JPS6361291B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to the gas phase catalytic dehydrogenation of ethane to ethylene in the presence of oxygen, i.e. the oxydehydrogenation of ethane to ethylene. Ethylene has traditionally been produced industrially by thermally decomposing ethane in an endothermic reaction carried out at temperatures of about 600-1000°C (US Pat. No. 3,541,179). Reaction times in such processes are very short, making it difficult or impossible to efficiently recover heat from the process stream. Additionally, given the high temperatures used,
The use of special alloys is required in the construction of the furnace or reaction vessel to carry out the reaction. The cracking reaction also produces relatively large amounts of low boiling byproducts such as hydrogen and methane, making recovery of ethylene from such byproducts complicated and more expensive. It is possible to oxydehydrogenate ethane using a variety of oxyhalogenation catalyst systems in an exothermic reaction. However, these reactions are at least ca.
achieved only at a temperature of 600°C (U.S. Patent No.
3080435 specification). In addition, the presence of halogen atoms in this case increases the difficulty of recovering the olefin produced. Also, special and expensive construction materials are required to resist corrosion by halogens and hydrogen halides within the reaction system. Furthermore,
In order to make this process economical, the halogen itself must be recovered and recycled. Oxydehydrogenation of selected _C3 alkanes by exothermic reactions at relatively high temperatures is also possible with selected catalysts containing vanadium (U.S. Pat.
3,218,368, 3,541,179 and 3,856,881) and selected catalysts containing vanadium and molybdenum (US Pat. No. 3,320,331). Use of catalyst systems containing molybdenum and vanadium for the gas phase oxidation of α,β-unsaturated aliphatic aldehydes, such as acrolein, to the corresponding α,β-unsaturated carboxylic acids, such as acrylic acid. is known. These catalyst systems are described in Belgian patents nos. 821322, 821324 and Belgian patent nos.
Elements as disclosed in each specification of No. 821325
Mo, V and X (where X is Nb, Ti or Ta
). However, prior to the present invention, it was not possible to readily oxydehydrogenate ethane to ethylene at relatively low temperatures and with relatively high conversion efficiency, selectivity, and productivity. The expressions conversion rate (%), selectivity (%), and productivity (productivity) used in the present invention are defined as follows. I (%) conversion of (ethane) = 100 × A / number of moles of ethane in the reaction mixture fed to the catalyst bed Ia where A is the total carbon-containing product excluding ethane in the effluent Mol ethane - total equivalent (carbon basis) Selectivity (or efficiency) % for ethylene (or acetic acid) = 100 × number of moles of ethylene (or acetic acid) produced / A Productivity (production capacity) of ethylene (or acetic acid) )
= pounds of ethylene (or acetic acid) produced per cubic foot of catalyst (in the catalyst bed) per hour of reaction time Ethane is produced using certain catalyst compositions containing molybdenum and any other various elements. ,500℃
It has been found that oxydehydrogenation to ethylene can be carried out with relatively high conversion efficiency, selectivity and productivity by gas phase reaction at temperatures of 450 DEG C. or lower, preferably below 450.degree. The purpose of the present invention is to process ethane at a relatively low temperature (500℃).
The object of the present invention is to provide a process for oxydehydrogenation of ethylene at relatively high levels of conversion, selectivity and productivity. Yet another object of the present invention is to eliminate the concomitant production of significant amounts of gaseous by-products such as methane and hydrogen, which make the cryogenic separation and purification of ethylene difficult and expensive. The object of the present invention is to provide a method for oxydehydrogenating ethane to ethylene. The above objects of the present invention are the elements Mo, X and Y.
Mo _a X _b Y _c [In this formula, X represents the element V alone or together with V.
Represents a combination with Nb or Ta, Y is Ce, Co,
Cu, Fe, K, Ni, P, Sb, Si, Sn and/or U, a is 1, b is 0.05 to 1, and c is 0.03 to about 2, provided that Fe, Co and ( or) with an overall value of c to Ni of <0.5]. The numbers a, b, and c indicate the relative gram-atomic proportions of the elements Mo, X, and Y, respectively, present in the catalyst composition. The Si used to form the catalyst compositions shown above is other than Si, which can be present in any carrier (support) that can be used to support the catalyst, as described below. Catalyst Elements Mo, It may also be a chemical combination of oxides. The catalyst is preferably made from a solution of soluble compounds (salts, complexes or other compounds) of each of the elements Mo, X and Y, or alternatively Si
In the case of Sb, it is also produced from a colloidal sol. The solution is 1-7 and preferably 2-6
Preferably, it is an aqueous system with a pH of . Solutions of the various compounds containing the elements are prepared by dissolving sufficient amounts of soluble compounds of each element to provide the desired a:b:c gram atomic ratios of the elements Mo, X, and Y, respectively. 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 selected such 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): The surface area is approximately 0.1 to 500 m ² /g, and the apparent porosity is
30 to 60%, at least 90% of the pores have a pore size of 20 to 1500 microns, and the particle or pellet form has a diameter of about 1/8 to 5/16 inch. This deposition immerses the support in the final mixture of all compounds, evaporates most of the solvent, and then leaves the system at approximately
This is achieved by drying at 80-220°C for 2-60 hours. The thus dried catalyst is then calcined to form the desired Mo _a X _b Y _c composition by heating in air or oxygen at about 220-550° C. for 1/2 to 24 hours. Supports that can be used are silica, aluminum oxide, silicon carbide, zirconia, titania and mixtures thereof. In this case the supported catalyst is usually about 10-50% by weight.
of the catalyst composition, the remainder being the carrier. The molybdenum is preferably in solution in the form of an ammonium salt of molybdenum, such as ammonium para-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 can also be used are partially water-soluble molybdenum oxide, molybdic acid and molybdenum chloride. Vanadium is preferably in solution in the form of ammonium salts of vanadium such as ammonium meta-vanadate as well as ammonium decarvanadate, or in the form of organic acid salts of vanadium such as acetate, oxalate and tartrate. to be introduced. 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 oxalates. 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. . 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 (SiO ₂ ) sol. Phosphorus is preferably introduced into the catalyst system as phosphoric acid or a water-soluble phosphate. It is believed that for the catalyst to be most effective, the Mo, X and Y metal components should be somewhat reduced below their highest possible oxidation state.
This is the NH ₃ that is introduced into the solution system that creates the catalyst.
This is achieved during heat treatment of the catalyst in the presence of an organic reducing agent such as a reducing agent or an organic complexing agent. 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 the catalyst bed. Supported or unsupported catalysts can be used in fixed or fluidized beds. Ethane The ethane source used as feedstock must be a gas stream containing at least 3% by volume ethane at atmospheric pressure. This gas flow is small i.e. <5% by volume.
Each may contain H ₂ , CO and C ₃ -C ₄ alkanes and alkenes. It may also contain large amounts, ie >5% by volume, of N ₂ , CH ₄ , CO ₂ and water vapor. The catalyst used in this invention is clearly unique in its ability to oxydehydrogenate ethane to ethylene. This is because these catalysts are propane,
This is because n-butane and butene-1 are not oxydehydrogenated, but rather these materials are combusted to carbon dioxide and other oxidized carbonaceous products. Reaction Mixture The components of the gaseous reaction mixture used as feed stream in the process of the invention and their relative proportions are as follows. 1 mole of ethane, 0.01-1/2
moles of molecular oxygen (as pure oxygen or in the form of air) and 0 to 0.4 moles of water (in the form of steam). Water or steam is used as a reaction diluent or as a heat regulator for the reaction. Other substances that can be used as reaction diluents or thermal regulators are nitrogen,
Inert gases such as helium, _CO2 and methane. In a normal reaction process without the addition of water, one mole of water is produced for every mole of oxydehydrogenated ethane. The water generated during this reaction produces about 0.05 to 0.25 moles of acetic acid for every mole of ethylene produced therein. However, the addition of water results in the production of additional amounts of acetic acid, ie, increased to about 0.25 to 0.95 moles of acetic acid for every mole of ethylene produced. The components of the reaction mixture are uniformly mixed before being introduced into the reaction zone. Each component is preheated separately or after mixing to about 200-500°C prior to introduction into the reaction zone. Reaction Conditions The preheated reaction mixture is contacted with the catalyst composition in the reaction zone under the following conditions. a pressure of about 1 to 30 atmospheres, preferably 1 to 20 atmospheres,
temperature of about 150-500℃, preferably about 200-400℃,
Contact time (reaction mixture on catalyst) of about 0.1 to 100 seconds, preferably about 1 to 10 seconds and a space velocity of about 50 to 500 h ^-1 , preferably 200 to 3000 h ^-1 . Contact time is defined as the ratio of the apparent volume of the catalyst bed to the volume of gaseous reaction mixture fed to the catalyst bed in a unit time under given reaction conditions. The above-mentioned reaction pressures are initially provided by the feed of gaseous reactants and diluent, and the pressure after the start of the reaction is preferably controlled by a suitable counterpressure regulator placed on the gaseous effluent side of the catalyst bed. can be maintained. The reaction temperature is preferably such that the catalyst bed is placed in a tubular conversion reactor whose walls are immersed in a suitable heat transfer medium such as tetralin, molten salt mixture, or other suitable heat transfer agent and heated to the desired reaction temperature. It is maintained by placing . According to the present invention, ethane is selectively oxydehydrogenated to ethylene and acetic acid without the addition of diluents other than water to give the following degrees of conversion %, efficiency % and productivity as the final product. be able to.

[Table] *Presence or absence of water added to ethane feed gas The following examples relate to the preparation of various catalyst compositions of the present invention and the use of such compositions in the oxydehydrogenation of ethane to ethylene. This will be described in detail along with comparative examples. Incidentally, the activity of each of these test catalysts was measured in a small U-tube reactor in which oxygen and ethane were supplied in a pulsatile flow (test method A), or in a continuous co-current flow of ethane and oxygen. In a standpipe reactor (test method B),
or by the back-mix 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.
The reaction zone containing the catalyst, a silica U-tube 20 inches long and 8 mm in diameter, 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. Preliminary investigation of the temperature situation in the sand bath showed that from top to bottom the temperature varied by less than 3 degrees above the fixed point set by the regulator. This microreactor was precisely coupled to a gas chromatograph to analyze the reaction product flow. Interrupt the helium supply line inside the chromatograph at a point immediately after the flow regulator, and connect it to the 8-hole 2
- Through the positioning valve [Union, Carbide Co., Model C4-70, Special Machinery Department] and from there the 6-hole manual sample injection valve [Union, Carbide, Model C4-70].
2112-50-2] to the U-tube reactor inlet leg, 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 flow from the reactor was routed back through a cooling trap and through an 8-hole valve which served to divert to either of the two analysis 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. Injection of feed gas (composition: 6.5% by volume oxygen, 8.0% by volume ethane, balance nitrogen) in pulsed streams of 2.0 ml was carried out by means of a gas-tight syringe through the port just before the catalyst. The gas passed through the reactor at 60 ml/min throughout and was carried over 3.0 g of catalyst diluted by helium carrier gas passing through an analytical gas chromatograph. Analysis of the resulting mixture was performed in a 10' x 1/8" diameter stainless steel column wrapped in Poropak(TM) R. The column was
℃ and heated at a rate of 10.degree. 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. Poropack R
is a fine particle spherical polystyrene resin cross-linked with divinylbenzene. Catalyst Test Method B The catalyst was tested in a tubular reactor under the following conditions. Ethane gas feed composition (vol%) is 9.0%
C ₂ H ₆ , 6.0% O ₂ and 85% N ₂ , the space velocity is
340hr ^-1 , total reaction pressure is 1 atm. The activity of the catalyst was then recorded as the temperature increased. The reactor consists of a 1/2" stainless steel standpipe and an approximately 12" deep molten salt bath (DuPont Hi-Tech™).
heat transfer salt].
A 1/8" thermocouple sleeve was passed through the length of the reaction tube and through the center of the catalyst bed. The temperature profile of the catalyst could be determined by sliding the thermocouple through the sleeve. The top of the catalyst bed is lower than the surface of the heat transfer salt.
26 ml of catalyst was introduced into the tube 4″ below.
The catalyst bed was 5-5.5" long so that it had a depth-to-section ratio of >10. The upper zone of the catalyst bed was enriched with glass beads, which served as a preheater. Gas outflow from the reactor The bodies were passed through a condenser and trap at 0°C.The gas and liquid products thus obtained were analyzed as described below. Catalyst Test Method C The reactor used in this high pressure study was centrally located. Magnedrive with bottom-stirring catalyst basket and side product effluent line
It was in a type autoclave. 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 16 to 20, 1969. ``Reactors, Vapor Phases,'' submitted as Proceedings 42E in the Second Part of the Symposium on ``Advances in High Pressure Technology,'' and available from AIChE, 345 47th Street, East New York, 10017, USA.
It is of the type depicted in Figure 1 of the paper by Bertie, Hambrick, Mallon, and Wrotzke entitled ``Catalytic Studies.'' A backmix autoclave has a stainless steel catalyst vessel located above the stirring fan blades. The fan blows gas upward and inward through the catalyst bed in a conventional manner. Two thermocouples measure the temperature at the inlet and outlet. Oxygen was fed into the reactor through the 1/4" line through the rotameter at a pressure of approximately 150 psig. The gaseous ethane-CO _x mixture was fed through the rotameter and then immediately before it was introduced into the reactor. The liquid was then pumped directly into the reactor via the same feed line as the gas, but after the gas was mixed the liquid inlet was connected to the line. Outflow gas was removed via a port on the reactor side. The condensable liquid product was removed by a series of cooling traps in two baths.
The first bath contained moist ice at 0° C. and had two cooling traps immersed therein. The second bath of dry ice and -78°C acetone had two cooling 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. An 8-hole sampling valve allowed direct sampling of both product and feed gas through lines connected directly to the reactor feed and product streams. No external recirculation was used. Determine the bulk volume of the weighed catalyst sample (approx.
150c.c.．． ), the sample was placed in a catalyst basket. In each case, the amount of catalyst charged was approximately
It was 131.1g. Stainless steel screens were placed above and below the catalyst bed to minimize catalyst wastage and circulation of catalyst fines. After loading the reactor with the catalyst basket and sealing the reactor, the process line was pressure tested at ambient temperature to a pressure of about 100-200 psig, above the expected maximum working pressure. Nitrogen was used for this test. When it was found that there were no leaks in the reactor, the pure
_N2 was passed through the reactor and the temperature was raised to between 275 and 325 °C. Gas feedstock composition in % by volume:
It was in the range of _76-97 % _C2H6 , 3-6% _O2 , 0-10% _H2O , and 0-10% _COx . After the desired temperature was obtained, the oxygen and ethane-CO _x mixture was adjusted to provide the desired steady state proportions 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 and steady state. The liquid product trap is then drained and the dry gas test meter reading is taken. The start time of operation was recorded. Effluent gas samples during operation were analyzed for C ₂ H ₆ , C ₂ H ₄ , O ₂ , CO, CO ₂ and other volatile hydrocarbons. At the end of the run, the liquid 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 in all tests conducted with test methods B and C were O ₂ , N ₂ and
5A molecular sieves (14/30 mesh) in a 10′ x 1/8″ column at 95°C for CO and (O ₂ ,
N ₂ , CO are the same), CO ₂ , ethylene, ethane, and H ₂ O in a 14′ x 1/8″ column.
(80/100 mesh) at 95°C. The liquid product, when fully obtained, was analyzed by mass spectrometry for H ₂ O, acetaldehyde, acetic acid, and other components. Poro Pack Q
(TM) is a microparticle 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. C ₂ H ₆ +1/2O ₂ →C ₂ H ₄ +H ₂ O C ₂ H ₆ +7/2O ₂ →2CO ₂ +3H ₂ O The reaction conditions for the above three test methods were as follows.

[Table] Of the catalysts prepared as described below, Catalysts 1 and 2 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 3 was evaluated using Test Method B and the test results are also shown in Table 1. In testing the catalysts of Examples 1 and 2, the lowest temperature at which catalytic activity was initially imparted by the catalyst was first tested, and this was taken as the temperature of initial activity, To. The selectivity of the catalyst for the oxydehydrogenation of ethane to ethylene with To was then determined in this manner. Next, to determine the minimum temperature above To at which 10% conversion of ethane to ethylene is achieved,
The activity of each catalyst was evaluated at a higher temperature and this temperature is shown in Table 1 as _T10 . The selectivity of the catalyst for the oxydehydrogenation of ethane to ethylene at T ₁₀ was also determined and shown in Table 1. Example 1 Mo ₁₆ V ₄ Fe ₁ or Mo ₁ V _0.25 Fe _0.0625 70 g of ammonium meta-vanadate (0.6 g atom V) and 424 g ammonium para-molybdate (2.4 g atom Mo) were evaporated onto stainless steel. 2 in water with stirring at 60-80°C in a dish. To the resulting solution was added 60 g of ferric nitrate nonahydrate (0.15 gram atom iron) dissolved in 100 ml of water. The resulting mixture was heated with stirring and 1040g
(1000 ml) of Norton silica alumina SA5218 1/4" spheres were added. It was then evaporated to dryness with stirring on a steam bath. Further drying was carried out at a temperature of 120° C. for 16 hours. The dried material was It was then transferred to a dish made from a 1-mesh stainless steel wire mesh sieve and calcined in a Matsufuru furnace for 5 hours at 400°C in an ambient air atmosphere.The amount of catalyst deposited on the support was calculated from the mass increase of the resulting catalyst. Example 2 Mo ₁₆ V ₄ Ta ₂ Fe ₁ or Mo ₁ V _0.25 Ta _0.125 Fe _0.0625 70 g of ammonium meta-vanadate (0.6 gram atom of V) and 424 g of ammonium para-molybdate ( (2.4 g at. 60 g of ferric nitrate Fe (NO ₃ ) ₃ ·9H ₂ O (0.15
gram atom of Fe) was added. Approximately 60% of the water was evaporated from the resulting mixture under stirring and heating. Transfer the resulting thick slurry to a stainless steel evaporating dish, add 1040 g (1000 ml) of Norton Silica-Alumina (No. SA-5218) 1/4″ spheres,
It was evaporated to dryness with stirring on a steam bath. 120 more
Drying was carried out at a temperature of 16 hours. The thus dried material was transferred to a basket made from a 10-mesh stainless steel wire mesh sieve and calcined at 400° C. for 5 hours in an air-borne Matsufuru furnace. The amount of catalyst deposited on the carrier, calculated from the weight increase of the resulting catalyst, was 19.2% by weight. Example 3 Mo ₁₆ V ₄ Ta _1.33 Fe _0.67 Si _1.33 or Mo ₁ V _0.25
Ta _0.083 Fe _0.042 Si _0.083 35.1 g of ammonium meta-vanadate (0.3 g atom of V) and 212 g of ammonium para-molybdate (1.2 g atom of Mo) are mixed at 60-80 °C in a stainless steel evaporating dish. While stirring
1.1 dissolved in water. The resulting solution contained 126 g tantalum oxalate sol (containing 228 g Ta ₂ O ₅ /equivalent) (0.1 gram atom Ta), 20.2 g ferric nitrate nonahydrate (0.05
gram atom of Fe) and dissolved in 197 ml of water
20 g of LUDOX AS-30 (0.1 g atom Si) was added. The resulting mixture was heated with stirring and 770g
(970ml) of Norton Silica Alumina SA5205
1/4" spheres were added. The 1/4" spheres were then evaporated to dryness with stirring on a steam bath and further dried for 16 hours at a temperature of 120°C. The thus dried material was then sieved through a 10 mesh stainless steel wire sieve. It was transferred to a rack and calcined for 5 hours in a Matsufuru furnace at 400°C in an ambient atmosphere.The amount of catalyst deposited on the carrier, calculated from the weight increase of the obtained catalyst, was 22.5%. Example 4 Mo ₁₆ V ₄ Nb ₂ Cu ₁ or Mo ₁ V _0.25 Nb _0.125
Cuo _0.0625 42 g ammonium meta-vanadate (0.36 g atom V) and 254 g ammonium para-molybdate (1.44 g atom Mo) were mixed at 60-80°C in a stainless steel evaporating dish at 1.2
dissolved in water. To the resulting solution was added 158 g of niobium oxalate (0.18 g atom Nb) and 22 g cupric nitrate (0.09 g atom Cu) dissolved in 60 ml water. Heat the resulting mixture with stirring and add
1040g (1000ml) Norton Silica Alumina
SA5218 1/4" spheres were added and then evaporated to dryness with stirring on a steam bath. Further at a temperature of 120 °C for 16
Drying was carried out for a period of time. The dried material was then transferred to a cage 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 15.9%. The catalysts of Comparative Examples 1 to 5 described below are outside the scope of the present invention. In other words, these comparative examples 1 to 3 are
0.5g Co and/or Fe per 1g atom Mo
atomic or more, and the catalysts of Comparative Examples 4 and 5
It does not contain Mo at all. These catalysts exhibited little or no selectivity for converting ethane to ethylene when tested according to Test Method A. Comparative Example 1 Mo ₁₆ Co ₁₄ Mn ₂ or Mo ₁ Co _0.875 Mn _0.125 1556 g of ammonium para-molybdate (8.82 g atoms Mo) was dissolved in 4.16 g of water with stirring at 60-80° C. in a stainless steel evaporating dish. . The resulting solution contained 178.4 g manganese nitrate (1.06 g atom Mn) and 2328 g cobaltous nitrate (8 g atom Mn) dissolved in 1760 ml of water.
Co) was added. Heat the resulting mixture with stirring and add
633 g of titanium hydrate pulp was added and the slurry was neutralized with an aqueous ammonia solution of 677 g dissolved in 1243 ml of water. Next, it was evaporated to dryness while stirring on a steam bath, and further dried at a temperature of 120°C for 16 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, 550
Roasted at ℃ for 12 hours. A catalytic test on this material using test method A revealed no selectivity to ethylene and complete combustion started at 210°C. Comparative example 2 Mo ₁₆ Fe _1.6 Co _6.4 W _3.2 Bi _1.6 Si _2.16 Ko _0.1 or
Mo ₁ Fe _0.1 Co _0.4 W _0.4 Bi _0.1 Si _0.135 K _0.006 648 g of ammonium para-tungstate (2.483 g atom W) and 2124 g ammonium para-molybdate (12.03 g atom Mo) were placed in a stainless steel evaporating dish. 3 was dissolved in water with stirring at 60-80°C. Add 1440g of cobaltous nitrate 6 to the resulting solution.
hydrate (4.81 g atom Co) and 486 g ferric nitrate nonahydrate (1.203 g atom Fe) and 584 g
of bismuth nitrate pentahydrate (1.204 g atom
Bi), dissolved in 300ml water and further 1400ml
A 1.35% potassium hydroxide solution (0.072 gram atom K) was added. Heat the resulting mixture with stirring and add
Added 320g Ludotux and 30.5% colloidal silica sol. Next, it was evaporated to dryness while stirring on a steam bath, and further dried at a temperature of 120°C for 16 hours. The dried material was then transferred to a basket made from a 10 mesh stainless steel wire mesh sieve and calcined in a Matsufuru furnace at 400° C. for 5 hours under an ambient atmosphere. The catalyst was mixed with 10% naphthalene by weight and pelletized into 5/16" x 5/16" 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 366°C. Comparative Example 3 Mo ₁₆ Fe ₈ or Mo ₁ Fe _0.5 35.3 g of ammonium para-molybdate (0.2
Gram atomic Mo) was dissolved in 20 ml of water with stirring at 60-80 °C in a stainless steel evaporating dish. To the resulting solution was added 35 g of ferric nitrate hexahydrate (0.1 gram atom of Fe) dissolved in 200 ml of water. The resulting mixture is heated with stirring, filtered,
It was then dried at a temperature of 120°C for 16 hours. The dried material was then transferred to a silica wash 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 V ₃ Sb ₁₂ Ce ₁ 8.7 g of vanadium pentoxide (0.096 g at.
Dissolved in ml of concentrated (16N) hydrochloric acid and 200ml of ethanol. To the resulting solution was added 114.4 g of antimony pentachloride (0.383 g atom Sb) dissolved in 80 ml concentrated HCl and 13.847 g cerium nitrate hexahydrate (0.032 g atom Ce) dissolved in 100 ml ethanol. . The resulting mixture was neutralized with 440 ml of concentrated ammonium hydroxide dissolved in 700 ml of water. Filter the precipitate, wash with 1000ml water on the filter, then
It was dried for 16 hours at a temperature of 120°C. This dried material was transferred to a cage made from a 10 mesh stainless steel wire mesh sieve and placed in a Matsufuru furnace for 12 hours in an air ambient atmosphere.
It was fired at 750℃. Catalytic testing of this material by Test Method A showed activity in burning ethane at 262°C, but no selectivity for ethylene production. Comparative Example 5 Sb ₅ V ₁ Nb ₁ Bi ₅ 28g of ammonium meta-vanadate (0.2404
Gram atomic V) was dissolved in 700 ml of water with stirring at 60-80°C in a stainless steel evaporating dish. The resulting solution contains 583 g bismuth nitrate pentahydrate (1.202 g atom Bi), 180 g antimony trioxide (1.202 g atom Sb) and 219 g (172 ml)
Niobium oxalate sol (0.2404 g atom Nb) dissolved in 720 ml of 3N nitric acid was added. Heat the resulting mixture while stirring and weigh 770g.
(1000ml) of Norton Silica-Alumina
SA5205 1/4" spheres were added and evaporated to dryness with stirring on a steam bath and further dried for 16 hours at a temperature of 120°C. The dried material was transferred to a cage made from a 10 mesh stainless steel wire mesh sieve. The catalyst was calcined at 400°C in a Matsufuru furnace for 5 hours under an air ambient atmosphere.The amount of catalyst deposited on the support, calculated from the weight gain of the resulting catalyst, was 36.1%.In Catalyst Test Method A When tested, this catalyst
It showed initial activity at 525°C. However, the percent selectivity of ethane to ethylene at this temperature was only 26%.

[Table] The catalysts of Examples 5 to 8 below were each prepared as described below, and these catalysts were tested according to Catalyst Test Method B at one or two points between temperatures of 300°C and 400°C. The conversion rate (%) and efficiency (%) of ethane to ethylene by oxydehydrogenation reaction were measured. The results will be summarized later in Table 2. Example ₅ Ammonium _{meta - vanadate ( 0.136}
g atom V) and 48.1 g ammonium para-molybdate (0.272 g atom Mo) in a stainless steel steam jacket evaporating dish at 85-95°C.
Dissolved in 0.3% water with stirring. A solution of 4.8 g of ferric nitrate [Fe ₂ [SO ₄ ] ₃ ·9H ₂ O] in 400 ml of water (0.017 g atom) was added to the resulting solution.
Fe) was added. The resulting mixture was heated with stirring and 130 g of a 4×8 mesh of Norton Silica-Alumina No. 5218 (irregular) 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 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 resulting catalyst, was 27.4%. Example 6 Mo ₁₆ V ₄ Sb ₂ or Mo ₁ V _0.25 Sb _0.125 70 g of ammonium meta-vanadate (0,6
gram atom V) and 424 g ammonium para-molybdate (2.4 g atom Mo) at 60-80°C with stirring in a stainless steel evaporating dish.
2.0 dissolved in water. 95 g of oxalic acid (in 500 ml of water) to the resulting solution
(0.75 mol H ₂ C ₂ O ₄ ) and 370 g colloidal antimony oxide (10% Sb) (0.3 gram atom Sb) were added. Heat the resulting mixture while stirring and weigh 1040g
(1000ml) Norton Silica-Alumina 5218 No. 1/
4" spheres were added. Then evaporated to dryness with stirring on a steam bath and further dried for 16 hours at a temperature of 120°C. The dried material was poured into a cage made from a 10 mesh stainless steel wire mesh sieve. The mixture was transferred and calcined for 4 hours at 400°C in a Matsufuru furnace under an ambient air atmosphere.The amount of catalyst deposited on the support, calculated from the weight increase of the resulting catalyst, was 16.8%. Example 7 Mo ₁₆ V ₄ Si ₃₂ or Mo ₁ V _0.25 Si ₂ 23.9 g ammonium meta-vanadate (0.204 g atom V) and 144.3 g ammonium para-molybdate (0.817 g atom Mo) was dissolved in 0.5 g of water at 85-95 °C with stirring.326 g of Ludox was added to the resulting solution.
AS' (30.1% SiO ₂ ) (1.633 g g atom Si) was added. The resulting mixture was heated with stirring, evaporated to dryness, and further dried at a temperature of 120° C. for 16 hours. The dried material was crushed into 4 x 8 meshes and then transferred to a basket made of 10 mesh stainless steel wire mesh sieves for 400 minutes under an ambient air atmosphere.
It was baked at ℃ for 4 hours. This was neat catalyst and no support was added. Example 8 Mo ₁₆ V ₈ Sn ₂ or Mo ₁ V _0.5 Sn _0.125 16.0 g of ammonium meta-vanadate (0.137
gram atom V) and 48.1 g ammonium para-molybdate (0.272 g atom Mo) in a stainless steel steam jacketed evaporating dish.
Dissolved in 0.5% water at 85-95°C with stirring. Add 7.7 g of stannic chloride ( _SnCl2.2H2O ) (0.034 g atom Sn) in 120 ml water and 5 ml of _the resulting solution.
of concentrated hydrochloric acid was added. The resulting mixture was heated with stirring and 140 g of a 4×8 mesh of Norton Silica-Alumina No. 5218 (irregular) was added, stirred and evaporated to dryness.
This was further dried at a temperature of 120°C for 16 hours. 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 resulting catalyst, was 23.1%. Examples 9-17 Catalysts 9-17 were made as described below and evaluated using Catalyst Test Method B. Each of these catalysts contains elements Mo,
Contains 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. The % oxydehydrogenation conversion of ethane to ethylene and the % efficiency evaluated at two hot spot temperatures between 300 and 400°C were determined for each of these catalysts. The results are shown later in Table 3. Example 9 Mo ₁₆ V ₄ Nb ₂ K _0.5 or Mo ₁ V _0.25 Nb _0.125 K _0.03 8.0 g of ammonium meta-vanadate (0.068
gram atom V) and 48.1 g of ammonium para-molybdate (0.272 g atom Mo) were dissolved in 0.5 g of water at 85-95° C. with stirring in a stainless steel steam jacketed evaporating dish. Add 0.85 g of potassium nitrate (KNO ₃ ) to the resulting solution
(0.0084 g atom K), 31 g niobium oxalate solution (14.6% Nb ₂ O ₅ ) (0.034 g atom Nb) and 2.8 g ammonium nitrate (NH ₄ NO ₃ ) (0.035
mol) was added. The resulting mixture was heated with stirring and 150 g of Norton Silica-Alumina No. 5218 4×8 mesh (irregular shape) was added. The mixture was then evaporated to dryness while stirring, and further dried at a temperature of 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 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 17.9%. Example 10 Mo ₁₆ V ₄ Nb ₄ P ₄ or Mo ₁ V _0.25 Nb _0.25 P _0.25 8 g of ammonium meta-vanadate (0,068
gram atom V) and 48.1 g of ammonium para-molybdate (0.272 g atom Mo) were dissolved in 0.5 g of water at 85-95° C. with stirring in a stainless steel steam jacketed evaporating dish. 7.8g phosphoric acid ( _85.6 % _H3PO4 ) into the resulting solution
(0.068 g atom P), 62 g niobium oxalate solution (14.6% Nb ₂ O ₅ ) (0.068 g atom Nb) and 5.6 g ammonium nitrate (0.07 mol NH ₄ NO ₃ )
added. The mixture was heated with stirring and 150 g of Norton Silica-Alumina No. 5218 4×8 mesh (irregular) 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 rack 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 Mo ₁₆ V ₈ Nb ₂ Ce ₂ or Mo ₁ V _0.5 Nb _0.125 Ce _0.125 15.9 g of ammonium meta-vanadate (0.136
gram atom V) and 48.1 g ammonium para-molybdate (0.272 g atom Mo) in a stainless steel steam jacketed evaporating dish.
Dissolved in 0.5% water at 85-95°C with stirring. A solution of 31 g of niobium oxalate (14.6% Nb ₂ O ₅ ) (0.034 g atom) in 100 ml water was added to the resulting solution.
Nb) and 14 g of cerium nitrate (41.8% _CeO2 ) (0.034 g atom of Ce) dissolved in 150 ml of water were added. Heat the resulting mixture with stirring and add 150 g
A 4×8 mesh (irregular shape) of Norton Silica-Alumina No. 5218 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 then transferred to a basket made from a 10-mesh stainless steel wire mesh sieve.
4 at 400℃ in a Matsufuru furnace under an ambient air atmosphere.
Baked for an hour. The amount of catalyst deposited on the carrier, calculated from the weight increase of the resulting catalyst, was 28%. Example 12 Mo ₁₆ V ₈ Nb ₂ Co ₂ or Mo ₁ V _0.5 Nb _0.125 Co _0.125 15.9 g of ammonium meta-vanadate (0.136
gram atom V) and 48.1 g ammonium para-molybdate (0.272 g atom Mo) in an evaporating dish with a stainless steel steam jacket.
Dissolved in 0.5% water at 85-95°C with stirring. A solution of 31 g of niobium oxalate (14.6% Nb ₂ O ₅ ) (0.034 g atom) in 100 ml water was added to the resulting solution.
Nb) and 8.5 g of cobalt acetate [Co(CH ₃ COO) _{2.4H 2} O] (0.034 g atom) dissolved in 150 ml of water.
Co) was added. The resulting mixture was heated with stirring and 150 g of Norton Silica-Alumina No. 5218 4×8 mesh (irregular shape) 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 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 stirring deposited on the carrier calculated from the weight increase of the resulting catalyst was 26.3%. Example 13 Mo ₁₆ V ₈ Nb ₂ Cu ₂ or Mo ₁ V _0.5 Nb _0.125 Cu _0.125 15.9 g of ammonium meta-vanadate (0.136
gram atom V) and 48.1 g ammonium para-molybdate (0.272 g atom Mo) in a stainless steel steam jacketed evaporating dish.
Dissolved in 0.5% water at 85-95°C with stirring. Add 31 g of niobium oxalate solution (14.6% Nb ₂ O ₅ ) (0.034 g atom) in 100 ml water to the resulting solution.
Nb) and 6.8 g cupric acetate [(CH ₃ COO) ₂ Cu H ₂ O] (0.034 g atom Cu) dissolved in 150 ml water.
added. The resulting mixture was heated with stirring and 150 grams of Norton Silica-Alumina No. 5218 4×8 mesh (irregular shape) 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 material was then 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 25.1%. Example 14 Mo ₁₆ V ₈ Nb ₂ Fe ₂ or Mo ₁ V _0.5 Nb _0.125 Fe _0.125 15.9 g of ammonium meta-vanadate (0.136
gram atom V) and 48.1 g ammonium para-molybdate (0.272 g atom Mo) in a stainless steel steam jacketed evaporating dish.
Dissolved in 0.5% water at 85-95°C with stirring. Add a solution of 31 g niobium oxalate (14.6% Nb ₂ O ₅ ) (0.034 g atom Nb) in 10 ml water to the resulting solution.
4.4 g oxalic acid and 6.4 g ferric oxalate [Fe ₂ (C ₂ O ₄ ) ₃ ] (0.034 gram atom Fe) in 150 ml water
A solution of The resulting mixture was heated with stirring and 150 g of Norton Silica-Alumina No. 5218 4×8 mesh (irregular shape) 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 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 23%. Example 15 Mo ₁₆ V ₈ Nb ₂ Ni ₂ or Mo ₁ V _0.5 Nb _0.125 Ni _0.125 15.9 g of ammonium meta-vanadate (0.136
gram atom V) and 48.1 g ammonium para-molybdate (0.272 g atom Mo) in a stainless steel steam jacketed evaporating dish.
Dissolved in 0.5% water at 85-95°C with stirring. To the resulting solution, add a solution of 31 g of niobium oxalate (14.6% Nb ₂ O ₅ ) (0.034 g atom) in 100 ml of water.
Ni) and 8.5 g of nitrous acetate [Ni(C ₂ H ₃ O ₂ ) _{2.4H 2} O] (0.034 gram atom of Ni) dissolved in 150 ml of water were added. Heat the resulting mixture with stirring and add 150g
A 4×8 mesh (irregular shape) of Norton Silica-Alumina No. 5218 was added. Next, this was evaporated to dryness while stirring, and further dried at a temperature of 120° C. for 16 hours. This dry material was then transferred to a well-constructed cage through a 10-mesh stainless steel wire sieve.
4 in a Matsufuru furnace at 400℃ under an ambient air atmosphere.
Baked for an hour. The amount of catalyst deposited on the carrier, calculated from the weight increase of the resulting catalyst, was 26.4%. Example 16 Mo ₁₆ V ₈ Nb ₂ Si ₃₂ or Mo ₁ V _0.5 Nb _0.125 Si ₂ 35.9 g of ammonium meta-vanadate (0.307
gram atom V) and 108.0 g ammonium para-molybdate (0.612 g atom Mo) in a stainless steel steam jacketed evaporating dish.
Dissolved in 0.5% water at 85-95°C with stirring. To the resulting solution was added 69.6 g of niobium oxalate solution (14.6% Nb ₂ O ₅ ) (0.076 g atom of Nb) and
244.2 g of "Ludox AS" colloidal silka sol (1.223 g atom Si) was added. The resulting mixture was evaporated to dryness by heating with stirring, and further dried at a temperature of 120° C. for 16 hours. The thus dried material was crushed into 4 x 8 meshes, 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. This is a neat catalyst and contains no support. Example 17 Mo ₁₆ V ₈ Nb ₂ U ₁ or Mo ₁ V _0.5 Nb _0.125 U _0.0625 15.9 g of ammonium meta-vanadate (0.136
gram atom V) and 48.1 g ammonium para-molybdate (0.272 g atom Mo) in a stainless steel steam jacketed evaporating dish.
Dissolved in 0.35% water at 85-95°C with stirring. To the resulting solution was added 31 g of niobium oxalate solution (14.6% Nb ₂ O ₅ ) (0.034 g atom Nb) and 7.2 g
launyl acetate [(CH ₃ COO) ₂ UO ₂・2H ₂ O]
(0.017 gram atom of U) was added. The resulting mixture was heated with stirring and 140 g of Norton Silica-Alumina No. 5218 4×8 mesh (irregular shape) 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 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 27%.

【table】

【table】

[Table] Example Catalyst composition %
℃%%

Claims (1)

[Claims] 1. Ethane in a gas phase, and the elements Mo, X and Y as Mo _a X _b Y _c [In this formula, X represents the element V alone, or
Represents a combination with Nb or Ta, Y is Ce, Co,
Cu, Fe, K, Ni, P, Sb, Si, Sn and/or U, a is 1, b is 0.05 to 1, and c is 0.03 to about 2, provided that Fe, Co and ( or) Exothermically catalytic oxydehydrogenation at a temperature of 500 °C in the presence of an oxydehydrogenation catalyst of a calcined composition containing a proportion of 0.5, assuming that the overall value of c for Ni is <0.5. A process for converting ethane to ethylene and acetic acid at low temperatures, comprising: 2 Oxydehydrogenation by contacting ethane with a calcined catalyst consisting of Mo, V and Nb and one element selected from the elements Cu, Ce and U in the gas phase at a temperature of 550°C or lower. 2. A process according to claim 1, wherein ethylene and acetic acid are produced exothermically by. 3. Ethane is exothermically oxydehydrogenated to ethylene and acetic acid by contacting the ethane in the gas phase at a temperature of 550° C. or lower with a calcined catalyst consisting of Mo, V, Nb and K to produce ethylene and acetic acid. The method described in. 4 The X component in the calcined catalyst used is element V and
The method according to claim 1, which comprises Nb. 5 The calcined catalyst used contains the elements Mo, V, Nb and
The method according to claim 1, wherein the method comprises Ce. 6 The calcined catalyst used contains the elements Mo, V, Nb and
The method according to claim 1, wherein the method is made of Cu. 7. Process according to claim 1, in which the calcined catalyst used consists of the elements Mo, V, Nb and U.