course of the experiment, samples of the effluent gas were analyzed for C ₂ H ₆ , ^C 2 ^{H 4 >>} ° 2 ^CD * ^C0 2 unci other volatile hydrocarbons At the end of the experiment, the liquid product was collected and the volume of the effluent gas noted, and the liquid products were analyzed by mass spectroscopy.

The reactor inlet and outlet gases from all tests performed under Test Procedures B and C were tested for Q ^ i ^ o ^unc * ^ ^au ^ ^e; * - ^ner 25 cm χ -3.2 mm Κοίοηηθ from 5A molecular sieves (14/30 mesh) at 95 ⁰ C and on (O ₂ , N ₂ * CO together) CO ₂ , ethylene, ethane and H ₂ O on a 35 cm χ 3.2 mm column made of "Poropak Q" 80/100 mesh) at 95 ° C. analyzed. The liquid product (when obtained in sufficient quantity) was _{analyzed for H 2} O, acetaldehyde, acetic acid and other components by mass spectroscopy. "Poropak Q ¹¹ ^ is a finely divided, spherical polystyrene resin crosslinked with divinylbenzene.

In all cases the percent conversion and percent were based Selectivity on the following stoichiometry:

C ₂ H ₆ + 1/2 O ₂ VC ₂ H ₄ + H ₂ O

C ₂ H ₆ + 7/2 O ₂ > 2CO ₂ + 3H ₂ O

without applying individual response factors to the eluted peak areas of the chromatogram,

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The reaction conditions of the three test methods were as follows: Catalyst Temp ·; Contact space velocity. test method pressure; at C. time; see hr ~

A 3.3 200-650 - -

B 1 x 300-400 10.6 340

C 6-10 275-325 10.0 / 5.25 kg / cm * 2200

15.6 / 8.75 kg / cm

Example 1 to 23

Catalysts 1-22 prepared below were tested in the Catalyst Test Procedure A evaluated. The composition of each catalyst is given at the beginning of the relevant example, the test results are shown in Table 1. The catalyst of Example 23 was evaluated in Test Method B, the results of which are also shown in Table 1.

The catalysts of Examples 1-23 were tested first to determine the low temperature at which catalytic activity was first demonstrated; this is called the temperature of initial activity (To). Then the selectivity of the catalyst for the oxydehydrogenation of ethane in ethylene was determined at this To. Each active catalyst was then evaluated at higher temperatures in order to determine the lowest temperature above To at which a 10% conversion of ethane to ethylene could be achieved; this temperature is referred to in Table 1 as T. _Q. The selectivity of the catalyst for the oxydehydrogenation of ethane in ethylene at T _1n was also determined and listed in Table 1.

Example 1_

250 g molybdenum trioxide (purity 99.95 %) were mixed with 7.8 g carbon

iRι
wax 6M \ —4 mixed with a polyethylene oxide wax and made into tablets

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in "cylindrical shape of θ mm diameter 6.3 mm length and processed with an axial hole of 2.4 mm diameter. The tablets were roasted to form a non-separated catalyst for 3 hours at 750 ⁰ C..
Example 2

Mo. ^ Mn ,,, - or Mo.Mn “ 1 ο 16 ■ ι Ί

88.28 g of ammonium paramolybdate (0.5 g atoms of Mo) became 177.89 g a 50.3- ^ solution of manganese nitrate (0.5 g atoms Mn), in 500 ecm of water dissolved, added.

The mixture obtained was heated to 90 ° C. with stirring. heated, then 14 Joiger aqueous ammonia was added to a pH of 5. It! was dried by evaporation with stirring on a steam bath. Further drying took place for 16 hours at 110 ^° C.

The dried material was put into a. Silica shell converted and calcined in a .Muffelofen 2 hours at 52o ⁰ C. in an ambient air atmosphere. The amount of the undeposited catalyst obtained was 107 g.

Example 3 Mo ₁₆ Nb ₄ or Mo ₁ Nb _{0 25}

42.4 g of ammonium paramolybdate (0.24 g atoms of Mo) were in 200 ecm Water with stirring at 60-80 ° C. in an evaporation vessel stainless steel solved.

74 ecm niobium oxalate solution (183.9 g / l; 0.06 g-atoms Nb).

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The resulting mixture was heated with stirring, and there were 87 g (100 ecm) Norton silica-alumina SA 5205 as 6.3 mm beads added. It was then dried by evaporation with stirring on a steam bath and a further 16 hours at 120.degree.

The dried material was transferred to a tray made of 10 mesh stainless steel wire screen and ^{calcined in a muffle furnace for 5 hours at 400 °} C. in an ambient air atmosphere. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 31.5 %.

Example 4

or Mp

495 g ammonium paramolybdate (2.8 g atoms Mo). were in 1 1 water with stirring at 60-80 ° C. in a stainless steel evaporation dish Steel loosened.

408 g of titanium lactate solution ¹¹ TYZOR LA "(0.7 g atoms of Ti) were added to the solution obtained.

The resulting mixture was heated with stirring and there were 1040 g (1000 ecm) Norton silica-alumina SA5218 was added as 6.3 mm beads. Then by evaporation with stirring on a steam bath and a further 16 hours at 120 ° C. dry net.

The dried material was transferred to a tray made of 10 mesh stainless Stahdraht and calcined in a muffle furnace for 5 hours at 4OQ ⁰ C. in an ambient air atmosphere. The amount of catalyst deposited on the support, calculated from the increase in weight of the catalyst, was 21.2 %.

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Example 5

Mon ₁₆ V _{1 4} (-8 · phase) or HoyVO, 000

273.5 g molybdenum trioxide (1.9 g atoms Mo), 51.2 g (0.4 g atoms Mo) 94- ^c / Siges molybdenum dioxide and 18.2 g vanadium pentoxide (0.1 g atoms V) were ground together in a ball mill for 24 hours. The powder was sealed in a silica tube and kept at 700 ° C. for 90 hours. heated. After it had cooled down, the

dene product has a surface area of 2.36 m / g, one density of 4.01 g / cc and a porosity of 0.076 cc / g. According to X-ray

refraction it was the pure θ phase (V Ho _nq %

U, Ub υ, 7 Z) c ^ λ.

B e is ρ ie 1 6

Ηο ,, υ ,, or Mo ₁ V
16 4 1 _above 25th

82 g of ammonium metavanadate (0.7 g atoms of V) and 495 g of ammonium paramolybdate (2.8 g atoms of Mo) were dissolved in 2 l of water with stirring at 60-80 ° C. in a stainless steel evaporation bowl.

The received; The mixture was heated with stirring and there were 1040 g (100Occm) Norton silica-alumina SA 5218 was added as 6.3 mm beads. Then by evaporation with stirring on a steam bath and a further 16 hours at 120 ° C. dried.

The dried material was transferred to a tray made of 10 mesh stainless Stahldrat and in a muffle furnace for 5 hours at 400 C. in an ambient air atmosphere calcined The deposited on the support amount of catalyst, calculated from the weight increase dos catalyst was 26,45 ^l; i.

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BATH

Bei Piel 7

^MO 16 ^W 5.3 ^{0d8r Ho} 1 ^W 0.33

209 g of ammonium tungstate (0.8 g-atom W) and 424 g Ammoniumpara- ■ molybdate (2.4 g atoms Mo) were dissolved in 4 1 of water with stirring at 60-80 ⁰ C. in an evaporation vessel made of stainless steel.

142 g of ammonium oxalate (1.0 g molecule) were added to the solution obtained. and 28 g of nitric acid, dissolved in 100 ecm of water, were added.

The resulting mixture was heated with stirring and there were 1040 g (1000 ecm) of the above-mentioned Norton silica-alumina SA 5218 beads were added. Then it was taken by evaporation Stir on a steam bath and continue for 16 hours at 120 C. dried.

The dried material was transferred to a tray made of 1 mesh stainless steel wire and calcined in a muffle furnace for 8 hours at 350 ° C. in an ambient air atmosphere. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 21.6 %.

Example 8

Mo ₁₆ W ₄ Fe ₁ or Mo ₁ V _{ü> 25} Fe _{n> n625}

70 g ammonium metavanadate (0.6 g atoms V) and 424 g ammonium paramolybdate (2.4 g atoms of Mo) were dissolved in 2 l of water with stirring at 60-80 ° C. in an evaporation dish made of stainless steel.

60 g of ferric nitrate nonahydrate (0.15 g atoms of iron) dissolved in 100 ecm of water were added to the solution obtained.

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The resulting mixture was heated with stirring, then 1040 g (1000 ecm) of the above Norton silica-alumina SA 5218 beads were added. Ururde then dried by evaporation with stirring on a steam bath and further for 16 hours at 12O ⁰ C..

The dried material was transferred to a tray made of 1 mesh stainless steel wire and dried in a muffle furnace at 400 ^° C. in an ambient air atmosphere for 5 hours. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 27.5 %. Example 9 Ho ₁ ^ V ₄ Mn ₄ . or Ho ₁ V ^ ₂₅ Mn ₀₁₂₅

35 g of ammonium metavanadate (0.3 g atoms V) and 212 g of ammonium paramolybdate (1.2 g atoms Mo) were dissolved in 1 1 water with stirring at 60-80 ⁰ C. in an evaporating dish made of stainless steel.

75 g of manganoacetate tetrahydrate (0.3 g atoms Mn), dissolved in 100 ecm of water, added.

The resulting mixture was heated with stirring. Then was through Evaporation with stirring on a steam bath and further 40

ο *

Dried for hours at 120 C.

The dried material was transferred to a silica shell and ^{calcined in a muffle furnace for 5 hours at 400 °} C. in a surrounding air atmosphere. The shortage of not; deposited catalyst was 222 g. Example . 10 Mo ₁₆ V ₄ Nb ₂ or Mo ₁ V ₀₁₂₅ Nb ₀

709814/1113

82 g of ammonium metavanadate (θ, 7 g atoms ) and 494 g of ammonium paramolybdate (2.8 g atoms of Mo) were dissolved in 2 liters of water with stirring at 60-80 ° C. in a stainless steel evaporation vessel.

550 g of niobium calcium hydroxide (0.35 g atoms Nb) and 28 g of ammonium nitrate, dissolved in 100 ecm of water, are added.

The resulting mixture was heated with stirring, then 1040 g (1000 ecm) of the above Norton silica-alumina SA 5218 beads were added. Further 16 hours at 120 ⁰ C. This was followed by evaporation with stirring on a steam bath and dried.

The dried material was transferred to a tray made of 10 mesh stainless steel wire and ^{calcined in a muffle furnace for 5 hours at 400 °} C. in an ambient air atmosphere. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 27.7 %.

The niobium oxalate sol with an equivalent of 95.3 g / l Nb ₂ O, - is a product of Kawecki Berylco Industries.

Example 11_

Mo ₁₆ W ₂ Nb ₄ or «o ^ ₁₂₅ Nb _Qj25

7.8 g of ammonium paratungstate (0.03 g-atom W) and 42.4 g of ammonium paramolybdate (0.24 g atoms Mo) were dissolved in 400 cc of water with stirring at 60-80 ⁰ C. in an l / erdampfungsschale stainless Steel loosened.

74 ecm of a niobium oxalate solution containing 183.9 g / l (0.06 g atoms of Nb) were added to the solution obtained.

709814/1113

The resulting mixture was heated with stirring, then 87 g (100 ecm) Morton silica-alumina DA5205 6 ½ mm beads were added. Further 16 hours at 12O ⁰ C. This was followed by evaporation under stirring on a Wassexdampfbad and dried.

The dried material was transferred to a tray made of 10 mesh stainless steel wire and calcined in a muffle furnace for 5 hours at 400 ⁰ C. in an ambient Luftsfcmosphäre. The amount of catalyst deposited on the carrier was 55.2 %, calculated from the increase in the weight of the catalyst. Example 12

^M0 16 ^W 3.3 ^Pd 1.9 ^{or Mo} 1 ^W 0.2 ^Pb 0.12

177 g Ammoniumparaujolframat (0.679 g-atoms' M) and 396 g of ammonium paramolybdate (2.087 g atoms Mo) were dissolved in 2 1 of water under stirring at 6-8O ⁰ C. in a stainless steel Uerdampfungsschale dissolved.

83 g of lead nitrate (0.252 g atoms of Pb) and 20 ecm of nitric acid, dissolved in 450 ecm of water, were added to the solution obtained.

The resulting mixture was heated with stirring, then 770 g (1000 ecm) of the above-mentioned Norton silica-alumina 5A5205 beads were added. Further 16 hours at 12O ⁰ C. This was followed by evaporation with stirring on a steam bath and dried.

The dried material was transferred to a tray made of 10 mesh stainless Stahdraht and calcined in a muffle furnace for 5 hours at 400 ⁰ C. in an ambient air atmosphere. The amount of catalyst deposited on the support, calculated from the weight

709814/1113

increase in catalyst was 37.2 %. Example 13

^M ° 16 ^Nb 4 ^W 1.6 ^Mn 4 ^{or Mo} 1 ^Nb 0.25 ^W 0.1 ^Mn 0.25

3348 g of niobium oxalate solution with 319.1 g of Nb ₃ O ₅ (2.4 g atoms of Nb) and 1696 g of ammonium paramolybdate (9.6 g atoms of Mo) were in 4 liters of water with stirring at 6 0-80 ° C. in a Dissolved stainless steel evaporation bowl.

240 g of ammonium paratungstate (0.92 g atoms of tungsten) and 880 g of a 50.3% manganese nitrate solution (2.46 g atoms of manganese), dissolved in 4000 ecm of water, added.

The resulting mixture was heated with stirring and .to a

Paste evaporated, this transferred to an oven and dried overnight in a circulating air stream at 80-90 ⁰ C. and then for 64 hours at 12O ⁰ C..

The dried material was transferred to a tray made of 10 mesh stainless steel wire and calcined for 5 hours at 36O ⁰ C. in an ambient nitrogen atmosphere in a muffle furnace. The amount of the catalyst not deposited was 2027 g, the catalyst was crushed to 25 mesh. Example 1_4

M η \ / Mh Mn πΗορ Mn U (Vi I— · Mn

MO ₁₆ U ₄ IMD ₁ Hn ₁ ooer ^llo ₁ Vo _j 2 ₅ ^ND 0.0625 " ⁿ O, 0625

210 g of ammonium metavanadate (1.8 g atoms V) and 1,272 g of ammonium paramolybdate (7.2 g atoms Mo) were dissolved in 5.5 1 of water while stirring .for 60-80 ⁰ C. in an evaporating dish made of stainless steel.

7098H / 1113

416 g of niobium oxalate sol (0.45 g-atoms Nb) and 160 g of manganese nitrate (50.3% solution; 0.45 g atoms of Mn), dissolved in 150 ecm of water, were added.

The resulting mixture was heated with stirring and 3120 g (3000 ecm) of the above Norton silica-alumina SA5218 beads were added. Anschießend further 16 hours at 12O ⁰ C. was by evaporation under stirring on a steam bath and dried.

The dried material was transferred to a tray made of 10 mesh stainless steel wire and ^{calcined in a muffle furnace for 5 hours at 400 °} C. in an ambient air atmosphere. The amount of catalyst deposited on the support, calculated from the increase in weight of the catalyst, was 27.8 %.

Example 1_5

. or ^^^

70 g ammonium metavanadate (0.6 g atoms V) and 424 g ammonium paramolybdate (2.4 g-atom 8 Mo) were dissolved in 2 l of water with stirring at 60-80 C in a stainless steel beaker.

66 g of tantalum oxalate solution (0.3 g atoms of Ta) and 60 g of ferric nitrate Fe (NOj) ₃ ^ H ₂ O (0.15 g atoms of Fe), dissolved in 100 ecm of water, were added to the solution obtained.

The resulting mixture was heated with stirring and about 60 % of the water was evaporated.

The resulting concentrated slurry was transferred to a stainless steel evaporating dish and 1040 g (1000

mentioned
ecm) the / Norton silica-alumina SA5218 beads were added.

7098U / 1113

Further 16 hours at 12O ⁰ C. This was followed by evaporation with stirring on a steam bath and dried.

The dried material was transferred to a 10 mesh stainless steel wire tray and placed in a muffle furnace at 400 ° C for 5 hours. calcined in a surrounding air atmosphere. The amount of catalyst deposited on the support, calculated from the increase in weight of the catalyst, was 19.2% by weight .

Example 1_6

Mo ₁₆ W ₄ Ta ₂ Mn ₁ or ^ ₁ ^ Ta ^^ n

280 g of ammonium metavanadate (2.4 g atoms V) and 1,696 g of ammonium paramolybdate (9.6 g atoms Mo) were dissolved in 7.5 1 of water with stirring at 60-80 ⁰ C. in an evaporating dish made of stainless steel solved.

1584 g of tantalum oxalate sol (1.2 g atoms Ta) and 216 g of a 50.3% manganese nitrate solution (0.6 g-atoms Mn), dissolved in 200 ecm of water, was added.

The resulting mixture was heated with stirring and there were

of said 4160 g (4000 cc) Norton silica-alumina SA5218 beads

added. Then, by evaporation under stirring on a steam bath and further for 16 hours at 12O ⁰ C..

The dried material was transferred to a tray of 10 mesh residue-free steel wire and calcined in a muffle furnace for 5 hours at 400 ⁰ C. in an ambient air atmosphere. The amount of catalyst deposited on the support, calculated from the. The increase in the weight of the catalyst was 19.2 %.

The tantalum oxalate sol containing the equivalent of 218.6 g / l Ta ₂ O ₅ is a product of Kawecki Berylo Industries.

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Example T7

Mo ₁₆ W ₄ Ti ₂ Mn ₁ or Μα ,, Ι / ^ ₂₅ Ti _{Q} 1} 35Mn ₀ ^ ₆₂₅

70 g of ammonium metavanadate (0.6 g atoms \ l) and 424 g of ammonium paramolybdate (2.4 g Atorne-Mo) were dissolved in 2 1 of water with stirring at 60-80 ⁰ C. in a stainless steel beaker.

175 g of titanium ammonium lactate (chelate) solution were added to the solution obtained (with 0.3 g atoms of Ti) and 54 g of 50.3% manganese nitrate solution (0.15 g atoms Mn), dissolved in 100 ecm of water, added.

The resulting mixture was heated with stirring and about 60 % of the water was evaporated.

The concentrated slurry obtained was turned into a stainless steel Transferred evaporation dish, then 1040 g (IOOO ecm)

of the mentioned
/ Morton silica-alumina SA5218 beads added. Further 16 hours at 12O ⁰ C. This was followed by evaporation with stirring on a steam bath and dried.

The dried material was transferred to a Tablött of 10 mesh stainless steel wire and calcined in a muffle furnace for 5 hours at 400 ⁰ C. in an ambient air atmosphere. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 27.8 gem .- ^. Example 1J3

^Mo 16 ^V 4 ^W 1.6 ^Mn 4 ^{or Mo} 1 ^U 0.25 ^W 0.1 ^Mn 0.25

350 g of ammonium metavanadate (3 g atoms V) and 2120 g Ammoniumpara-, molybdate (12 g atoms Mo) were dissolved in 10 1 of water with stirring at 60-80 ⁰ C. in a stainless steel evaporating dish.

7098H / 1113

313 g of ammonium paraffin (1.13 g atoms W) and 750 g manganoacetate tetrahydrate (3.06 g atoms Mn), dissolved in 6000 ecm of water, added.

The resulting mixture was heated with stirring and dried by evaporation with stirring on a water bath. Further drying was carried out for 24 hours at 12O ⁰ C.

The dried material and / urde on a tray made of 10 mesh stainless steel wire converted and calcined in a muffle furnace for 5 hours at 400 ⁰ C. in an ambient air atmosphere. The amount of the undeposited catalyst thus obtained was 1453 g. 2720 g of dried material were obtained after the drying stage at 120.degree. 1636 g. Of this dried material were used in the calcination stage at 400 C. and yielded 1453 g of calcined catalyst.
Example 1 £

^Mo i6 ^Bi 1.3 ^Ti 1.3 ^Mn 2.6 ^Si 2.6 ° ^{der M} ° 1 ^Bi 0.08 ^Ti 0.08 ^Mn 0.16 ^Si 0.16 457 g ammonium paramolybdate (2.6 g-atoms Mo ) were in 0.7 l of water with stirring at 60-80 ° C. dissolved in a stainless steel evaporation dish.

To the solution obtained, 249 g titanium lactate solution ¹¹ TYZOR LA "(0.21 g atoms Ti) and 104 g bismuth nitrate pentahydrate (0.21 g atoms Bi) were dissolved in 110 ecm water, the 25 ecm concentrated nitric acid and 153 g a 50.3% manganese nitrate solution (0.43 g atoms Mn) and then 86 g of colloidal silica ^{solution 11} LUDOX LS "were added.

7098U / 1113

264A107

The resulting mixture was heated with stirring and 770 g (1000 ecm) Norton silica-alumina SA5205 beads (6.3 mm) were added. Then, by evaporation under stirring on a steam bath and u / pus for 16 hours at 12O ⁰ C..

The dried material was transferred to a 10 mesh stainless steel wire tray and placed in a muffle furnace at 400 ° C for 5 hours. calcined in a surrounding air atmosphere. The amount of catalyst deposited on the support, calculated from the increase in the weight of the catalyst, was 32.5 %.

¹¹ TYZOR LA ¹¹ ^ iSt a colloidal titanium lactate sol from E. I.

DuPont, and LUDOX LS ^ is a colloidal silica solution from the same company, j Example 20

^Ho 16V ^a 1.33 ^Fe 0.67 ^Si 1.33 ^{or Mo} 1 ^V Q, 25 ^Ta 0, 0B3 ^Fe ö, 042 ^Si 0.083 35.1 g ammonium metavanadate (0.3 g atoms M) and 212 g ammonium paramolybdate ( 1.2 g atoms of Mo) were dissolved in 1.1 l of water with stirring at 60-80 ° C. in a stainless steel evaporation dish.

126 g of titanium oxalate sol (containing the Equivalent of 228 g Ta ₂ O ₅ / l; 0.1 g atoms Ta) and 20.2 g ferric

nitrate nonahydrate (0.05 g atoms Fs) and 20 g LUDOX AS-30 (0.1 g atom Si), dissolved in 197 ecm of water, were added.

_% The mixture obtained was heated with stirring, and 770 g (970 ecm) of Norton silica-alumina SA 5205 spheres (· 6,3πκη) were added. Then, by evaporation under stirring on a Waseerdam'pfbad and further 16 hours at 12O ⁰ C..

7098U / 1113

verified]

The dried material was transferred to a tray made of 10 mesh stainless steel wire and calcined in a Muffölofen 5 hours at 40G ⁰ C. in an ambient air atmosphere. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 22.5 pounds. Example 21_

" ⁰ IoVS, 3 ^ND 0.67 ^Mn 1 ^{Or Mo} 1 ^l O, 25 ^Ti 0.08 ^rjb 0.042 ^Mn 0.0625 210 g ammonium metavanadate (1.8 g atoms V) and 1272 g ammonium paramolybdate (7.2 g Atoms Ho) were dissolved in 5.5 l of water with stirring at 60-80 ° C. in a stainless steel evaporation dish.

351 g of titanium ammonium lactate, "TYZuR LA" were added to the solution obtained. (0.6 g-atoms Ti) and 216 g niobium oxalate sol (0.3 g-atoms. \ 'B) and

/ ((λ, 45 g-atoms Hn) 160 g of a 50.3% solution of manganese nitrate in 2Ό0 ecm of water

dissolved, added.

The resulting mixture was heated with stirring and there were

, (6.3 rom)

3120 g (3000 ecm) Norton silica-alumina SA5218 beads / added. Then, by evaporation with stirring on a steam bath and further 16 hours at 120 ° C. dried.

The dried material was transferred to a tray made of 10 mesh stainless steel wire and calcined in a muffle furnace for 5 hours at 400 ° C. in a surrounding air atmosphere. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 37.8 %. Example 22,

^Ho 16 ^Di 1.3 ^Fe 1 _t 3 ^Tl 0.5 ^Ni 7 _f 3 ^Co 1.3 ^Ha 1, i ^Mn 2.1 ^P 0.13 ^Si 19.6 ^{or Mo} 1 ^Bi O _l OO ^Fe O, C8 ^Tl ü, ü3 ^fJi ü _f 456 ⁰⁰ O ₁ UO ^ U ₁ UoNXmPc ₁ OUa ⁵ M, 23

708814/1113

0.29 g of 85- ^ strength phosphoric acid (0.0025 g-atoms of P) and 53 g of ammonium paramolybdate (0.3 g atoms Mo) were dissolved in 0 _# 3 1 of water with stirring at 60-8O ⁰ C. in a Prozellanverdampfungsschale solved. Then 67 ecm of a silica brine LUDOX AS ^ and 50 ecm of conc. Ammonium hydroxide added.

10.1 g of ferric nitrate nonahydrate (0.025 g atoms Fe), 39.99 g nickel nitrate hexahydrate (0.1375 g atoms Ni), 6.41 g magnesium nitrate hexahydrate (0.025 g atoms Mg), 7.25 g cobalt nitrate hexahydrate (0.025 g-atoms Co), 14.27 g of a 50.3- ^ igen Manganese nitrate solution (0.025 g atoms Mn), 4.0 g thallium nitrate trihydrate (0.015 g-atoms Tl), dissolved in 250 ecm of water, added.

The mixture obtained was heated with stirring, and 12.13 g of bismuth nitrate (0.025 g atoms of Bi) dissolved in 30 ecm of water and 4 ecm of conc. Nitric acid added. Then, by evaporation under stirring on a steam bath and further for 16 hours at 12O ⁰ C..

The dried material was transferred to a silica shell and ^{calcined in a muffle furnace for 6 hours at 525 °} C. in a surrounding air atmosphere. The amount of catalyst not deposited was 90 g.

Example 23

Mo ₁₆ V ₄ Nb ₂ Cu ₁ or Mo ₁ V ₀ , ₂ 5 ^Nb 0 _f 125 ^Cu 0.0625

42 g of ammonium metavanadate (0.36 g atoms V) and 254 g of ammonium paramolybdate (1.44 g atoms Mo) were dissolved in 1.2 1 of water with stirring at 60-80 ⁰ C. ■ in a stainless steel evaporating dish solved.

709814/1113

158 g of niobium oxalate (0.18 g-Atame Nb) and 22 g of cupric nitrate (0.09 g atoms of Cu), dissolved in 60 ecm of water, added.

The resulting mixture was heated with stirring and 1040 g (1000 ecm) Norton silica-alumina SA5218 beads (6.3 mm) were added. Then uiurde by evaporation under stirring on a Jniasserdampbad and further 16 hours at 12O ⁰ C. dried.

The dried material and / urde on a tray on 10 mesh stainless steel wire converted and calcined in a muffle furnace for 5 hours at 400 ⁰ C. in an ambient air atmosphere. The amount of the catalyst deposited on the carrier was calculated from

the weight increase of the catalyst, 15.9 %,

The catalyst obtained in Example 23 was evaluated according to test method B; the results are shown in Table 1. Example 24 to 28

The catalysts of Examples 24-28 are not according to the invention catalysts j they were prepared as follows and according to catalyst test procedures A tested. They showed little or no selectivity for converting ethane into ethylene. The catalysts of Example 24-26 contained excess amounts of Fe and / or Co, i.e. - ^ 8 g-atoms Fe and / or Co per 16 g-atoms Mo, and the catalysts of Examples 27-28 did not contain any Mo.

Example 24_

Mon ₁₆ Co ₁₄ Mn ₂ or Μ ° ι ^ ο _η , ₈₇₅ Μη _{η> 125}

1556 g of ammonium paramolybdate (8.82 g atoms Mo) were dissolved in 4.16 1 of water with stirring at 60-80 ⁰ C. in a stainless steel evaporating dish.

7098 14/1113

178.4 g of manganese sulfate (1.06 g-atoms Mn) and 2328 g of cobalton nitrate (8 g atoms of Co), dissolved in 1760 ecm of water, were added.

The resulting mixture was heated with stirring, and 633 g of titanium hydrate mass was added. The slurry was neutralized with 667 g of aqueous ammonia dissolved in 1243 ecm of water. Then, by evaporation under stirring on a steam bath and further for 16 hours at 12O ⁰ C..

The dried material was transferred to an evaporating dish and ealciniert in a muffle furnace for 8 hours at 400 ⁰ C. in an ambient air atmosphere. The catalyst was pelletized and roasted for 12 hours at 55O ⁰ C.. The test results for this material according to Procedure A showed no selectivity for ethylene, but sine complete, starting at 21O ⁰ C. combustion.
Example 25

^Ho i6 ^Fe 1 _f 6 ^Co 6.4 ^W 3.2 ^Bi 1y6 ^Si 2 _f 16 ^K 0 _f 1 or ^Mo 1 ^Fe 0.1 ^Cr 0 _r 4 ^W 0.2 ^Bi 0.1 ^Si 0.135 ^K 0.006

648 g Ammoniumparatuolframat (2.483 g-atom W) and 2124 g of ammonium paramolybdate (12, Q3 g atoms Mo) were dissolved in 3 1 water under Rüh bsi ren 60-80 ⁰ C. in a? stainless steel evaporation tray solved,

1400 g of cobalt nitrate hexahydrate (4.81 g atoms of Co), 486 g of ferric nitrate nonahydrate (1.203 g atoms of Fe) and 584 g of bismuth nitrate pentahydrate (1.204 g atoms of Bi) and 300 ecm of a 1.55% potassium hydroxide solution ( 0.072 g-atoms K), dissolved in 1400 ecm of water, added.

709814/1113

The resulting mixture was heated with stirring, and 320 g of LUDOX, a 30.5-yd colloidal silica sol, were added. Then, by evaporation under stirring on a steam bath and further for 16 hours at 12O ⁰ C..

The dried material was transferred to a tray made of 10 mesh stainless steel wire and ^{calcined in a muffle furnace for 5 hours at 400 °} C. in an ambient air atmosphere. The catalyst was mixed with 10% of its weight of naphthalene and tabletted to form 8 × 8 mm cylinders. The tablets were roasted for 6 hours at 45O ⁰ C.. The results according to the test procedure A for this material show no selectivity for ethylene at the oxidation of ethane at 366 ⁰ C. Example 26
Mo ₁₆ Fe ₈ or Mo ₁ Fe _{0 5}

35.3 g of ammonium paramolybdate (0.2 g atoms Mo) were dissolved in 200 cc of water with stirring at 60-80 ⁰ C. in a stainless steel evaporating dish. 35 g of ferric nitrate hexahydrate (0.1 g atoms Fa), dissolved in 200 ecm of water, are added to the solution obtained.

The resulting mixture was heated with stirring and then filtered. Then, 16 hours at 12O ⁰ C. was dried.

The dried material was transferred to a silica shell, and vice in a muffle furnace for 4 hours at 400 ⁰ C, in a

* bound atmosphere of pure oxygen calcined. The received The amount of catalyst was 34 g. The results according to test method A

sigen for this material has a beginning at 276 ⁰ C. reaction, but no selectivity for the Äthylanherstallung.

709814/1113

I have passed]

example 2Ί_

8.7 g vanadium pentoxide (0.096 g atoms V) were concentrated in 350 ecm.

/ HCl- ■ ^for -

16N-Sa ¹ Ure and 200 ecm ethanol with stirring at 55 C. in einor

Glass evaporation dish dissolved.

114.4 g of antimony pentachloride (0.383 g atoms of Sb), in 80 ecm of conc. HcI dissolved, and 13.847 g cerium nitrate hexahydrate (0.032 g atoms Ce), dissolved in 100 ecm ethanol, supplied.

The mixture obtained was concentrated with 440 ecm. Ammonium hydroxide, dissolved in 700 ecm of water, neutralized. The precipitate was filtered off and washed on the filter with 1000 ecm of water and then dried at 120 ° C. for 16 hours. <

The gotrocknete material was applied to a tray of 10 mesh stainless steel - '^ raht converted and calcined in a muffle furnace for 12 hours at 75O ⁰ C. in an air atmosphere. The Testargebnisse this material for ancestors A gave a burning of ethane at 262 ⁰ C., but no selectivity for the formation of ethylene.
Example 28_

28 g of ammonium metavanadate (0.2404 g-Atotiie V) were dissolved in 700 cc of water with stirring at 60-8O ⁰ C. in a stainless Gtahlverdaropfungsschalo.

583 g of wioiriutnitotpontahydrate (1.202 g-Atomo Ui) and 180 g of antimony trioxide (1.202 g-Atonio 5b) as well as

7098U / 1 1 13

BATH ORIGINAL

219 g (172 ecm) niobium oxalate sol (0.2404 g-atoms Nb), in 720 ecm 3N nitric acid dissolved, added.

The resulting mixture was heated with stirring and 770 g (1000 ecm) Norton silica-alumina SA 5205 beads were added. Then, by evaporation under stirring on a steam bath and further for 16 hours at 12O ⁰ C..

The dried material was transferred to a tray made of 10 mesh stainless steel wire and ^{calcined in a muffle furnace for 5 hours at 400 °} C. in an ambient air atmosphere. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 36.1 %.

In the test according to method A, this catalyst showed an initial effectiveness at 525 ^° C. However, the percentage selectivity of ethane in ethylene was only 26 % at this temperature.

■ 709814/11 13

Table 1 Results of the Catalyst Tests - Method A (or B *)

t • 70981 ι
Ex. Catalyst- ^
composition Mon Temp.d.
At first
active it.
⁰ C, (Tp) Selectively,
for C ₂ H ₄ ;
% bsi To Temp.f 10 %
Umiüandl of
C ₂ H ₆ ; ⁰ C (T ₁₀ ) Selectively.
J "CH;
% at T ₁₀ 4/1 1 Mon ₁₆ Mn ₁₆
Mo ₁₆ Nb ₄ 418 A.
100 500 88 Il ·; 2
3 Mo ₁₆ Ti ₄ 320
516 100
100 550-600
634 35
74 4th 390 100 600 65 5 Mon ₁₆ V ₄ 444 About 100 562 59 ^ 6th Mon ₁₆ W ₅ March 500 100 540 100 ' 7th Mo ₁₆ V ₄ Fe ₁ 388 100 650 78
ι 8th Mon ₁₆ V ₄ Mn ₄ . 370 100 435 ⁸⁷ X 9 Mo ₁₆ V ₄ Nb ₂ 502 100 505 100 N> 10 215 100 286 100 pounds

Table 1 continued

11 12 13 14 15 16 * 17th 18th 19th 20th 21 * 22nd

23 *

Mon ₁₆ W ₂ Nb ₄

_{# 6} Mn ₄

MOi ₆ V ₄ Ta ₂ Fe ₁ MOi ₆ V ₄ Ta ₂ Mn ₁

Mo ₁₆ V ₄ W ^ ₆ Mn ₄

About 400 > 80 474 approx 100 328 100 243 100 310 85 309 100 215 100 - <255 100 460 100 . 220 84 260 100 422

Mo ₁₆ V ₄ Nb ₂ Cu ₁ 260

95

524 588 400 300 418 385 295 295 505 289 400 ^ 600

330

67

72

10 100

97

63 100

100

ioo £ 0

88 80

78

- rf -Vi ^26U107

Examples 29 to 46

Catalysts 29 through 46 were prepared according to the following procedures

produced and evaluated in catalyst test method B. Everyone

Catalyst from Examples 29-31 contained the elements Mo and V, and

the catalysts of Examples 32-46 contained the elements Mo

-Element

and V and an X ocfer Y /. The composition of each catalyst is given at the beginning of the corresponding example, the test results can be found in Table 2.

Catalysts 29-46 were one or two different "Hot-spot" temperatures between 300 and 400 C. for determination the percentage conversion and effectiveness at each temperature for the oxydehydrogenation of ethane to ethylene evaluated.

Example 29 Mo ₁₆ U ₄ or Mo ₁ W ^ ₂₅

40.9 g of ammonium metavanadate (0.35 g atoms V) were dissolved in 1 1 of water under -Rühren at 85-95 ⁰ C. in a vessel equipped with steam jacket evaporation vessel of stainless steel.

"40.9 g of oxalic acid (0.454 mol) in 400 ecm of water and 247 g of ammonium paramolybdate (1.4 g atoms of Mo), dissolved in 600 ecm of water, were added.

The obtained mixture was heated with stirring and dried by evaporation with stirring. Further drying er.folgte 16 hours at 12O ⁰ C.

The dried material was crushed to 4-8 mesh, transferred to a tray made of 10 mesh stainless steel wire and ^{calcined in a muffle furnace for 4 hours at 400 °} C. in an ambient air atmosphere. No carrier was added to the pure catalyst.

7 09814/1113

Example! 30th

^Mo 16 ^V 6.7 ^{or Mo} 1 ^V 0.42

57 g of ammonium metavanadate (0.487 g-atoms V) were dissolved in 1.5 1 water (9O ⁰ C.), then 66 g of glycerol and 216 g of ammonium paramolybdate (1.22 g atoms Mo), dissolved in 220 cc of water, added under stirring at 60-80 ⁰ C. in an evaporating dish made of stainless steel.

The resulting mixture was heated with stirring, and 1000 g (1000 ecm) of Norton silica-alumina No. 5218 pellets (6.3 mm) were added. Then was removed by evaporation with stirring on a steam bath and further for 16 hours at 12O ⁰ C..

The dried material was transferred to a tray made of 10 mesh stainless steel wire and ^{calcined in a muffle furnace for 4 hours at 400 °} C. in an ambient air atmosphere. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 18.5 %.

Example 31_

Mo ₁₆ V ₈ or Ho ₁ V ^ ₅

16 g of ammonium metavanadate (0.136 g-atoms V) and 48.1 g of ammonium paramolybdate (0.272 g atoms Mo) were dissolved in 0.5 1 of water with stirring at 85-95 ⁰ C. in a vessel equipped with steam jacket evaporation stainless steel vessel dissolved.

4.8 g of ammonium oxalate / (NH ₄ I ₂ C ₂ O ^. H ₂ Q7 (0.034 mol) in 50 ecm of water were added to the solution obtained.

The resulting mixture was heated with stirring and 140 g of Norton 4x8 mesh No. 5218 silica-alumina (irregular Shape) added. This was followed by evaporation

7098U / 1 1 13

dried with stirring and a further 16 hours at 120.degree.

The dried material was transferred to a tray made of 10 mesh stainless steel wire and ^{calcined in a muffle furnace for 4 hours at 400 °} C. in an ambient air atmosphere. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 22 %.

Example 32_

Mo ₁₆ U ₈ Fe ₁ or Mo ₁ ^^ Fe

15.9 g of ammonium metavanadate (0.136 g atoms of M) and 48.1 g of ammonium paramolybdate (0.272 g of atoms of Mo) were dissolved in 0.3 l of water with stirring at 85-95 ° C. dissolved in a stainless steel evaporation dish provided with a steam jacket.

4.8 g of ferric sulfate (Fe ₂ ZsO ^ ₅ ' ⁹ H ₂ O) (0.017 g atoms of Fe) in 400 ecm of water were added to the solution obtained.

The resulting mixture was heated with stirring and 130 g of Norton silica-alumina No. 5218 of 4x8 mesh (irregular shape) was added. It was then dried by evaporation with stirring and a further 16 hours at 120 ^{° C.}

The dried material was transferred to a tray made of 10 mesh stainless steel wire and calcined for 4 hours at · 4OQ ⁰ C. in an ambient air atmosphere in a muffle furnace. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 27.4 %. The test results for this material are shown in Table 2. Example - 33

^Mo 16 ^y 2 ^Nb 2 ^{or Mo} 1 ^V 0 _f 125 ^Nb 0.125 /

7098U / 11 13

16 g of ammonium metavanadate (0.136 g-atoms V) and 192.4 g Ammoniurnparamolybdat (1.09 g atoms Mo) were dissolved in 0.8 1 of water with stirring at 85-95 ⁰ C. indicates, in a steam-jacketed V / erdampfungsschale from stainless steel solved.

To the resulting solution 124 g Niobiumoxalatlösung ujurden (14.6% Nb ₂ O ^) in 100 cc water (0.136 g-atom of Nb) was added "

The obtained mixture was heated with stirring and dried by evaporation with stirring. Further drying took place at room temperature under total vacuum for 3 days.

The dried material was crushed to 4-8 mesh and transferred to a 10 mesh stainless steel wire tray and placed in a muffle furnace at 400 ° C for 4 hours. calcined in a surrounding air atmosphere. No carrier was added to the pure catalyst.

Example 34_ Ho ₁₆ V ₄ Nb ₂ or Mo ^^ Nb

40.9 g of ammonium metavanadate (0.350 g-atoms V) were dissolved in 1.0 1 stainless steel water with stirring at 85-95 ⁰ C. indicates, in a steam-jacketed evaporating dish ·

159.2 g of niobium oxalate solution (14.6 % Nb ₂ O ₅ ), diluted with 100 ecm of water (0.175 g atoms of Nb), and 247 g of ammonium paramolybdate (1.399 g atoms of Mo), dissolved in 800 ecm of water were added to the solution obtained , added.

The obtained mixture was heated and dried by evaporation with stirring. Further drying was carried out for 16 hours at 12O ⁰ C.

.709814 / 1113.

The dried material was crushed to 4x8 mesh and transferred to a tray made of 10 mesh stainless steel wire and ^{calcined in a muffle furnace for 4 hours at 400 °} C. in an ambient air atmosphere. No carrier was added to the pure catalyst.
Example 3J?

"° 16 ^V 4.6 ^Nb 0.6 ^{Or Mc} Vo, 288 ^Nb O, u375

81.8 g ammonium metavanadate (0.7 g atoms W) and 494 g ammonium paramolybdate (2.8 g atoms Mo) were in 1.5 1 water with stirring at 85-95 ° C. in a steaming bowl with a steam jacket solved from stainless steel.

318.4 g of niobium oxalate solution (14.6 %

I -

Nb ₂ Oc) in 200 ecm of water (0.35 g atoms of Nb) 'was added. The resulting slurry was filtered and the filtrate was allowed to stand at room temperature for 3 days. More crystals formed and were filtered off. The final filtrate was evaporated to dryness with stirring in a stainless steel evaporator. Further drying was carried out for 16 hours at 12O ⁰ C.

The dried material was on. 4 χ .8 mesh crushed and transferred to a tray made of 10 mesh stainless steel wire and ^{calcined in a muffle furnace for 4 hours at 400 °} C. in a surrounding air atmosphere. No carrier was added to the pure catalyst. The analysis showed the above composition.

Example. 36

Mon ₁₆ U ₆ Nb ₂ or Mon ₁ %

7098 TA / 1113

61.4 Q of ammonium metavanadate (0.525 g-atoms V) were added in 1.0 1 Water with stirring at 85-95 C. in a steam jacket v / seen stainless steel evaporation tray detached.

275 g of niobium oxalate solution (8.45 % Nb ₂ O ₅ ) (0.175 g atoms of Nb) and 247 g of ammonium paramolybdate (1.399 g atoms of Mo), dissolved in 800 ecm of water, were added to the solution obtained.

The resulting mixture was heated and dried by evaporation with stirring. Further drying was carried out for 16 hours at 12O ⁰ C.

The dried material was crushed to 4x8 mesh and transferred to a tray made of 10 mesh stainless steel wire and ^{calcined in a muffle furnace for 4 hours at 400 °} C. in an ambient air atmosphere. No carrier was added to the pure catalyst.
Example 37

^Ho 16 ^V 8 ^Nb 0 _f 5 ^{or Mo} 1 ^U 0.5 ^Nb 0.031

16 g ammonium metavanadate (0.136 g atoms V) and 48.1 g ammonium paramolybdate (0.272 g-atoms Mo) were in 0.5 l of water with stirring at 85-95 ° C. in a steam jacket Detached stainless steel evaporation tray.

7.75 g of niobium oxalate solution (14.6 % Nb ₂ O ₅ ) * (0.0085 g atoms of Nb) were added to the solution obtained.

The resulting mixture was heated with stirring and 140 g of Norton silica-alumina No. 5218 of 4x8 mesh (irregular shape) was added. Then, it was dried by evaporation with stirring, and further 16 hours at 120 ⁰ C..

.7098U / 1113

The dried material was transferred to a tray made of 10 mesh stainless steel wire and ^{calcined in a muffle furnace for 4 hours at 400 °} C. in an ambient air atmosphere. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 23.2 %.

Example 38

Mo ₁₆ V ₈ Nb ₂ or Mo ₁ V _Q> 5Nb ^ ₁₂₅

15.9 g ammonium metavanadate (0.136 g atoms V) and 48.1 g ammonium paramolybdate (0.272 g-atoms Mo) were in 0.5 l of water with stirring at 85-95 ° C. in an evaporation vessel provided with a steam jacket solved from stainless steel.

31.0 g of niobium oxalate solution (14.6 % Nb ₂ O ₅ ) (0.034 g atoms of Nb) were added to the solution obtained.

The resulting mixture was heated with stirring and 145 g of Norton Kieselsäure-Toner.de No. 5218 of 4x8 mesh (irregular shape) was added. Then, it was dried by evaporation with stirring, and further 16 hours at 12O ⁰ C..

The dried material wurda on a tray made of 10 mesh stainless Stahlstraht converted and calcined in a muffle furnace for 4 hours at 400 ⁰ C. in an ambient Luftatmosphära. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 19.7 %. Example 39

^Mo 1 ^U D, 806 ^Nb 0.63

.709814 / 1 1 13

- «r -SO 26U107

22.5 g ammonium metavanadate (0.192 g atoms V) and 42.1 g ammonium paramolybdate (0.238 g-atoms Mo) were in 0.5 l of water with stirring at 85-95 ° C. in a steam jacket Evaporation tray made of stainless steel detached

137.7 g of niobium oxalate solution (14.6 % Nb ₂ O ₅ ) (0.151 g atoms of Nb) and 12.6 g of ammonium nitrate (NH ₄ NO ₅ ) (0.157 mol) were added to the solution obtained.

The resulting mixture was heated with stirring and 160 g of Norton silica-alumina No. 5218 of 4x8 mesh (irregular shape) was added. Then, by l / erdampfen with stirring, and further 16 hours at 120 ⁰ C. dried.

The dried material was transferred to a Tabl.ett of 10 mesh stainless steel wire and in a muffle oven for 4 hours bsi 400 ⁰ C. in an ambient air atmosphere calcined * The deposited on the supported catalyst amount was calculated from the weight increase of the catalyst, 20.3 % » Example 40

42.4 g ammonium metavanadate (0.362 g atoms V) and 48.1 g ammonium paramolybdate (G, 272 g-atoms Mo) were dissolved in 0.5 l of water with stirring bsi 85-95 C. in an evaporation shell provided with a steam jacket solved from stainless steel.

57.4 g of niobium oxalate solution (14.6 % Nb ₂ O ₅ ) (0.063 g atoms of Nb) and 5.0 g of ammonium nitrate (NH ₄ NO ₅ ) (0.062 mol), dissolved in 30 ecm of water, were added to the solution obtained .

7 098U / 1 1 13

The resulting mixture was heated with stirring, and 160 g of Norton 4 × 8 mesh No. 5218 silica-alumina (irregular shape) was added. Then, it was dried by evaporation with stirring, and further 16 hours at 12O ⁰ C..

The dried material was transferred to a tray made of 1μ mesh stainless steel wire and calcined in a muffle furnace for 4 hours at 400.degree. C. in an ambient air atmosphere. The amount of catalyst deposited on the support, calculated from the increase in weight of the catalyst, was 24.2 %.

Example 41_

Mo ₁₆ V ₄ Sb ₂ or Ho ₁ V ₁ J ₂₅ Sb ₀

70 g of ammonium metavanadate (0.6 g atoms) and 424 g of ammonium paramolybdate (2.4 g atoms of Mo) were dissolved in 2.0 l of water with stirring at 60-80 ° C. in a stainless steel evaporation dish.

95 g of oxalic acid in 500 ecm of water (0.75 mol of H ₂ C ₂ O ₄ ) and 370 g of colloidal antimony oxide (10 % Sb) (0.3 g atoms of Sb) were added to the solution obtained.

The resulting mixture was heated with stirring and 1040 g (1000 ecm) Norton silica-alumina No. 5218 6.3 mm spheres were added. Then, by evaporation under stirring on a steam bath and further for 16 hours at 12O ⁰ C..

■ - 49a -

.709814 / 11 13

The dried material was transferred to a tray made of 10 mesh stainless steel wire and ^{calcined in a muffle furnace for 4 hours at 400 °} C. in an ambient air atmosphere. The amount of catalyst deposited on the carrier, calculated from the increase in weight of the catalyst, was 16.8 %, Example 42

• " ⁰ 16 ^V 4 ^Si 32 ^{or Mo} 1 ^V 0.25 ^Si 2

23.9 g ammonium meta anadate (0.204 g atoms U) and 144.3 g ammonium paramolybdate (0.817 g-atoms Mo) were in 0.5 l of water with stirring at 85-95 ° C. in an evaporation dish provided with a steam jacket solved from stainless steel.

326 g of "LUDOX AS" (30.1 % SiO ₃ ) (1.633 g atoms of Si) were added to the solution obtained.

The obtained mixture was heated with stirring and dried by evaporation with stirring. Further drying was carried out for 16 hours at 12O ⁰ C.

The dried material was crushed to 4x8 mesh and up Transferred a tray of 10 mesh stainless steel wire and place in a muffle furnace at 400 ° C for 4 hours. in an ambient air atmosphere calcined. No carrier was added to the pure catalyst.

- 50 - 0 9 8 14/1113

Example 43 Mo,, UnSn ^ or Mo ,, U _n crSn.-. * jc

16.0 g of ammonium metavanadate (0.137 g-atoms V) and 48.1 g of ammonium paramolybdate (0,2.72 g atoms Mo) were made with stirring at 85-95 ⁰ C. in a vessel equipped with steam jacket evaporation vessel in 0.5 1 of water stainless steel solved.

7.7 g of stannous chloride (SnCl ₂ .2HO) (0.034 g atoms of Sn) in 120 ecm of water and 5 ecm of conc. Hydrochloric acid added.

The resulting mixture was heated with stirring and 140 g of Norton silica-alumina No. 5218 of 4x8 mesh (irregular shape) was added. Then further 16 hours at 12O ⁰ C. was removed by evaporation with stirring and dried.

The dried material was transferred to a tray on 10 mesh stainless steel wire and ^{calcined in a muffle furnace for 4 hours at 400 °} C. in a surrounding air atmosphere. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 23.1 %.

Example 44 Mo ₁₆ V ₈ Ta ₂ or Mo ^ ya ^^

16.0 g of ammonium metavanadate (0.137 g-atoms V) and 48.1 g of ammonium paramolybdate (0.272 g atoms Mo) were dissolved in 0.5 1 of water with stirring at 85-95 ⁰ C. indicates, in a steam-jacketed stainless steel evaporating dish galoes.

43.3 g of tantane oxalate solution (17.38 % , diluted with 100 ecm of water (0.034 g atoms of Ta) were added to the solution obtained.

.709814 / 1113

107

The resulting mixture was heated with stirring and 140 g of Norton silica-alumina No. 5218 of 4x8 mesh (irregular shape) was added. Then ujas dried by evaporation with stirring, and further 16 hours at 120 ⁰ C..

The dried material was transferred to a tray made of 10 mesh stainless steel wire and ^{calcined in a muffle furnace for 4 hours at 400 °} C. in an ambient air atmosphere. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 23.4 %. Example 45_

^Mo 16 ^V 4 ^Ti 2 ^{Od8r M} ° 1 ^U 0.25 ^Ti 0.125

82 Q ammonium metavanadate (0.7 g atoms V) and 494 g ammonium paramolybdate (2.8 g atoms of Mo) were dissolved in 2.0 l of water with stirring at 60-80 ° C. in an evaporation dish made of stainless steel.

204 g of "TYZOR LA" (titanium lactate with 8.2 % Tij 0.35 g atoms of Ti) and 28 g of ammonium nitrate (0.35 mol NH ^ NO ₅ ), dissolved in 100 ecm of water, were added to the solution obtained.

The mixture obtained was heated with stirring, and 1040 g (1000 ecm) of Norton silica-alumina Wr. 5218 added as 6.3 mm beads. Anschießend further 16 hours at 12O ⁰ C. was by evaporation under Rührsn on a steam bath and dried.

7098U / 11 13

- sr - ^5S

The dried material was transferred to a 10 mesh stainless steel wire tray and placed in a muffle furnace at 400 ° C for 4 hours. calcined in a surrounding air atmosphere. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 30.4 %. Example 46

Mo ₁₆ U ₈ W ₂ or ^ V ^ W ^^

15.9 g of ammonium metavanadate (0.136 g-atoms V) and 48.1 g of ammonium paramolybdate (0.272 g atoms Mo) were dissolved in 0.5 1 of water with stirring at 85-95 ⁰ C. indicates, in a steam-jacketed stainless steel evaporating dish solved.

8.6 g of ammonium taujolstate (92% WO) in 100 ecm of water (0.034 g atoms of W) were added to the solution obtained.

The resulting mixture was heated with stirring, and 145 g of Norton 4x8 mesh No. 5218 silica-alumina (irregular shape) was added thereto. Then, it was dried by evaporation with stirring, and further 16 hours at 12O ⁰ C..

The dried material was transferred to a tray made of 10 mesh stainless steel wire and ^{calcined in a muffle furnace for 4 hours at 400 °} C. in an ambient air atmosphere. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 26.1 %.

7098U / 11 13

Tabel

Test results of the catalysts 29 up to V / experienced B

46

CD CO CO

3eisp. catalyst
composition Metal oxides—
in the cat.
■% catalyst
"hot spot";
⁰ C. Athanum
uiandl .; Effective
in ethylene;
α /
P. 29 Mon ₁₆ V ₄ 100 300 2 87 30th ^Mon 16 ^v 6.7 18.5 325
400 4th
22nd 78
47 31 Mon ₁₆ V ₈ 22nd 305
400 track
9 45 32 Mo ₁₆ V ₈ Fe ₁ 27.4 300
400 Track .
9 45 33 Mo ₁₆ V ₂ Nb ₂ •
100 300 12th 86 34 Mo ₁₆ V ₄ Nb ₂ 100 300 29 83 35 Mon ₁₆ V ₄ . ₆ Nb ₀ . _6th 100 300
378 29
65 »K)
81 cd
51 Sl-e-

Mo ₁₆ V ₆ Nb ₂

100

300

Table 2 continued

37 Mo ₁₆ V ₈ Nb _{0 #} 38 Mo ₁₆ V ₈ Nb ₂ ^ 39
ο
(O
™ 40
* ^ ^Μο 16 ^ν 12.9 ^Ν
Μο 16 ^ν 21.3 ^Ν ^ 41 Mo ₁₆ V ₄ Sb ₂ «Ο
42 Mo ₁₆ V ₄ Si ₃₂ 43 Mo ₁₆ V ₈ Sn ₂ 44 Mon ₁₆ V ₈ Ta ₂ 45 Mo ₁₆ V ₄ Ti ₂ 46 ^MO 16 ^V 8 ^W 2

23.2 322 1.4 100 • ι 77 π K) 400 12th 76 55 CD 19.7- 300 12th 91 -P-- 400 50 68 4- 20.3 300 -Track -_ 61 CD 400 8th 85 24.2 315 2 83 400 20th 46 16.8 300 6th 95 400 23 75 100 300 1 99 400 14th 50 23.1 328 Track ■ - _ _ 400 7th 52 ι 23.4 300 4th 85 <$ 400 25th 69 30.4 300 2 400 15th 26.1 300 Track · 400 7th

Examples 47 to 58

Catalysts 47 to 58 were prepared according to the following procedure and evaluated in test procedure B. The catalysts

of Example 47-57 contained the elements Mo, \ l and Nb and / or 'an element - ·

/ X and Y. The catalyst of Example 58 contained Mo and I / as well W and Mn. The composition of the catalysts is given at the beginning of the corresponding example; the test results are in Table 3 listed.

The catalysts of Examples 47 to 58 were evaluated at two "hotspot" temperatures at 300-400 C. to determine the percentage conversion and effectiveness at each of these temperatures for the hydroxydehydrogenation of ethane to ethylene. Example 47

^Ho 16Wo, 5 ° ^{der Mo} ₁ ^U a, 25 ^Wb D, 125 ^K 0.031

8.0 g of ammonium metavanadate (0.068 g atoms ) and 48.1 g of ammonium paramolybdate (0.272 g atoms of Mo) were dissolved in 0.5 l of water with stirring at 85-95 ° C. in a stainless steel evaporation dish provided with a steam jacket solved.

0.85 g of potassium nitrate (KWO,) (0.0084 g atoms of K) and 31 g of niobium oxalate solution (14.6 % Nb ₂ O ₅ ) (0.034 g atoms of Nb) and 2.8 g of ammonium nitrate ( NH ₄ NO ₅ ) (0.035 mol) was added.

The resulting mixture was heated with stirring and 150 g of Norton silica-alumina No. 5218 of 4x8 mesh (irregular shape) was added. Then it was dried by evaporation with stirring and a further 16 hours at 120 ° ς _{# »}

7 0 9 8 14/1113

The dried material was transferred to a tray on 10 mesh stainless steel wire and ^{calcined in a muffle furnace for 4 hours at 400 °} C. in an ambient air atmosphere. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 17.9 %. Example 48_

^M0 16 ^U 4 ^Nb 4 ^P 4 ^{Or Mo} 1 ^V 0.25 ^Nb 0.25 ^P 0.25

8 g Amrnoniummetavanadat (0.068 g-atoms \ l) and 48.1 g Arnmoniumparamolybdat (0.272 g atoms Mo) were dissolved in 0.5 1 of water with stirring at 85-95 ⁰ C. in a provided with a steam jacket l'erdampfungsschale from stainless steel solved.

7.8 g of phosphoric acid (85.6 % H ₃ PO.) (0.068 g atoms P) and 62 g niobium oxalate solution (14.6 % Nb ₂ O ₅ ) (0.068 g atoms Nb) and 5, 6 g of ammonium nitrate (0.07 mol of NH ₄ NO ₃ ) were added.

The resulting mixture was heated with stirring and 150 grams of Norton 4x8 mesh # 5218 silica-alumina (irregular Shape) added. Then, by evaporation with stirring and further 16 hours at 120 ° C. dried.

The dried material was transferred to a tray made of 10 mesh stainless steel wire and calcined in a muffle furnace for 4 hours at 400 ° C. in an ambient air atmosphere. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 25.3 %.

Example 49 Mo ₁₆ U ₈ Nb ₂ Ce ₂ or Mo ₁ V _Qf 5Nb ^ ₁₂₅ Ce ₀ ^ ₂₅

7 0 9 8 U / 1 1 1 3

15.9 g ammonium rivetavanadate (0.136 g atoms M) and 48.1 g ammonium paramolybdate (0.272 g atoms Mo) were dissolved in 0.5 l of water with stirring at 85-95 ° C. in a steam jacket Dissolved stainless steel vial.

31 g of niobium oxalate solution (14.6 % Mb ₂ O ₅ ) in 100 ecm of water (0.034 g atoms of Nb) and 14 g of cerium nitrate (41.8 % CeO ₂ ) (0.034 g atoms of Ce) in 150 ecm of water dissolved, added.

The resulting mixture was heated with stirring and 150 grams of Norton 4x8 mesh # 5218 silica-alumina (irregular Shape) added. Then by evaporation with stirring

i
and further 16 hours at 12O ⁰ C..

The dried material was transferred to a tray made of rustproof 10 mesh steel wire and calcined in a muffle furnace for 4 hours at 400.degree. C. in an ambient air atmosphere. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 28 %.

Example 50+

Mo ₁₆ V ₈ Nb ₂ Co ₂ or Mo ^ ₀ , ₅ ^Nb 0.125 ^Co 0.125 '

15.9 g ammonium metavanadate (0.136 g atoms V) and 48.1 g ammonium paramolybdate (0.272 g-atoms Mo) were in 0.5 l of water with stirring at 85-95 ° C. in an evaporation dish provided with a steam jacket solved from stainless steel.

31 g of niobium oxalate solution (14.6 % Nb ₂ O ₅ ) in 100 ecm of water (0.034 g atoms of Nb) and 8.5 g of cobalt acetate / Co (CH ₃ COO) ₂ .4H ₂ g7 (0.034 g -Atome Co), dissolved in 150 ecm of water,

added.

709814/1113

The resulting mixture was heated with stirring and 150 g of Norton silica-alumina No. 5217 of 4x8 mesh (irregular shape) was added. Then, it was dried by evaporation with stirring, and further 16 hours at 12O ⁰ C..

The dried material was transferred to a tray made of 10 mesh stainless steel wire and calcined in a muffle furnace at 400 ° C. for 4 hours in an ambient air atmosphere. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 26.3 %.

Example _51_

Mo _1n VnNb ₉ Cr ₇ or Mo ₁ V _n (-ND _n ^ «, - Cr _oc

15.9 g ammonium metavanadate (0.136 g atoms V) and 48.1 g ammonium

i
paramolybdate (0.272 g atoms Mo) were dissolved in 0.6 1 of water with stirring at 85-95 ⁰ C. in a vessel equipped with steam jacket evaporation vessel of stainless steel.

31 g of niobium oxalate solution (14.6 % Nb ₂ O ₅ ) in 100 ecm of water (0.034 g atoms of Nb) and 8.4 g of chromium acetate / Cr (C ₂ H ₃ O ₂ ) ₃ .2H ₂ o7 ( 0.034 g atoms of Cr), dissolved in 150 ecm of water, added.

The dried material was transferred to a tray made of 10 mesh stainless steel wire and calcined in a muffle furnace for 4 hours at 400 ° C. in an ambient air atmosphere. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 24.2 %.

709814/1113 "

B is ρ ie 1 52

Mo ₁₆ V ₈ Nb ₂ Cu ₂ or ^^ 0.5 ^ 0.125 ^ 0.125

15.9 g of ammonium metavanadate (0.136 g-atoms V) and 48.1 g Ammoniurnparamolybdat (0.272 g-atoms of Ho) were dissolved in 0.5 1 of water with stirring at 85-95 ⁰ C. in a vessel equipped with steam-jacketed stainless steel Verdanipfungsgefäß solved.

31 g of niobium oxalate solution (14.6 % Nb ₂ O ₅ ) in 100 ecm of water (0.034 g atoms of Nb) and 6.8 g of cupric acetate / ^ CH ₃ COO) ₇ Cu.H ₂ D / (0.034 g Atoms Cu), dissolved in 150 ecm of water, added.

The mixture was heated with stirring, and 150 g of Norton silica-alumina Wr. 5218 of 4X, 8 mesh (irregular Shape) added. Then, by evaporation with stirring and further 16 hours at 120 ° C. dried.

The dried material was transferred to a tray made of 10 mesh stainless steel wire and ^{calcined in a muffle furnace for 4 hours at 400 °} C. in an ambient air atmosphere. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 25.0 %. Example 53

M π ι / IM h r ρ η fi ο τ * M ο 1 / M h

15.9 g ammonium metavanadate (0.136 g atoms V) and 48.1 g ammonium paramolybdate (0.272 g atoms of Mo) were dissolved in 0.5 l of water with stirring at 85-95 ° C. in an evaporation vessel provided with a steam jacket solved from stainless steel.

7 0 9 8 U / 1 1 1 3

To the obtained solution 31 g Niobiumoxalatlösung (14.6 ° / o Nb ₂ O ₅₎ in 100 cc water (0.034 g-atom of Nb) and 6.4 g of ferrioxalate /.Fe were ₉ (C ₂ D.) y / (0.034 g atoms Fe), dissolved in 150 ecm of water plus 4.4 g of oxalic acid, added.

The resulting mixture was heated with stirring and 150 grams of Norton 4x8 mesh # 5218 silica-alumina (irregular Shape) added. It was then dried by evaporation with stirring and a further 16 hours at 120.degree.

The dried material was transferred to a 10 mesh stainless steel wire tray and placed in a muffle furnace at 400 ° C for 4 hours. calcined in a surrounding air atmosphere. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 23 %. Example 54

^Μο 16 ^υ 8 ^Νϋ 2 ^Μη 2 ^{Or Mo} 1 ^V 0.5 ^Nb D, 125 ^Mn 0, i25

15.9 g ammonium metavanadate (0.136 g atoms V) and 48.1 g ammonium paramolybdate (0.272 g atoms of Mo) were dissolved in 0.4 l of water with stirring at 85-95 ° C. in an evaporation vessel provided with a steam jacket solved from stainless steel.

31 g of niobium oxalate solution (14.6 % Nb ₂ O ₅ ) (0.034 g atoms of Nb) and 8.4 g of manganese acetate (0.034 g atoms of Mn), dissolved in 100 ecm of water, were added to the solution obtained.

The resulting mixture was heated with stirring, and 140 g of Norton silica-alumina No. 5218 of 4x8 mesh (irregular shape) was added. Then, it was dried by evaporation with stirring, and further 16 hours at 12O ⁰ C..

709814/1113.

The dried material was transferred to a tray made of 10 mesh stainless steel wire and ^{calcined in a muffle furnace for 4 hours at 400 °} C. in a surrounding air atmosphere .

Example 55_

Ho ₁₆ U ₈ Mb ₂ Ni ₂ or Mo ₁ V ^ Nb ^ ₁₂₅ Ni _0} ^

15.9 g of ammonium metavanadate (0.136 g-atoms of U) and 48.1 g of ammonium paramolybdate (0.272 g atoms Mo) were dissolved in 0.5 1 of water with stirring at 85-95 ⁰ C. in a vessel equipped with steam-jacketed evaporator ungsgefäß stainless Steel loosened.

31 g of niobium oxalate solution (14.6 % Nb ₂ O ₅ ) in 100 ecm of water (0.034 g atoms of Nb) and 8.5 g of nickel acetate (Ni (C ₂ H ₃ 0 ₂ ) _{2 .4H 2} O) were added to the solution obtained. (0.034 g atoms Ni), dissolved in 150 ecm of water, added.

The resulting mixture was heated with stirring and 150 g of Norton silica-alumina No. 5218 of 4x8 mesh (irregular shape) was added. Then, it was dried by evaporation with stirring, and further 16 hours at 12O ⁰ C..

The dried material was transferred to a tray made of 10 mesh stainless Stähldrahlt and calcined in a muffle furnace for 4 hours at 400 ⁰ C. in an ambient air atmosphere. The amount of the catalyst deposited on the carrier was calculated from. the weight increase the catalyst, 26.4 %,

Example 5 (5 Mo ₁₆ U ₈ Nb ₂ Si ₃₂ or Mo ₁ VQ ₅ Nb ₀₁₂₅ Si ₂

7098U / 1113

^26U107

35.9 g of ammonium meta anadate (0.307 g atoms) and 108.0 g of ammonium paramolybdate (0.612 g atoms of Mo) were dissolved in 0.5 l of water with stirring at 85-95 ° C. dissolved in a stainless steel evaporation dish provided with a steam jacket.

69.6 g of niobium oxalate solution (14.6 % Nb ₂ O ₅ ) (0.076 g atoms of Nb) and 244.2 g of ¹¹ LUDOX AS colloidal silica sol (30.1 % SiO ₂ ; 1.223 g) are added to the solution obtained. Atoms Si) added.

The obtained mixture was heated with stirring and dried by evaporation with stirring. It was then ^{dried at 120 °} C. for a further 16 hours.

The dried material was crushed to 4x8 mesh and transferred to a tray made of 10 mesh stainless steel wire and dried in a muffle furnace for 4 hours at 400 ° C. in an ambient air atmosphere. No carrier was added to the pure catalyst.
Example 57
Ho ₁₆ U ₈ Nb ₂ U ₁ odsr ^ l / ^ Nb ^^ U

15.9 g ammonium metavanadate (0.136 g atoms V) and 48.1 g ammonium paramolybdate (0.272 g-atoms Mo) were taken in 0.35 l of water Stirring at 85-95 ° C. dissolved in a stainless steel evaporation dish provided with a steam jacket.

31 g of niobium oxalate solution (14.6 % -, Nb ₂ O ₅ ) (0.034 g atoms of Nb) and 7.2 g of uranyl acetate / "(CH ₃ COO) ₂ UO _2. 2H ₂ 07 (0.017 g -Atome U) added.

709814/1113

The resulting mixture was heated with stirring and 140 g of Norton silica-alumina No. 5218 of 4x8 mesh (irregular shape) was added. Then, it was dried by evaporation with stirring, and further 16 hours at 12O ⁰ C..

The dried material was transferred to a floor made of 10 mesh stainless steel wire and calcined in a muffle furnace for 4 hours at 400 ° C. in an ambient air atmosphere. The amount of catalyst deposited on the carrier, calculated from the increase in the weight of the catalyst, was 27 %. Example 5J3

^Mo 16Vi, 6 ^Mn 4 ^{Or M} ° 1 ^U 0.25 ^W 0.1 ^Mn 0.25

350 g ammonium roetavanadate (3 g atoms V) and 2120 g ammonium paramolybdate (12.0 g atoms Mo) were dissolved in 10 l of water with stirring at 60-80 ° C. in a stainless steel vaporization dish.

313 g of ammonium paratungstate in 5 liters were added to the solution obtained Dissolved water (1.13 g atoms W), and 750 g Manganac3tat.4H “0 (3.06 g atoms Mn), dissolved in 1 liter of water, added.

The resulting mixture was heated with stirring and evaporation dried with stirring. Further drying took place at 120 ° C. for 16 hours.

The dried material was crushed to 4x8 'mesh and up Transferred a tray of 10 mesh stainless steel wire and placed in a muffle furnace at 400 ° C for 5 hours. in a surrounding air atmosphere calcined. The pure catalyst was obtained.

709814/1113

Table 3
Catalyst Test Results on Catalyst 47-58 in Procedure B

Ex. Catalytic
Add. Metal oxides
.in cat. catalys.
hot spot
⁰ C. Athan
umiuandl. effectiveness
■ in ethylene
• * 47 17-9 338
400 VO CvI -J CD
U) VO 709 I 48 25.3 319
378 trace
3.3 Ul I
CO I OO ί 49 Mo ₁₆ V ₈ Nb ₂ Ce ₂ 28 • P-U)
88 8.6 84
56 it 50 ^Mo 16 ^V 8 ^Nb 2 ^Co 2 26.3 300
4oo 6th
29 94
59 51 Mo ₁₆ V ₈ Nb ₂ Cr ₂ 24.2 300
4oo 2.2
I3.5 87
65 52 Mo ₁₆ V ₈ Nb ₂ CU ₂ . 25.1 300
400 6th
42 79
52 53 Mo ₁₆ V ₈ Nb ₂ Fe ₂ 23 300
4oo 8th
42 82
57 54 Mo ₁₆ V ₈ Nb ₂ Mn ₂ 25.4 300
4oo 4th
28 97
74 55 26.4 300
4oo 5
33 93
59

Table 3 continued

56

57 Mo ₁₆ V ₈ Nb ₂ U ₁ 58

100 300
^ oo 13th
50 82
50 27 300
i + 00 12th
53 91
6k 100 300
IfOO 8th
58 58
58

Examples 59 to 61

The catalyst of Example 35 (Mo., U. ₆ ^Wb ng) was used in three experiments (Examples 59 to 61) in the oxydehydrogenation of ethane in ethylene in the absence or presence of added water to demonstrate its ability under these circumstances To produce acetic acid. In Examples 59 and 60 no water was added; in Example 61 this was the case. The reaction conditions present (pressure, temperature, inlet composition of the gas test, inlet speed of the water and its outlet rate) and the test results (% selectivity, productivity and % conversion) are shown in Table 4. The catalyst was evaluated in Example 59-61 according to Test Method C,

70 9 8 U / U 13

Table 4

Oxydehydrogenation of ethane with catalyst Md ^ V ^ ₆ Nb _{Q ß} in the

Production of acetic acid

Example total pressure 'Reakt.- Gas inlet- · Water inlet- Wasserauslaßatiü, temp. 5 additional setting; % fast . swiftly.

° 2 ^C 2 ^H 6 mol / hr ^

C.

59 5.25 275 3.2 89.1 0.0 0.37

60 5.25 322 6.0 90.0 0.0 0.83

61 8.75 323 6.5 85.8 0.98 1.5

Table 4 (continued)

E.g. Äthanumuiandl. Effective in ^C ? ^H 4 Productive. Effectiveness in CH, COOH productive. % C ₂ H ^ J % . kg / m cat / hour CH3COOH; % kg / m ³ cat./hour

59 3 ,1 85 , 0 60 6th , 9 73 ,1 61 7th , 5 67 7098

60, 8th 13th , 2 119 2 18th ,8th 131, 2 18th , 4

20.8 64
76.8

Presumably to / ei groups of catalysts of the above examples, deposited on a carrier or not, new. These catalysts include the following preparations:

New catalyst I:

Mo _h U.Nb.A _k

A stands for Ce, K, P, Ni and / or U, h has a value of 16,

i has a value from 1 to 16, preferably 1 to 8, j has a value from 1 to 10, preferably 0.2 to 10, and k has a value from 0 to 32, preferably 0.1 to 5

new catalyst II:

^Mon A ^L n

L stands for Nb and / or Pb, 1 has a value of 16, m has a value of 1 to 16, preferably 1 to B, and η has a value of 1 to 10, preferably 0.2 to 10.

In the tests for the catalyst evaluation in Examples 1-23 and 29-61 the outflowing gas streams did not contain any hydrogen, methane or higher alkanes formed by the process. The products formed were in all cases ethylene, acetic acid, water, CG and CO2

7 0 9 8 U / 1 1 1 -3

Claims (7)

- Process for converting ethane to ethylene at low Temperature, characterized in that ethane is exothermic Oxydehydrogenated in the gas phase at a temperature of ^ 450 C. 2.- The method according to claim 1, characterized in that a calcined preparation of the elements Mo, X and Y in the ratio is used as the oxydehydrogenation catalyst used, where X stands for Cr, Mn, Nb, Ta, Ti, V and / or W, Y for Bi, Ce, Co, Cu, Fe, K, Mg, Ni, P, Pb, Sb, Si, Sn, Tl and / or U is a has a value of 1, b has a value between 0 and 2 and c has a value from Q to 2 with the condition that the total value of c for Fe, Co and / or Ni <0.5. 3.- The method according to claim 2, characterized in that b has a value from 0.05 to 1.0 and X comprises V and / or Nb. 4.- The method according to claim 2, characterized in that b one Has a value of 0.05 to 1.0 and X comprises W, ¥ and / or Nb. 5 * - Method according to claim 3 and 4, characterized in that c has a value from 0.05 to 1.0. .6, - Method according to claim 1 to 5, characterized in that it is carried out at a temperature of 455O ⁰ C.. 7.- The method according to claim 1 to 6, characterized in that it takes place in the presence of added water. 7098U / 1113 ORIGINAL INSPECTED I- vT - 8, - Calcined preparation from the elements Mo, V, Nb and A im l / ratio: Mo, U.Nb .A ₁ h ι jk u / obei A stands for Ce, K, P, Ni and / or U, h has a value of 16, i has a value from 1 to 16, j has a value from 1 to 10, and k has a value from ^ 0 to 32. 9, - Calcined preparation from the elements Mo, W and L im relationship mo for L stands for Nb and / or Pb, 1 has a value of 16, m has a fourth from 1 to 16 and η has a value from 1 to 1D. The patent attorney: 7 0 9 8 14/1113