JPS6059012B2 - Molybdenum-containing catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel molybdenum-containing catalyst for the oxydehydrogenation of ethane to ethylene.

For example, it has been customary for ethylene to be produced industrially by thermally decomposing ethane in an endothermic reaction carried out at a temperature of about 6,000 to 1,000 DEG C. (U.S. Pat. No. 3,541,172).

Since the reaction time in this method is very short,
This makes it difficult or impossible to efficiently recover heat from the process stream. In addition, the high temperature reactions used require the use of special alloys in the construction of the furnace or reaction vessel. The cracking reactions also produce relatively large amounts of low boiling byproducts such as hydrogen and ethane, making recovery of ethylene from such byproducts complicated and expensive. It is possible to oxydehydrogenate ethane using a variety of oxyhalogenation catalyst systems in an exothermic reaction. However, these reactions are at least about 5
achieved only at temperatures between 00 and 600 °C (U.S. Pat. No. 3
080435 specification). In addition, the presence of halogenated atoms in this case increases the difficulty in recovering the olefins produced. Special and expensive construction materials are also required to withstand corrosion from halogens and hydrogen halides within the reaction system. Furthermore, in order to carry out the process economically, the halogen itself must be recovered and recycled. ΣC3 selected by an exothermic reaction at a relatively high temperature
Oxydehydrogenation of alkanes can also be performed using selected vanadium-containing catalysts (U.S. Pat. No. 3,218,368;
No. 541,179 and US Pat. No. 3,856,881) or selected catalysts containing vanadium and molybdenum (US Pat. No. 3,320,331).

Also, the productivity (production capacity) of α,β unsaturated ethylene (or acetic acid), such as acrolein, = bonds of ethylene (or acetic acid) produced per cubic foot of catalyst (in the catalyst bed) per hour of reaction time. Several novel catalysts of the present invention have the general formula (in which a is 1, b is 0.05 to 1, C is 0 to 1, and d is 0.03 to about 2, and when X is Ta) , Y is Fel or Fe and Si, and when X is Nb, Y is Fe, Cu, Si, K
, P, Ce, CO, Nl or U, and when c is O, Y is Fe, Sb, Si. or Sn)
A molybdenum-containing catalyst for the oxydehydrogenation of ethane to ethylene is comprised of a calcined composition having the formula:

It is also known to use catalyst systems containing molybdenum and vanadium for the gas phase oxidation of tri-aliphatic aldehydes to the corresponding alpha, beta monounsaturated carboxylic acids, such as acrylic acid.

These catalyst systems are described in Belgian patent nos. 8213n and 8213n.
As disclosed in the specifications of No. 21324 and No. 821325, it contains the elements MO, V and X (wherein X is Nb, Ti or Ta).
However, prior to the proposal of the catalyst of the present invention, these known catalysts could be used to dehydrogenate ethane, for example, to ethylene at a relatively low temperature with favorable conversion (%), selectivity (%), and productivity. It was impossible.

Here, conversion rate, selectivity and productivity are defined as follows.

1. Conversion rate (%) 1a. However, A is the molar ethane-equivalent sum of all carbon-containing products excluding ethane in the effluent (carbon basis). Selectivity for ethylene (or acetic acid) (
or efficiency)% of soluble compounds.

These compounds of the various elements selected must be mutually soluble to the extent possible. The Si compound is usually added in the form of a colloidal silica sol. If any of the compounds of such selected elements other than Si are not mutually soluble with the other compounds, they can be added last to the solution system. A catalyst composition is then made by removing water or other solvent from the mixture of compounds in the solution system by evaporation. When using a catalyst deposited and supported on a carrier, the desired elemental compound is usually deposited on a fine porous carrier having the following physical properties (but not limited to these):

The surface area is about 0.1-500j ('1y1 apparent porosity is 30-60%, at least 90% of the pores are 20-150
It has a pore size of 0 microns.

and the particle or pellet form has a diameter of about 118 to 5116 inches. This deposition is accomplished by immersing the support in the final mixture of all compounds, evaporating most of the solvent, and then drying the system at about 80 DEG-220 DEG C. for 2-6 hours. The thus dried catalyst is then heated at about 220-550 tC in air or oxygen at 112-2
The desired MOaVbX is obtained by baking by heating in a laboratory.
cY, to produce a composition. Supports that can be used are silica, aluminum oxide, silicon carbide, zirconia, titania and mixtures thereof.

In this case, the supported catalyst usually contains about 10 to 5 weight percent of the catalyst composition, the remainder being the support.

The molybdenum is preferably present in solution in the form of an ammonium salt of molybdenum, such as ammonium molybdate, or in the form of an organic acid salt of molybdenum, such as acetate, oxalate, mandelate and glycolate. Introduce. Other water-soluble molybdenum compounds that may also be used include partially water-soluble molybdenum oxide, molybdic acid, and molybdenum chloride. Vanadium is preferably introduced into the solution in the form of ammonium salts of vanadium such as ammonium metavanadate as well as ammonium decarvanadate, or in the form of organic acid salts of vanadium such as acetate, oxalate and tartrate. .

Other water-soluble vanadium compounds that can also be used are partially water-soluble vanadium oxides and vanadium sulfates. Niobium and tantalum are preferably introduced into the solution in the form of oxalate.

Other sources of these metal salts in soluble form are compounds in which the metal is coordinated, bound or complexed to beta-diketonates, carboxylic acids, amines, alcohols or alkanolamines. Iron, nickel, cobalt, copper, uranium, cerium and potassium are preferably introduced into the solution in the form of nitrates.

Other water-soluble compounds of these elements that can be used are water-soluble chlorides and organic acid salts such as acetates, oxalates, tartrates, lactates, salicylates, formates and carbonates of such elements. be. Antimony and tin are preferably introduced into the catalyst system in the form of water-insoluble oxides.

Water-soluble compounds of these elements that can be used are antimony trichloride, stannic chloride, stannous chloride, stannic sulfate and stannous sulfate. Other water-insoluble compounds of these elements that can be used are stannous hydroxide and stannous oxalate. Silicon is preferably introduced into the catalyst system in the form of an aqueous colloidal silica (SiO2) sol.

Phosphorus is preferably introduced into the catalyst system as phosphoric acid or a water-soluble phosphate. For the catalyst to be most effective,
We believe that the MO, V, X, and Y metal components are somewhat reduced below their highest possible oxidation state.
It will be done.

This is accomplished during heat treatment of the catalyst in the presence of a reducing agent such as NH3 or an organic reducing agent such as an organic complexing agent that is introduced into the solution system that makes up the catalyst. Reduction of these catalysts can also occur in reactors in which the oxidation reaction is carried out by passing hydrogen or a hydrocarbon such as ethane, ethylene or propylene through a catalyst bed. A fixed bed or a fluidized bed can be used for the catalyst supported or unsupported on a carrier.

By way of example, the catalyst of the present invention can be used to selectively oxydehydrogenate hydrocarbons, such as ethane, without the addition of diluents other than water, to produce final products such as ethylene and acetic acid with conversion rates (%) as shown below. ), efficiency (%), and productivity.

In this case, in a normal reaction process without addition of water, 1 mol of water is produced for every mol of oxydehydrogenated ethane, for example. The water thus produced during this reaction produces about 0.05 to 0.25 moles of acetic acid for every mole of ethylene produced therein. However, when water is added, an additional amount, approximately 0.
This results in increased production of acetic acid from 25 to 0.95 moles. The following examples, along with Comparative Examples 1-5, illustrate the preparation of various catalyst compositions of the present invention and their use, as one example, in the oxydehydrogenation of ethane to ethylene.

The activity of these catalysts is tested in a small U-tube reactor in which oxygen and ethane are fed in a pulsatile flow (Test Method A).
Alternatively, it was measured using either a standpipe reactor in which ethane and oxygen are continuously flowed in parallel (Test Method B), or by a back-mixing (Back-Mlx) autoclave method (Test Method C).

These test methods are described in detail below. Catalyst Test Method A Test catalysts were screened for determination of ethane oxydehydrogenation activity in a beating microreactor.

A reaction zone containing this catalyst, a silica U-shaped tube having a length of 20 P and an inert diameter of 8 tubes, was heated by immersing it in a fluidized sand bath whose temperature was controlled by a thermocouple regulator. The temperature regulating and measuring thermocouples were immersed in a bed of fluidized sand at least 3 inches above the level of the catalyst in the U-tube. Put it in a sand bath. A preliminary investigation of the temperature conditions showed that from top to bottom the temperature varied by less than 3 degrees from the fixed point set by the regulator. This microreactor was precisely coupled to a gas chromatograph to analyze the reaction product flow.

Intercept the helium supply line inside the chromatograph at a point immediately after the flow regulator and connect it with the valves at ports 8 and 21 [Union, Carbide Co., Model C, Special Mechanical Department].
4-70] and has a port 6 therefrom [Union, Carbide, Model 2112-50-2]
by directing the inlet leg of the U-tube reactor through the
The helium carrier feed flowing through the microreactor was collected from the chromatograph. The system is equipped with an injection port with a rubber septum at the reactor inlet. The product gas stream from the reactor was channeled back through a cold trap and through a valve with a port 8 serving to branch to one of the two analytical systems of the chromatograph. Each valve is equipped with a bypass valve that can be adjusted to equalize the pressure drop across the chromatographic columns within that analytical system. The injection of a pulsed stream of 2.0 ml of feed gas (composition: 6.0% melt oxygen, 8.0% ethane by volume, balance nitrogen) was carried out by means of a gas-tight syringe through the port just before the catalyst.

The gas was passed over the catalyst 3.0y diluted by helium carrier gas which passed through the reactor and through the analytical gas chromatograph at a rate of 60 ml/min throughout. Analysis of the resulting mixture was carried out using a 10″× POrOpak (T.M.)
It was carried out in a 1/8" diameter stainless steel column.

The column started at 30°C and was heated at a rate of 10°C per minute. The retention times under these conditions were 2 minutes for air, 2.5 minutes for carbon dioxide, 3.4 minutes for ethylene, and 4.0 minutes for ethane. The identity of the product was then confirmed by chromatography of a pure known sample and mass spectrometer examination of each distinct peak. Polopak R is a polystyrene resin in the form of fine particles and spheres crosslinked with divinylbenzene. Catalyst Test Method B The catalyst was tested in a tubular reactor under the following conditions.

The ethane gas supply composition (volume %) was 9.0% C2H6,
6.0%02 and 8.5%N2, space velocity 340F
1r-1, the total reaction pressure is 1 atm.

We also noted the activity of the catalyst as the temperature rose. The reactor consists of 117 stainless steel standpipes, approximately 1
A 2" deep molten salt bath (heated using DuPont Hi-Tech™ heat transfer salt) was used. 11
An 8" thermocouple sleeve was passed through the entire length of the reaction tube and through the center of the catalyst bed.

The temperature status of the catalyst could be determined by sliding a thermocouple through the sleeve. 26 ml of catalyst was introduced into the tube so that the top of the catalyst bed was 4″ below the surface of the heat transfer salt. The upper zone of the catalyst bed was enriched with glass beads, which served as a preheater.The gas effluent from the reactor was passed through a condenser and a trap at 0°C.The gas and liquid thus obtained were The products were analyzed as described below. Catalyst Test Method C The reactor used for this high pressure study was a bottom-stirred Magnedrive autoclave with a centrally located catalyst basket and side product effluent lines. It was hot.

A variable speed, magnetically driven fan continuously recirculated the reaction mixture over the catalyst bed. This reactor was presented at the 64th International Conference of the American Institute of Chemical Engineers held in New Orleans, Louisiana, USA from March 16th to 20th, 1962. 1 Submitted as Proceedings 42E to the Second Part of the Symposium on Advances in High-Voltage Technology and published in New York, United States of America, 1
0017, 47th Street, East, New York,
It is of the type depicted in Figure 1 of the paper by Barday, Hambrick, Maron, and Wrock et al. entitled ``Reactors, Four, Vapor Phase, Catalytic Studies,'' available from AIChE, 34. The backmix autoclave has a stainless steel catalyst vessel located above the stirring fan blades.

The fan blows the gas upwardly and inwardly through the catalyst bed in a conventional manner. Two thermocouples measure the temperature at the inlet and outlet.

114 through a rotameter at a pressure of approximately 150 pSig.
Oxygen was fed into the reactor through a line. A gaseous ethane-COO mixture was fed via a rotameter, which was then combined with the feed oxygen just before introduction into the reactor. The liquid was then mixed with gas. It was pumped directly into the reactor via the same feed line, but after the gases were mixed, a liquid inlet was connected to the line. Outflow gas was removed via a port on the reactor side. Condensable liquid The product was removed by a series of cold traps in two baths, the first bath being O
It had two cooling traps immersed in it, containing moist ice at ℃. The second bath of dry ice and -78°C acetone had two cold traps. The non-condensable components of the discharge stream were discharged via a dry gas test meter at atmospheric pressure to determine their total volume. A sampling valve with port 8 allowed direct sampling of both product and feed gas via lines connected directly to the reactor feed and product streams.
No external recirculation was used. The bulk volume of the weighed catalyst sample was determined (approximately 150 cc.) and the sample was placed into the catalyst basket. In each case, the amount of catalyst charged was about 131.1y. Stainless steel screens were placed above and below the catalyst bed to minimize catalyst wastage and circulation of catalyst fines. After placing the catalyst basket in the reactor and sealing the reactor, the process line is heated to approximately 100-200 mL above the expected maximum working pressure.
Pressure tests were performed at ambient temperatures up to a pressure of pSig.
Nitrogen was used for this test. When it was determined that there were no leaks in the reactor, pure N2 was passed through the reactor and the temperature was lowered to 27°C.
The temperature was increased between 5°C and 325°C. Gas feed composition is 76-97% C2l (6, 3-6%02,
It was in the range of 0-10% H2O and 0-10% COx. After the desired temperature was obtained, the oxygen and ethane-COO mixture was adjusted to provide the desired volatile ratio at the desired overall flow rate. The concentration of each component in the effluent gas was measured by the gas chromatography analysis described below. Approximately 0.5 to 1 hour was allowed for the reactor to reach the desired temperature stability. The liquid product trap was then drained and the dry gas test meter reading was taken to note the start time. The effluent gas samples during the operation process are C2H6, C2H4, and O. ,C
Analyzed for O, CO, and other volatile hydrocarbons. At the end of the run, the liquid raw product was collected and the volume of effluent gas was recorded. These liquid products were analyzed by mass spectrometry. The reactor inlet and outlet gases for all tests conducted with test methods B and C were 02, N2 and C
For O, a 10″ x 1182-column molecular
(14130 mesh) at 95°C and (0.
N2, C0 are the same), CO2, ethylene, ethane and H2O in a 14 x 118" column Polopak Q (8
01100 mesh) at 95%. The liquid product is extracted with H2O by mass spectrometry when it is sufficiently obtained.
l Acetaldehyde, acetic acid and other components were analyzed.

Polopak Q (T.M.) is a particulate spherical polystyrene resin crosslinked with divinylbenzene. The conversion (%) and selectivity (%) in all these cases were based on stoichiometry according to the following equations, without applying individual response factors to the eluted peak areas of the chromatograms.

C2H6+11202→C2H4+l(20C6H6+
7no2()2-2C02+3H20 The reaction conditions for the above three test methods were as follows.

Catalysts 1 to 4 of each catalyst prepared as described below were evaluated using catalyst test method A.

The composition of each catalyst is shown at the beginning of each example, and the test results are shown in Table 1 below. The catalyst of Example 4 was evaluated using Test Method B and the test results are also shown in Table 1. In testing the catalysts of these Examples 1-4, the catalytic activity was initially provided by the catalyst. The lower temperature was tested first and was taken as the temperature of initial activation (TO). Then T like this. The selectivity of the catalyst for oxydehydrogenation of ethane to ethylene was measured. Next, ethane to ethylene is 1
In order to determine the lowest temperature above TO at which 0% conversion is achieved, the activity of each catalyst was evaluated at a higher temperature and this temperature is shown in Table 1 as TIO. The selectivity of the catalyst for the oxydehydrogenation of ethane to ethylene in TIO was also determined and shown in Table 1. Example 1tM016v4F
e1 MOLvO.25Fe0.6Z 70y ammonium metavanadate (0.6 g atom V) and 424y ammonium molybdate (2.4 g atom MO) were dissolved in a stainless steel evaporating dish from 60 to 80 g. It was dissolved in 21 water with stirring.

To the resulting solution was added 60y of ferric nitrate nonahydrate (0.15 g atom iron) dissolved in 100 ml of water.

The resulting mixture was heated with stirring and heated to 1040y (10
00ml) of NOrtOn silica-alumina SA52l8ll4'' spheres were added.

It was then evaporated to dryness while stirring on a steam bath. 12 more
Drying was carried out at a temperature of 0° C. for 1 hour. The dried material was then transferred to a dish made from a 1 mesh stainless steel wire mesh sieve and calcined in a Matsufuru oven at 400'C in an ambient air atmosphere for 5 hours.

The amount of catalyst deposited on the carrier, calculated from the weight increase of the resulting catalyst, was 27.5%. Example 2 M016■4Ta2Fe1 or MOLvO-25Ta
Ammonium metavanadate (4) of 0.125Fe0.12570V. 6 g atoms ■) and 424y para-ammonium molybdate (2.4 g atoms MO) were dissolved in 2e water in a stainless steel beaker with stirring at 60-80<0>C.

Add 66 g of tantalum oxalate solution (4) to the resulting solution.
60y of ferric nitrate Fe(NO3)3.9H20 dissolved in 100mt of water
(4). 15 g atoms of Fe) were added.

Approximately 60% of the water was evaporated from the resulting mixture under stirring and heating. The resulting thick slurry was transferred to a stainless steel evaporating dish, 1040y (1000ml) of Norton Silica Alumina (NO-SA-5218) 114'' spheres were added and evaporative drying was carried out with stirring on a steam bath. The dried material was transferred to a cage made from a 10 mesh stainless steel wire sieve and calcined in air at 400°C in a Matsufuru furnace for 5 hours.The resulting catalyst was deposited on a support calculated from the weight gain. The amount of catalyst is 19.
It was 2%.

Example 3 M016v4Ta1・33Fe0・67si1・(
Or MOLvO・25Ta0-083
Ammonium metavanadate (4) of Fe0-012si0-08335.1y. 3 gram atom V) and 21
2y of rose-ammonium molybdate (1.2 g atom MO) in a stainless steel evaporating dish for 60 min.
Dissolved in 1.1e water with stirring at ~80°C.

126q of tantalum oxalate sol (22
8yTa20. /e) (0.1 gram atom of Ta), 20.2y of ferric nitrate nonahydrate (0
．． 05 g atoms Fe) and 20y LUDOX AS-30 (0
．． 1 gram atom of Si) was added.

The resulting mixture was heated with stirring and heated to 770y (970y).
m1) Norton Silica Alumina SA52O5ll4
``Added a sphere.

Next, it was evaporated to dryness while stirring on a steam bath, and further 120'
It was dried at a temperature of C for 16 hours. The thus dried material was then transferred to a basket made from a 10 mesh stainless steel wire mesh sieve and calcined for 5 hours in a Matsufuru furnace at 400° C. under an ambient atmospheric atmosphere.

The amount of catalyst deposited on the carrier calculated from the weight increase of the resulting catalyst was 22.5%. Example 4 M016V4NY)2CU1 or MOL■0・25N
Ammonium metavanadate (4) of b0, 125C, 062542y. 36g atom V) and 254y
ammonium molybdate (1.44 g atom MO) in a stainless steel evaporating dish.
'C and dissolved in 1.2g of water with stirring.

To the resulting solution was added 158y of niobium oxalate (4). 18
Gram atoms of Nb) and 22q of cupric nitrate (a) dissolved in 60ml of water. 09 gram atoms of Cu) were added.

The resulting mixture was heated with stirring and added to 1040
y (1000mt) of Norton Silica Alumina SA5
2l8ll4'' spheres were added and then evaporated to dryness with stirring on a steam bath.

Further, drying was performed at a temperature of 120° C. for 16 hours. This dry material was then transferred to a cage made from a 10 mesh stainless steel wire sieve and placed under an ambient atmosphere for 40 minutes.
It was fired for 5 hours in a Matsufuru furnace at 0'C.

The amount of catalyst deposited on the carrier, calculated from the weight increase of the resulting catalyst, was 15.9%. Comparative Examples 1 to 5 described below
These catalysts are outside the scope of this invention. That is, these Comparative Examples 1 to 3 contain 0.5y or more atoms of CO and/or Fe per 1y atom of MO, and Comparative Examples 4 to
Catalyst No. 5 does not contain any MO. These catalysts exhibited little or no selectivity for converting ethane to ethylene when tested according to Test Method A. Comparative example 1 M016c014Mn2 or MOlcOO・875M
Ammonium molybdate (8.82 g atom MO) of n0.12515569 was dissolved in 4.16 e of water with stirring at 60-80°C in a stainless steel evaporating dish.

178.4q of manganese sulfate (1.
06 g atom Mn) and 2328 g cobaltous nitrate (8 g atom CO2) dissolved in 1760 mt water.
) was added.

The resulting mixture was heated with stirring, a 633y titanium hydrate bulb was added, and the slurry was neutralized with an aqueous ammonia solution dissolved in 677g and 1243mt of water.

Next, it is evaporated to dryness while stirring on a steam bath, and further heated to 120°C.
It was dried at a temperature of 2 hours. The dried material was then transferred to an evaporation desk and calcined for 8 hours in a Matsufuru furnace at 400° C. under an ambient atmosphere. The obtained catalyst was made into pellets and roasted at 550°C for 1 hour. Catalytic testing of this material using test method A revealed no selectivity to ethylene and complete combustion started at 210°C. Comparative example 2 M016Fe1・6c06・4w3・2B11・6si
2.16K0.1 or MOlFeO.1C00.4W
0.2B10.1Sj0.135K0.006648V
of rose-ammonium tungstate (2.483 g atom W) and 2124 f rose-ammonium molybdate (12.03 g atom MO) were mixed with stirring at 60-80 °C in a stainless steel evaporating dish. dissolved in water.

To the resulting solution were added 14009 cobaltous nitrate hexahydrate (4.81 g atom CO) and 486y ferric nitrate nonahydrate (1.203 g atom Fe) (8).
y of bismuth nitrate pentahydrate (1.204 g atoms Bl), 300 ml of water and a further 1400 TrL1
1.35% potassium hydroxide solution dissolved in (4). 07
2 gram atoms of K) were added.

The resulting mixture was heated with stirring and to it was added 320y of Ludox and 30.5% colloidal silica sol.

Next, it was evaporated to dryness while stirring on a steam bath, and further heated to 120°C.
It was dried for a period of time at a temperature of . This dry substance is then mixed with 10
It was transferred to a cage made from a mesh stainless steel wire sieve and fired in a Matsufuru furnace at 400'C in an ambient atmosphere for 5 hours. The catalyst was mixed with 10% of its weight of naphthalene and pelletized into 5116" x 5116" cylinders and roasted at 450'C for 6 hours. Catalytic test results of this material according to Test Method A showed no selectivity to ethylene by oxidation of ethane at 366C. Comparative Example 3 M016Fe8 or MOlFeO. 5 35.3 Da rose ammonium molybdate (4).
2 g atoms MO) was dissolved in 200 ml of water with stirring at 60-80° C. in a stainless steel evaporating dish.

35' ferric nitrate hexahydrate (4) dissolved in 200 ml of water was added to the resulting solution. 1 gram atom of Fe) was added. Heat the resulting mixture while stirring and ? 1, then 1
It was dried at a temperature of 20°C for an hour.

The dried material was then transferred to a silica dish and calcined at 400° C. in a Matsufuru furnace for 4 hours under an ambient atmosphere of pure oxygen.

The amount of catalyst obtained was 34 g. Catalytic testing of this catalyst according to Test Method A showed that the reaction started at 276°C but had no selectivity for ethylene production. Comparative Example 4 v3sb12ce1 8.7y of vanadium pentoxide (4). 096 g atom of V) in a glass evaporating dish at 55°C with stirring.
Dissolved in 5ml concentrated (16N) hydrochloric acid and 200ml ethanol.

To the resulting solution was added 114.4y of antimony pentachloride (a) dissolved in 80ml of concentrated HCe. 383 gram atom S
b) and 13.8479 cerium trinitrate hexahydrate (4) dissolved in 100 ml of ethanol. 0.32 gram atoms of Ce) was added.

The resulting mixture was neutralized with 440 ml of concentrated ammonium hydroxide dissolved in 700 ml of water.

The precipitate was filtered, washed on the filter with 1000 ml of water and then dried for an hour at a temperature of 120°C. The dried material was transferred to a cage made from a 10 mesh stainless steel wire sieve and placed in an air ambient atmosphere for 1 hour.
5! It was fired at 750°C in a Matsufuru furnace for 30 minutes.

J catalyst test results for this material according to test method A, 2
It showed activity in combusting ethane at 67C but did not show selectivity for ethylene production. Comparative Example 5 S1). VlNblBl5 28fI ammonium metavanadate (0.240
4 g atoms of ■) were dissolved in 700 ml of water with stirring in a stainless steel evaporating dish at 60-80°C.

583f1 bismuth nitrate pentahydrate (
1.202 g atom Bl), 180 f1 antimony trioxide (1.202 g atom Sb) and 219
Niobium oxalate sol (4) dissolved in 720 ml of nitric acid to y (172 mt). 2404 gram atoms of Nb) were added. The resulting mixture was heated with stirring and heated to 770y (
1000mL) of Norton Silica Alumina SA52O
5 1 4" spheres were added and evaporated to dryness with stirring on a steam bath and further dried at a temperature of 120°C for an hour. The dried material was transferred to a cage made from a 10 mesh stainless steel wire screen and air It was calcined at 400°C in a Matsufuru furnace in an ambient atmosphere for 5 hours.The amount of catalyst deposited on the carrier was 36.1%, calculated from the weight increase of the obtained catalyst.
It was hot. When tested using Catalyst Test Method A, the catalyst exhibited initial activity at 525°C. However, the % selectivity of ethane to ethylene at this temperature is only 26
It was %. The catalysts of the following Examples 5-8 were each prepared as described below and were subjected to oxidation of ethane at one or two points between 300°C and 400°C according to Catalyst Test Method B. The conversion rate (%) and efficiency (%) to ethylene by the dehydrogenation reaction were measured.

The results will be summarized later in Table 2. Example 5 M016■8Fe1 or MOLVO◆5Fe0-06
2515.9y ammonium metavanadate (a)
．． 136 gram atoms ■) and 48.1y ammonium paramolybdate (4). 272 gram atom MO)
and a stainless steel steam jacketed evaporating dish inside the 85~
It was dissolved in 0.3' water at 95°C with stirring.

To the resulting solution was added 4.8y of ferric sulfate (
Solution of Fe2[SO4]3-9H20) (a). 017
Gram atoms of Fe) were added. The resulting mixture was heated with stirring, and 130y of Norton Silica Alumina 52
One meter of 4×8 mesh (irregular type) was added and evaporated to dryness with stirring.

This was further dried at a temperature of 120°C for 16 hours. The thus dried material was then transferred to a cage made from a 10 mesh stainless steel wire screen and calcined in a Matsufuru furnace at 400'C for 4 hours under an ambient air atmosphere.

The amount of catalyst deposited on the carrier, calculated from the weight increase of the resulting catalyst, was 27.4%. Example 6 M016■4Sb7 or MOLVO. 5SbO. lg
, 7 Oy of ammonium metapanadate (a). 6 g atom of V) and 424y of rose-ammonium molybdate (2.4 g atom MO) at 60-80 TeC with stirring in a stainless steel evaporating dish.
dissolved in water.

95y of oxalic acid (in 500 mt of water) was added to the resulting solution.
(4). 75 mol H2C2O4) and 370y of colloidal antimony oxide (10% Sb) (a). 3 gram atoms of Sb) were added.

The resulting mixture was heated with stirring and heated to 1040y (1
000m1) Norton Silica Alumina 5218 No.1
Added '4'' sphere.

Next, it was evaporated to dryness while stirring on a steam bath, and further heated to 120°C.
It was dried for 16 hours at a temperature of . The dried material was transferred to a cage made from a 10 mesh stainless steel wire mesh sieve and calcined at 400° C. for 4 hours in a Matsufuru furnace under an ambient air atmosphere.

The amount of catalyst deposited on the carrier, calculated from the weight increase of the resulting catalyst, was 16.8%. Example 7M016■4
Si32 or MOLVO. 23.9y of ammonium metavanadate (4) in a 25Si2 stainless steel steam jacketed evaporating dish. 204 gram atoms of V) and 144.3y of ammonium vara-molybdate (a). 817 g atoms MO) with stirring.
Dissolved in 0.5e of water at ~95°C.

326y “LudOx AS” (30.1% SlO2) (1.6
33 gram atoms of Si) were added.

The resulting mixture was heated with stirring, evaporated to dryness, and further dried at a temperature of 120° C. for 1 hour.

This dry material was crushed into 4×8 mesh and then
The mixture was transferred to a cage made with a 0-mesh stainless steel wire mesh sieve, and baked at 400° C. for 4 hours in an ambient air atmosphere. No support was added which was the net catalyst. Example 8 M016■8・Sn2 or MOLvO・5sr10・
12516.0y ammonium metavanadate (a). 137 g atoms ■) and 48.1y of ammonium rose-molybdate (4). 272 grams atom MO)
was dissolved in 0.5e water at 85-95°C with stirring in a stainless steel steam-jacketed evaporating dish.

To the resulting solution was added 7.7y of stannic chloride (
Sllce2・2H29) (4). 0.34 gram atoms of Sn) and 5 ml of concentrated hydrochloric acid were added. The resulting mixture was heated with stirring, 4×8 mesh (irregular shape) of 140y Norton Silica Alumina 521 square was added, stirred and evaporated to dryness.

This was further dried at a temperature of 120° C. for 1 hour. This material was then transferred to a cage made from a 10 mesh stainless steel wire screen and calcined at 400° C. for 4 hours in a Matsufuru furnace under an ambient air atmosphere. The amount of catalyst deposited on the carrier calculated from the weight increase of the obtained catalyst is 23.1
It was %. Examples 9-17 Catalysts 9-17 were prepared as follows and evaluated using Catalyst Test Method B.

Each of these catalysts contains the elements MO, V and Nb as well as one other x and Y element. The composition of each catalyst is shown at the beginning of each example. 300~ for each of these catalysts
Ethane to ethylene oxydehydrogenation conversion % and efficiency % evaluated at two hotspot temperatures between 400 °C
was measured.

The results are shown later in Table 3. Example 9 M016V4Nb>KO・5 or MOLVO・25N
Y) Ammonium metavanadate (4) of 0.125K0.0318.0y. 068 gram atom V) and 48
．． 1y ammonium rose-molybdate (a). 27
2 g atoms of MO) were added to 0.5' of water with stirring in a stainless steel steam-jacketed evaporating dish.
It was dissolved at 5-95°C.

Add 0.85y of potassium nitrate (KNO3) to the resulting solution.
(stomach). 0084 gram atom K), 31f1 niobium oxalate solution (14.6% Nb2O5) (a). 034
gram atom Nb) and 2.8y ammonium nitrate (NHlNO3) (4). 035 mol) was added.

The resulting mixture was heated with stirring and 4×8 mesh (irregular shape) of 150y Norton Silica Alumina 521m was added. The mixture was then evaporated to dryness while stirring, and further dried at 120'C for 16 hours. The thus dried material was then transferred to a basket made from a 10-mesh stainless steel wire mesh sieve and placed under an ambient air atmosphere for 400 min.
It was baked in a Matsufuru furnace at ℃ for 4 hours.

The amount of catalyst deposited on the carrier, calculated from the weight increase of the resulting catalyst, was 17.9%. Example 10 N4016V4Nb4P4 or MOLVO・25Nb
0.25P0-Otsu8y ammonium metavanadate (4). 068. Gram atom V) and 48.1y of ammonium rose-molybdate (a). 272 g atom MO) was dissolved in 0.5 f water at 85-95° C. with stirring in a stainless steel steam-jacketed evaporating dish.

Add 7.8y of phosphoric acid (85.6% H3P) to the resulting solution.
O4) (4). 068 gram atoms of P), 62y of niobium oxalate solution (14.6% Nb2O5) (a). 06
8 gram atoms of Nb) and 5.6y of ammonium nitrate (0.07 moles of NH4NO3) were added. The mixture was heated with stirring and 150 f of 4×8 mesh (irregular shape) of 521 square meters of Meton silica alumina was added. Next, this was evaporated to dryness while stirring, and further dried at a temperature of 120° C. for 16 hours. The dried material was transferred to a cage made from a 10 mesh stainless steel wire mesh sieve and calcined in a Matsufuru furnace at 400° C. for 4 hours under an ambient air atmosphere.

The amount of catalyst deposited on the carrier calculated from the weight increase of the catalyst thus obtained was 25.3%. Example 11 M016V8Nb2Ce2 or MOLvO・5Nb0
・125ce0・12515・9y ammonium metavanadate (a). ■) of 136 gram atoms and 48.
1y ammonium rose-molybdate (a). 272
gram atomic MO) in 0.5e water with stirring in a stainless steel steam-jacketed evaporating dish.
It was dissolved at 95°C.

Add to the resulting solution 31y of niobium oxalate solution (14.6% Nb7O5) in 100ml water (4). 034 gram atoms of Nb) and 14y of cerium nitrate (41.8% CeO2) dissolved in 150 ml of water (4). 034 gram atoms of Ce) were added.

The resulting mixture was heated with stirring and a 4×8 mesh (irregular shape) of 150y Norton Silica Alumina 521 square was added.

Next, this was evaporated to dryness while stirring, and further dried at a temperature of 120° C. for an hour. The thus dried material was transferred to a cage made from a 10 mesh stainless steel wire mesh sieve and heated to 400°C in a Matsufuru furnace under an ambient air atmosphere.
It was baked for 4 hours.

The amount of catalyst deposited on the carrier, calculated from the weight increase of the resulting catalyst, was 28%. Example 12M016V8Nb
2C02 or MOLVO・5Nb0・125C00・
12515.9y ammonium metavanadate (a). 136 g atoms of V) and 48.1y of vara-ammonium molybdate (4). 272 gram atom MO
) was dissolved in 0.5e water at 85-95°C with drying in a stainless steel steam-jacketed evaporating dish.

Add 31y of niobium oxalate solution (14.6% Nl) in 100ml of water to the resulting solution.05)(4). 034 g atoms of Nb) and 8.5y of cobalt acetate [CO(CH3COO)2.4H20] (a) dissolved in 150 ml of water. 0.34 gram atoms of CO) were added.

The resulting mixture was heated with stirring and 4×8 mesh (irregular shape) of 150y Norton Silica Alumina 521m was added.

Next, this was evaporated to dryness while stirring, and further heated to 1ei1! at a temperature of 120'C. Dry for a while. The thus dried material was then transferred to a cage made from a 10 mesh stainless steel wire mesh sieve and calcined for 4 hours at 400° C. in a Matsufuru furnace under an ambient air atmosphere.

The amount of catalyst deposited on the carrier, calculated from the weight increase of the resulting catalyst, was 26.3%. Example 13 M016V8N■CU2 or MOL■0. , Nb0.
125CU0.12, 15.9y of ammonium metavanadate (4). 136 g atom V) and 48.1
ammonium molybdate of y (4). 272 g atom MO) in 0.5 e water with stirring in a stainless steel steam-jacketed evaporating dish.
Dissolved at °C.

Add 31y of niobium oxalate solution (14.6% Nb2O5) (a) to the resulting solution in 100ml of water. 034 gram atoms of Nb) and 6.8y of cupric acetate [(CH3COO)2CU-H2O] (a) dissolved in 150 mt of water.
．． 0.34 gram atoms of Cu) were added.

The resulting mixture was heated with stirring and a 4×8 mesh (irregular shape) of 150y Norton Silica Alumina 521 square was added.

Next, this was evaporated to dryness while stirring and further dried at a temperature of 120'C for 16 hours. The thus dried substance is then
Transfer to a cage made from a 0-mesh stainless steel wire mesh sieve and heat in a Matsufuru furnace under an ambient air atmosphere for 4 hours.
It was baked at 00°C for 4 hours.

The amount of catalyst deposited on the carrier, calculated from the weight increase of the resulting catalyst, was 25.1%. Example 14 M016V8Nb7Fe2 or MOL o-5NY)
o●125Fe0・12515.9f ammonium metavanadate (4). 136 gram atom V) and 48
．． 1y ammonium rose-molybdate (a). 27
2 g atoms of MO) in 0.5 e water with stirring in a stainless steel steam-jacketed evaporating dish.
Dissolved at ~95°C.

To the resulting solution was added a solution of 31q of niobium oxalate (14.6% Nb2O.) (0.034 g atom of Nb) in 10 ml of water, 4.4y of oxalic acid and 6.4y of sulfuric acid in 150mt of water. Iron [Fe2(C2O4)3] (
4). A solution of 0.34 gram atoms of Fe) was added.

The resulting mixture was heated with stirring and 4×8 mesh (irregular shape) of 150y Norton Silica Alumina 521m was added.

Next, this was evaporated to dryness while stirring, and further dried for one hour at a temperature of 120°C. The material thus dried is then
Transfer from a mesh stainless steel wire sieve to a basket and heat in a Matsufuru furnace under an ambient air atmosphere for 400 minutes.
It was baked at ℃ for 4 hours.

The amount of catalyst deposited on the carrier, calculated from the weight increase of the resulting catalyst, was 23%. Example 15 M016■8Nb2N12 or MOLVO・5Nb0
・125Ni0・12515.9y ammonium metapanadate (4). 136 gram atom V) and 48.
1y ammonium rose-molybdate (4). 272
gram atomic MO) in 0.5e water with stirring in a stainless steel steam-jacketed evaporating dish.
It was dissolved at 95°C.

Add 31y of niobium oxalate solution (14.6% Nb2O5) (a) to the resulting solution in 100ml of water. 034 g atoms of Nb) and 8.5 q of diacetate (Ni(C2H3O2)2.4H2) dissolved in 150 ml of water.
0] (0.034 gram atom of Nl).

The resulting mixture was heated with stirring and a 4×8 mesh (irregular shape) of 150y of Norton Silica Alumina 521 was added.

Next, this was evaporated to dryness while stirring, and further heated to 120°C.
Dry at a temperature of ■ hours. The dried material was then transferred to a cage made from a 10 mesh stainless steel wire screen and calcined in a Matsufuru furnace at 400'C under an ambient air atmosphere for 4 hours.

The amount of catalyst deposited on the carrier, calculated from the weight increase of the resulting catalyst, was 26.4%.

Example 16 M016■8Nb2Sj3.

or MOLVO. 5NbO. l. Ammonium metavanadate (4) of Si235.9y. 307 gram atoms ■) and 108.0y ammonium rose-molybdate (a). 612 g atom MO) was dissolved in 0.5e water at 85-95° C. with stirring in a stainless steel steam-jacketed evaporation dish. Add 69.6y of niobium oxalate solution (14.6%Nb2) to the obtained solution.
O5) (4). 076 gram atom Nb) and 244.2
y(7)66LudOxAS'' colloidal silica sol (1.223 gram atoms Si) was added.

The resulting mixture was heated and evaporated to dryness with stirring, and further dried at a temperature of 120° C. for 1 hour. The thus dried material was crushed to 4.times.8 mesh, transferred to a cage made from a 10 mesh stainless steel wire screen, and calcined at 400.degree. C. for 4 hours in a Matsufuru furnace under an ambient air atmosphere. This is the net catalyst and does not contain any support. Example 17M016■8Nb2U1 or MOLVO
・5Nb0・125U0-12515.9y ammonium metavanadate (a). 136 gram atom V)
and 48.1y of rose-ammonium molybdate (a)
．． 272 g atom MO) was dissolved in 0.35 e of water at 85-95° C. with stirring in a stainless steel steam-jacketed evaporating dish.

Add 31y niobium oxalate solution (14.6
%Nb2) (a). 034 gram atom Nb) and 7.2
y of uranyl acetate [(CH3COO)2U02・2H2
0] (4). 017 gram atoms of U) were added.

The resulting mixture was heated with stirring and a 4×8 mesh (irregular shape) of 140y Norton Silica Alumina 521m was added.

Next, this was evaporated to dryness while stirring, and further dried at a temperature of 120°C for 1eif! Intermittent drying was performed. The thus dried material was then transferred to a cage made from a 10 mesh stainless steel wire mesh sieve and calcined for 4 hours at 400°C in a Matsufuru furnace under an ambient air atmosphere. The calculated amount of catalyst deposited on the carrier was 27%.

Claims (1)

[Claims] 1 General formula Mo_aV_bX_cY_d (in this formula,
a is 1, b is 0.05 to 1, c is 0 to 1, and d is 0.03 to about 2; when X is Ta, Y is Fe, or Fe and Si; is Nb, Y is Fe, Cu, Si, K
, P, Ce, Co, Ni or U, and when c is 0, Y is Fe, Sb, Si or Sn). Molybdenum-containing catalyst for hydrogenation. 2. A molybdenum-containing catalyst according to claim 1, which is a calcined composition consisting of the elements Mo, V, Nb and K. The molybdenum-containing catalyst according to claim 1, which is a fired composition consisting of three elements Mo, V, Nb and Ce. 4. The molybdenum-containing catalyst according to claim 1, which is a calcined composition consisting of the elements Mo, V, Nb and U.