CA1096891A - Low temperature oxydehydrogenation of ethane to ethylene - Google Patents

Low temperature oxydehydrogenation of ethane to ethylene

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Publication number
CA1096891A
CA1096891A CA 261807 CA261807A CA1096891A CA 1096891 A CA1096891 A CA 1096891A CA 261807 CA261807 CA 261807 CA 261807 A CA261807 A CA 261807A CA 1096891 A CA1096891 A CA 1096891A
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Prior art keywords
process
grams
nb
catalyst
mo
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CA 261807
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French (fr)
Inventor
Frank G. Young
Erlind M. Thorsteinson
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Union Carbide Corp
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Union Carbide Corp
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/88Molybdenum
    • B01J23/887Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8876Arsenic, antimony or bismuth
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24Chromium, molybdenum or tungsten
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32Manganese, technetium or rhenium
    • B01J23/34Manganese
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85Chromium, molybdenum or tungsten
    • B01J23/88Molybdenum
    • B01J23/887Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8877Vanadium, tantalum, niobium or polonium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14Phosphorus; Compounds thereof
    • B01J27/186Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/52Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals using catalysts, e.g. selective catalysts

Abstract

LOW TEMPERATURE
OXYDEHYDROGENATION
OF ETHANE TO ETHYLENE

ABSTRACT OF THE DISCLOSURE

Ethane is catalytically oxydehydrogenated to ethylene in a gas phase reaction, in the presence or absence of water, at temperatures of ?C 550°C. using a catalyst comprising oxides of the elements MoaXbYc ) wherein X = Cr, Mn, Nb, Ta, Ti, V and/or W, Y = Bi, Ce, Co, Cu, Fe, K, Mg, Ni, P, Pb, Sb, Si, Sn, Tl and/or U, . a = 1, b - 0 to 2, c = 0 to 2, with the proviso that the total value of c for Co, Ni and and/or Fe is < 0.5.
Acetic acid is also produced.

S P E C I F I C A T I O N

1.

Description

1~ 9 6 89 ~ 10516 BACKGROUND OF THE INVENTION
. . . .. ....
Field of the Invention . . .
The invention relates to the gas phase catalytic dehydrogenation of ethane to ethylene in the pres~nce of oxygen, i.e., the oxydehydrogenation of ethane to ethylenc.
DESCRIPTION OF THE PRIOR ART
Ethylene has been conventionally prepared, commercially, by thermally cracking eth~ne in an endothermic reaction which is carried out at temperatures of about 600 to 1000C. (UOS. Patent 3,541,179). The reaction time in such procesæ is very short, which makes it difficult or ~mpossible to eficiently recover heat from the process stream. Further, the high temperatures which are used require the use of special alloys in the construction of the furnaces or ~he reaction vessels in which the reaction is con~ucted. The cracking reaction also causes the formation of relatively large amounts of low boiling by-products such as hydrogen and methane which complicates, and makes more expensive, the recovery of the ethylene from such by-produc~s.
It is possible to oxydehydrogenate ethane by using a variety o-E oxy~alogenation catalyst systems ln an exothermic reaction. ~hese reactions, however, have only been accomplished at temperatures of at least about 500 to 600C. (U.S. Patent 3,080,435). Furthermore, the presence of the halogen atoms increases the di~ficulty of

2.

~Q ~ 6 ~ ~ 1 10516 recovering any olefins which are produced. Also, exotic and expensive materials of construction are required to withstand corrosion by the halogens and hydrogen halides in the reaction systems. Further, the halogens themselves must be recovered and recycled to make the system economical.
The oxyd.ehydrogenation of selected ~ C3 alkanes, at relatively high temperatures in an exothermic reaction has also been accomplished with ~elected catalysts which contain vanadium (U.S. Patents 3,218,368, 3,541,179 and

3,856,881) and vanadium and molybdenum ~U.~. Patent 3,320,331).
The use of molybdenum and vanadium containing catalyst systems for the gas phase oxidation of alpha-beta unsaturated aliphatic aldehydes, such as acrolein, to the ; corresponding alpha,beta unsaturated carboxylic acids, such as acrylic acid, has been known. These catalyst systems include those containing ~he elements Mo, V and X, where X is ~b, Ti or Ta as disclosed in Belgian Patents 821,322; 821,324 and 821,325.
Prior to the present invention, however, it has not been possible to readily oxydehydrogenate e~hane to ethylene at relatively low temperatures with relatively high levels of conversion, selectivity and productivity.
The terms percent conversion, percent selectivi~y and productivity which are employed herein with respect to the present invention are defined as follows:

3.

~Q ~ 6 8 9 1 10516 I % conversin ~ 100 x A
(of ethane) moles of ethane in the reaction mixture which is fed to the catalyst bed Ia wherein A = the molar ethane-equivalent sum (carbon basis) of all carbon-containing products, exclud~ng the ethane in the ef~luent II % selectivity moles of ethylene (or (or efficiency) = 100 x acetic acid) produced ~or ethylene A
(or acetic acid~
III productivity ~ pounds o ethylene (or acetic acid) for ethylene produced per cubic foot of catalyst (or acetic acid) (in the catalyst bed) per hour of reaction time. - -SUMMARY OF THE INVENTION
Ethane is oxydehydrogenated to ethylene in a gas phase reaction at relatively high levels of conversion, selectivity and productivity and at temperatures of less than about 550C. and preferably of less than 450C., with certain catalyst compositions containing molybdenum and various other optional elements. ~:
An ob~ect of the present invention is to provide a process whereb~ etha~e can be oxydehydrogenated to e~hylene at relat *ely low temperatures with relatively hi~h levels of con~ersionl selectivity and productivity.
A further object of the present invention is to provide a process whereby ethane can be oxydehydrogenated in the presence of water at ~elatively lo~ temperatures : ~ :
to produce relati~ely high levels of conversion, :~:: selectivit~ and productivity with respect to the products ethylene and acetic ac~d.

4.

~Q~6891 10516 A further object of the present invention is to provide a process whereby ethane can be oxydehydrogenated to ethylene without the concurrent production of signifi-cant amounts of gaseous by-products such as methane and hydrogen that would render the cryogenic separation and purification of the ethylene difficult and costly.
A further object of the present invention is to provide novel catalys t compositions for the vapor phase oxydehydrogenation of ethane to ethylene at relatively low t~mperatures.
These and other objects of the present inven-tion are ~chieved by using as a catalys t, in the exothermic vapor phase oxydehydrogenation of ethane, a composition comprising the elements Mo, X and Y in the ratio MoaXbYc X is Cr, Mn, Nb, Ta, Ti, V and/or W, and preferably Mn, Nb, V and/or W, Y is Bis Ce, Co, Cu, Fe, K, Mg, Ni, P, Pb, Sb, Si, Sn, Tl and¦or U, and preferably Sb, Ce, and/or U
a is 1, b is 0 to 2, and preferably O~OS to 1.0, and c is 0 to 2, and preferably O.OS to 1.0, with the proviso that the total value of c for Co, Ni and/or Fe is C 0.5.

1~ 6 8~ 1 The numerical values of a, b, and c represent the relative gram-atom ratios o the elements Mo, X and Y, respectively, which are present in the catalyst composition.
me Si used in forming the catalyst c~mposition shown above is other than that which may be present in any qupport on which the catalyst may be employed, as dis-closed below.
The Catalyst The elements Mo, X and Y are present in the catalyst composition in combination with oxygen in the form, it is believed of various oxides, as such, and possibly as chemical combinations of oxides such as splnels and~perovskites.
The catalyst is preferably prepared fr~m a solution of soluble compounds (salts, complexes or other compounds) of each of the elements Mo, X and Y or, in the case of Si and Sb, aLso a colloidal sol. The solu-tion is preferably an aqueous system having a pH of 1 to 2 7, and preferably 2 to 6. The solution of the element containing compounds iq prepared by dissolving suff~cient quantities of soluble compounds of each of the elements, so as to provide the desired a:b:c gram-atom ratios of the elements Mo, X and Y, respectively. To the extent possible the selected compounds of the various elements should be mutually soluble. The Si compounds are usually ~a 9 6 8~ 1 10516 added in the form of a colloidal silica sol. Where any of the selected compounds of such elements, other than Si, are not mutually soluble with the other compounds, they can be added last to the solution system. The catalyst composition is then prepared by removing the water or other solvent from the mixture of the compounds in the solution system.
The water or other solvent can be removed by evaporation from the mixture resulting from the combination of all the compounds and solvents.
Where the catalyst is to be used on a support, the compounds of the decired elements are deposited on a particulate porous support usually having the foll~wing physical properties, but not limited to these: a surface area of about 0.1 to 500 square meters per gram; an apparent porosity of 30 to 60%; wi~h at least 90% of the pores having a pore diameter ~n the range of 20-1500 microns; and the form of the particles or pellets being about 1/8 to S/16 inch in diameter. The deposition is accomplished by immersing the support in the ultlmate m~turè of all the compounds, evaporating off the ma~or portion o~ the solvent, and then drying the system at about 80 to 220C. for 2 to 60 hours~ The dried catalyst is then calcined by being heated at about 220 to 550C. in air or oxygen for 1/2 to 24 hours to produce the desired MaXb~c `
composition.

7.

~ ~ S 89 ~ 10516 The supports which may be used include s~lica, aluminum oxide, sillcon carbide, zirconia, ~itania and mixtures thereof.

When used on a support, the supported catalyst usually comprises about 10 to 50 weight % of the catalyst composition, with the remainder being the support.
The molybdenum is preferably introduced into solution in the form of ammonium salts thereo~ such as ammonium paramolybdate, and organic acid salts of molybdenum such as acetates, oxalates, mandelates and glycolates. Other water soluble molybdenum compounds which may be used are partially water ~oluble molybdenum oxides, molybdic acid, and the chlorides of molybdenum.
The vanadium, when used, is preferably introduced into solution in the form of ammonium salts thereof such as ammonium meta-vanadate a~d ammonium decavanadate, and organic acid salts of vanadium such as acetates, oxalates and tartrates. Other water soluble vanadium compounds which may be used are partiall~ water soluble vanadium oxides, and the sulfates of v~nad;um.
The niobium and tantalum, whP~ used, are preferably introduced into solu~ion in the form of oxalates.
Other sources of these metals in soluble form, which may be used are compounds in which the metal is coordinated, bonded, or complexed to a beta-diketonate, a carboxylic acid, an ~mine, an alcohol or an alkanolamine.

~ g 6 ~ ~ ~ 10516 The titanium, when used, is preferably introduced into solution in the form of a water soluble chelate coordinated with ammonium lactate. Other soluble titanium compounds which may be used are those in which titanium is coordinated, bonded, or complexed to a beta-diketonate, a carboxylic acid, an amine, an alcohol or an alkanolamine.
The iron, nickel, cobalt, manganese, copper, chromium, bismuth, uranium, cerium, potassium, thallium, magnesium and lead, when used, are preferably introduced into solution in the form of nitrates. Other water soluble compounds of these e~lements which may be used are the water soluble chlorides and organic acid salts such as acetates, oxalates, tartrates, lactates, salicylates, formates and car~onates of such elements.
The antimony and tin, when used, are preferably introduced into the catalyst system in the form of water insoluble o~ides. Water soluble compounds of these elements which may be used are antimony trichloride, stannic chloride, stannous chloride, stannic sulfate and s~annous sulate. Other water insoluble compounds of these elemen~s which may be used are staDnous hydroxide and stannous oxalate.
~ The tungsten, when used, is preferably introduced ; into solution in the form of ammonium salts such as ~mmonium para~ungstate~ Other water soluble tungsten compou~ds which may be used are the tungstic acids.

9.

' '. , ~689~ 10516 When silicon is used it ic preferably intro-duced into the catalyst system in the fonm of an aqueous colloidal silica (SiO2~ sol.
When phosphorus is used it is preferably intro-duced into the catalyst system as phosphoric acid or as a water soluble phosph te.
It is believed that, for the catalysts to be st effective, the Mo, X and Y metal components should be slightly reduced below their highest possible oxidation states. This may be àccomplished during the thermal treatment of the catalyst in the presence of reducing agents such as NH3 or organic reducing agents, such as the organic complexing agents, which are introduced into the solution systems from which the catalysts are prepared.
The catalyst may also be reduced in the ~actors in which the oxidation reaction is to be conducted by the passage of hydrogen or hydrocarbon reducing agents such as ethane, ethylene, or propylene through the catalyst bed.
: The catalysts, supported or unsupported can be 20: used in a fixed or flu~dized bed.
The Ethane The raw material which is used as the source of the ethane should beia gas stream which contains, at .
10 .

,. .

atmospheric pressure, at least 3 volume per cent of ethane. It may also contain minor amounts, i.e., ~ 5 volume percent, of each of H2, CO and the C3-C~ alkanes and alkenes. It may also contain major amounts, i.e., > 5 volume percent of N2, CH4, C02 and water, as st~am.
The catalysts of the present invention appear to be ~pecific with respect to their ability t5 oxydehydrogenate -ethane to ethylene, since the catalysts do not oxydehydrogenate propane, n-butane and butene-l, but rather burn these materials to carbon dioxide, and other oxidized carbonaceous products.
The Reaction MLxture The components of the gaseous reaction mixture which is used as the feed stream in the process of the present invention and the relative ratios of the components in such mixture are the following:
one mole of eth~ne, 0.01 to 1/2 mole of molecular oxygen (as p~re oxygen or in the form of air), and O to 0.4 mole of water ~in the orm of steam).
The water or steam is used as reaction diluent and as a heat moderator for the reaction. Other materials which may be used as reaction diluents or heat moderators are such inert gases as nitrogen, helium, C02, and methane.
During the normal course of the reaction, in the absence of added water, one mol of water is formed per mol 1~6891 10516 of ethane that is oxydehydrogenated. This water that i5 generated during the reaction will, in turn, cause the formation of some acetic acid, i.e., about 0.05 to 0.25 mols, per mol of ethylene that is formed. The water that is added to the feed stream will cause the formation of addit~onal amounts of acetic acid, i.eO, up to about 0.25 to 0.95 mols of acetic acid per mol of ethylene that is fonmed.
The components of the reaction mixture are uniformly admixed prior to being introduced into the reaction zone. The components are preheated, individually or after being admixed, prior to their being introduced into the reaction zone, to a temperature of about 200 to 500C.
Reaction Conditions The preheated reaction mixture is brought into contact with the catalyst composition, in the reaction zone, under ~he following conditions:
pressure of about 1 to 30, a~d preferably of about 1 to 20,atmospheres, temperature of about 150 to 550C., and preferably, of about 200 to 400C., contact time (reaction mixture on catalyst) of about 0.1 ~o 100, and preferably of about 1 to lO,seconds, and, space velocity of about 50 to 5000 h-l, preerably 200 to 3000 h 1.

12.

~6~91 1o5l6 The contact time may also be defined as the ratio be~ween the apparent volume of the catalyst bed and the volume of the gaseous reaction mixture fed to the catalyst bed under the given reaction conditions in a unit of time.
The reaction pressure is inltially provided by the feed of gaseous reactants and diluents, and after the reaction is commenced, the pressure may be maintained, preferably, by the use of suitable back-pressure controllers placed on the gaseous effluent side of the catalyst bed.
~ he reaction temperature is preferably provided by placing the catalys~ bed within a tubular converter whose walls are lmmersed in a suitable heat transfer medium, such as tetralin, molten salt mixtures, or other suitable heat tr~nsfer agent, which is heated to the desired reaction temperature.
The process of the present invention can be used without added diluents, other than water, to selectively oxydehydrogenate ethane to ethylene and acetic acid to prov~de % conversion, % efficiencies and productivities, relative to these end products, of the order of 1~6 P~
U~ U)~ U~
1~ 0~0 0 U o o U
~ ~ c~
P~
p t:
Ul o ~ U~
C~ ~o X e~
o o U~
~U ~o U~ ,, .
~q oo 1~ oo o o o o g C~7 e~

~d o P~
_~ ~ Q ~
~3C ~3C ~ Gl $ O O
~ '`I ~ ~`I a c~ ~ ~ ~ ~ ~ a ' ~ ~ ¢ J cl O
o a~ c~ o c~
.JJ ~ 4 ~ ~ ~
~rl ~ ~ a~ ~ a~ ~ o 14 ~

6~

The preferred catalysts for achieving the highest conversion and efficiencies relative to ethylene and acetic acid are those calcined compositions containing the elements Mo, M, Nb and Mn in the ratio ModMeNb ~ g ~n which M = V and/or W, d = 16, e - l to 16, and preferably 1 to 8, f ~ 1 to 10, and preferably 0.2 to 10, o,/
~ g = O to 32, and preferably ~.to 5. .
The following examples are merely illustrative of the present invention and are not intended as a limit-ation upon the scope thereof.
The examples provided below disclose the prep-&ration of various catalyst c~mpositions, and the use o~
such compositions in the oxydehydrogenation of ethane to ethylene.
The activity of each experimental catalyst was detenmined in either a microscale U shaped tubular reactor Into which a pulsed flow of oxygen and ethane were ~ed (Test Procedure A); or in a straight tubular reactor in which the ethane and oxygen were concurrently fed continuously (Test Procedure B); or in a back-mix autoclave process ~::; (Test Procedure C). These test procedures are described : ~ in m~re detail below.

15.

l~g~

Catalyst Test Procedure A
Catalysts were screened for activity for the (oxy) dehydrogenation of ethane in a pulse micro-~eac~or eystem. The reaction s~ction, a 20" long by 8 mm diameter silica U-tube, holding the catalyst under test wa8 heated by immersion in a fluidized sand-bath, whose temperature was con~rolled by a thermocouple con-troller. The thenmocouples for temperature control and measurement were immersed in the fluidized sand, which extended at least three inches above the level of the catalyst in the U-tube. Preliminary exploration of the - temperature profile in the sa~d-bath showed Less than a 3-degree variation from top to bottom from the fixed-point set by the controller.
The microreactor was close-coupled to a gas chromatograph for analysis of the product streams. The helium carrier supply ~lowing through the microreactor was taken from ~he chromatograph by interrupting the helium-supply line inside the chromatograph at a point directly after the flow-controller, leading ~t through an 8-port, 2-position valve, [Union Carbide Corporation, Special Instruments Division, Model C4-70], and thence through a 6-port man~al sample injection valve [Union Carbide Model 2112-50-2], to the inlet leg of the U-tube reactor. The system was equipped with an injection port holding a rubber septum at the reactor inlet. Product 16.

1~39~8~1 gas from the reactor was led through a cold-trap, back through the 8-port valve, which served to switch the product stream to either of the two analysis systems of the chromatograph. Each valve was equipped with an adjustable by-pass valve to equalize the pressure-drop of the chromatograph column in its analysis system.
Injection of 2.0 ml pulses of feed gas, com-position: (% by volume) oxygen 6.5%, ethane 8.0%, balance nitrogen, was made by gas~tight syringe, through the port directly ahead of the catalyst. The gas was diluted and carried over the catalyst, 3.0 grams, by the helium carrier gas, which passed at all times through the reactor at 60 ml/min and through the gas-chromatograph for analysi~.
Analysis of the product mi~ture was made on a 10' x 1/8" dia. stainless steel column packed with Poropak (T~M.~ R. The column was heated at 10C/minute, starting at 30C. Under these co~ditions the retention times were: air, Z.0 min.; carbon dioxide, 2.5 min.;
ethylene, 3.4 min,, ethane, 4.0 min. The identity of the products was confinmed by chromatography of known pure samples, and by sub~ecting the separated peaks ~o mass spectrometric examination. Poropak R is a par-ticulate, spherical shaped polystyrene resin cross-linked with divinyl benzene~

17.

6 ~9 ~ 10~16 Catalyst Test Procedure B
The catalysts were tested in a tubular reactor under the following conditions: ethane gas feed composi-tion (~L by volume), 9.0~/O C2H6 , 6~0% 2 , and 85% N2;
space velocity of 340 ~r~l; 1 atm total reaction pressure.
As the temperature was raised, the catalyst activity was noted. The reactor consisted o~ a 1/2" stainless steel, straight tube heated by means of a molten salt bath (using DuPont HITEC (T.M.) heat transfer salt) of approximately 12't depth. A 1/8" thermocouple sleeve ran the entire length of the center of reactor tube and catalyst bed. The catalyst temperature profile could be obtained by ~liding the thermo~ouple through the sleeve.
Twenty-six ml of catalyst were introduced into the tube so that the top of the catalyst bed was 4" below ~he surface of the heat transfer salt The catalyst bed was 5-5 1~2" in length so that it had a depth cross-section ratio ~10. The zone above the catalyst bed was filled with glass beads to serve as a preheater. The gaseous effluent from the reactor was passed through a condenser and trap at 0. The gas and liquid products thus obtained were analyzed as described below.

Catalyst Test Procedure C
The reactor used in this high pressure study was a bottom-agitated "Magnedrive" autoclave with a centrally positioned catalyst basket and a side product 1~.

~ 8~El 10516 effluent line. A variable speed, magnetically driven fan continuously recirculated the reaction mixture over the catalyst bed. The reactor is of the type depicted in Figure 1 of the paper by Berty, Hambrick, Malone and Ullock, entitled "Reactor for ~apor-Phase Catalytic Studies", presented as Preprint 42E at the Symposium on Advances in High-Pressure Technology - Part II, Sixty-fourth National Meeting of the American Institute of Ch~mical Engineers (AIChE), at New Orleans, Louisiana, on March 16-20, 1969 and obtainable fr~m AIChE at 345 East 47th Street, New York, ~ew York 10017, which -disclosure is incorporated herein by re~erence.
The back mix autocla~e has a catalyst container made of stainless steel positioned above the blades of the agitator fan. Thus, the fan blows the gas upward and inward in a convectional manner through the catalyst bed. Two thermocouples measure the inlet and outlet gas temperatures. Oxygen was fed through a rotameter at about 150 psig into the reactor through a 1/4" line.
The gaseous~ ethane-COx mixtures were fed through a rotometer and then joined wlth ~he oxygen feed before being i~rodueed into ~he reactor. The liquids were pumped directly into the reactor through the same ~eed line as the gases, but the liquids inlet joined the line after the gases were mixed~ Effluent gases were removed through a port in the side of the reactor.

lq.

l~q6~1 Condensable liquid products were removed by a series of cold traps in two baths. The first bath contained wet ice at 0C and had two cold traps immersed in it. The second bath, of dry ice and acetone at ~78C, contained two cold traps. The non-condensable components of the exit stream were vented through a dry gas-test meter at atmospheric pressure to determine their total volume.
An eight port sampling valve permitted the direct sampling of both product and feed gases through lines connected directly to the reactor feed and product streams. No external recycling was employed, The bulk volume of the weighed catalyst sample was determined (about 150 cc.), and the sæmple was placed in the catalyst basket, The quantity of catalyst charged in each case was about 131.1 gms. Stainless steel screens were placed above and below the catalyst bed to minimize catalyst attrition and circul~tion of catalyst fine particles. After the catalyst basket was charged to the reactor, and the reactor sealed, the process lines ~ere pressure tested at ambient temperatures to a pressure about 1~0 to 200 psig in excess of the max~mum anticipated working pressure. Nitrogen was used for this test.
When the reactor was shown to be leak free, pure N2 was passed through the reactor, and the tempera-ture was raised between 275C and 325C. The gas feed composition was varied in the range, (% by volume), 2~.

76% to 97% C2H6, 3/O to 6% 2~ % to L0% H20, and 0% to 10% COx. After the desired temperature was attained, the oxygen and ethane-COx mixtures were adjusted to give the desired steady state ratio at the desired overall flow rate. The concentrations of the components in the effluent gas were determined by the gas chromatographic analysis described below, A period of about 0.5 to one hour was allowed for the reactor to reach a steady state at the desired temperature. The liquid product traps were then drained, a dry gas test meter reading was taken, and the time was noted as the beginning of a run. During the course of a run, the effluent gas samples were analyzed for C2H6, C2H4, 2~ C0, C02, and other volatile hydrocarbons. At the en~ of a run, the liquid product was collected, and the volume of effluent gas was noted.
The liquid products were analyzed by mass spectroscopy.
The reactor inlet and outlet gases rom all of the tests conducted under Test Procedures B and C were analyzed for 2~ N2 and CO on a 10' x 1/8" column of 5A
molecular sieves (14/30-mesh) at 95C, and for (2~ N2 C0 together), C02, ethylene, ethane, and H20 on a 14~ x 1/8" column of"Poropak ~ (80/100-mesh) at 95C.
The liquid produc~ (when enough was obtained) was analyzed for H20, acetaldehyde, acetic acid, and other components by mass spectroscopy. Poropak Q (T.M.) is a particulate, spherical shaped polyst~rene resin cross-linked with divinyl benzene.

21, In all cases % conversion and % selectivity were based on ~he stoichiometry:
C2H ~ 1/2 2 ~~~i~ C2H4 + H20 C2H6 + 7/2 2 ~~~;~ 2C02 + 3H20 without applying individual response factors to the eluted peak areas of the chromatograms.
The reaction condition of the three test procedures were as follows - Contact Space Cataly~t Pressure Temp., Time, Ve~ocity Teqt Procedure Atmospheres C. Seconds h-A ~3.3 200 to 650 B 1 300 - 400 10.6 340 C 6-10 275 - 325 10.0/75psi 2200 ~5~6/125psi Examples 1-23 Catalysts 1-22 were prepared as disclosed below, and evaluated in Catalyst test Procedure A. The composition of each catalyst is given at the heading of the respective examples, and the test results are given in Table I below.
The catalyst of Example 23 was eval~ated in test Procedure B, and these test results are also shown in Table I.
In testing the catalysts of Eæamples 1-23, each catalyst was first tested to find the lowest temperature at which catalytic activity was first provided by the catalyst. This was designated as the temperature of Initial Activity (To). The selectivity of the catalyst for oxygehydrogenating ethane to ethylene at such To was then determined. Each active catalyst was then evaluated at higher temperatures to determine t~e lowest temperature, above To, at which a 10% conversion of e~hàne ~ to ethylene could be achieved, and this temperature is reported ; ~ in Table I as Tlo. The selectiYity of the catalyst for ~ g ~ 10516 oxydehydrogenative ethane to ethylene at Tlo was also determined and reported in Table I.

Mol Two hundred fifty (250) grams of molybdenum trioxîde (99.95% pure) was mixed with 7.8 grams of Carbowax(~M) 6M, a polyethyleneoxide wax; and pelleted into 5/16" diameter cylinders, 0.2490"1Ong and having an axial hole 3l32'' in diameter. The pellets were roasted at 750C for 3 hours to produce an unsupported catalyst.

Mo Mn or Mo Mn Eighty-eight point twenty-eight ~88.28) grams of ammonium paramol~bdate ~0.5 gram a~oms of Mo) were added to 177.89 grams of a 50.3 percent solution of manganous nitrat~ Co~5 gram atoms Mn) dissolved in 500 ml water.
The resulting mixture was heated to 80-90C
while ~tirring and 14% aq. ammonia was added to give a pH
of 5. This was followed by drying by evaporation with stirr~ng on a steam bath. Further drying was carried out at a temperature of 110 for a period of 16 hours.
The dried material was then transferred to a silica dish and calcined in a mufle f~rnace for 2 hours at 520 in an ambient atmosphere of air. The amount of unsupported catalyst obtained is 107 grams.

9~8~i 10516 EXA~?LE 3 Mo Nb or Mo, Nb lS 4 1 O. 25 Forty-two point four (42 . 4) grams of ammonium paramolybdate (0.24 gram atoms of Mo) were dissolved in 200 milliliters of water while stirring at 60-80, in a stainless steel evaporating dish.
To t~e resulting solu~on was added 74 ml of niobium oxalate solution (containing 183.9 gm/l) (0.06 gram atoms Nb).
The resulting mixture was heated while stirring and 87 grams (100 ml) Norton silica-alumina SA5205 1/4"
sphere~ were added. This ~as followed by drying by evaporation with stirring on a steam bath. Further drying was carried out at a temperature of 120 for a period of 16 hours.
The dried material was then trans~erred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 5 hours at 400 in an ambient atmosphere of air. The zmount of catatlyst deposited on the support calculated from the weight increase of the catalyst obtained is 31.5%.

Mo Ti or Mo Ti 16_ 4 l 0.25 Four-hundred ninety-five (495) grams of ammonium paramolybdate (2.8 gram atoms of Mo) were dissolved in 1 liter of water while stirring at 60-80, in a 6tainless steel avaporating dish.

1~ ~ 6 ~ ~ 10516 To the reQulting solution were added 408 grams of Titanium lactate solution, "TYZOR LA" ~0.7 gxam atoms Ti).
The resulting mixture was heated while stirring and 1040 grams (1000 ml)~Norton''silica-alumina SA5218 1/4" spheres were added. This was followed by drying by evaporation w~th s~irring on a steam bath.
Further drying was carried out at a temperature of 120 for a period of 16 hours.
The dried material was then transferred to a tr~y fabricated from 10-mesh stainle8s 8teel,wire screen and calcined in a muffle furnace for 5 hours at 400 in an ambient atmosphere of air. The amount of catalyst deposited on the support calculated from the weight increase of the catalyst obtained is 21.2%.

; ~ Mo V (~-phase) or Mo V
16 1~4 ''1 0~088 Two hundred se~ent~-threé'point five (273.5) grams (1.9 g~atoms Mo) of moly~denum trioxide, 51.2 grams (0.4 g 20~ ~atoms~Mo> of 94 percent mol~bdenum dioxide? and 18.2 grams (0.1 g~atomsj o f ~anadium pentoxide were ground together on a~ball~mill fo~ 24 hours. The powder was sealed in a silica tube~and heat~et at 700G for 90 hours. After cooling the~;unsupported product had a surface area of 2.36 m~/gm, a~density o 4.01 gm/cc, and a porosity of 0.076 X-ray'diffraction showed that it was the pure O-phase, (V~ Mo ~ O
0.08 ;0.92~5 14.

Mo V or Mo V
16 4 1 0.25 Eighty-two (82~ grams of ammonium meta-vanadate (0.7 gram atoms of V) and 495 grams of ammonium paramolybdate (2. 8 gram atoms of Mo~ were dissolved in 2 liters of water while stirring at 60-80, in a stainless steel evaporating dish.
The resulting mix~ure was heated while stirring and 1040 grams (1000 ml)'Norton"silica-allumina SA5218 1/4"
spheres were added. This was followed by drying by evaporation~
with stirring on a steam bath. Further drying was carried out at a temperature of 120 for a period of 16 hours.
The d*ied material was then transferred to a ~ra~ fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 5 hours at 400 in an ambient atmosphere of air. The amount of catalyst deposited on the support caLculated rom the weight increase of the catalyst obtained is 26.45%.
E~AMPLE 7 Mo W or Mo W
16 ~3 1 0.33 Two-hundred nine (209) grams of ammonium tungstate (0.8 gram atoms of W) and 424 grams of ammonium paramolybdate ~2.4 gram atoms of Mo) were dissolved in 4 liters of water while stirring at 60-80, in a stainless ~teel evaporating dish.
To ~he resulting solution were added 142 grams of ammonium oxalate (1.0 gram molecule) and 28 grams of nitric acid dissolved in lOC ml water.

~ 6.

1(3 ~68~:1 The resulting mixture was heated while st~rring and 1040 grams (1000 ml)"Norton silica-alumina SA5218 1/4" spheres were added. This was followed by drying by evaporation with stirring on a steam bath.
Further drying was carried out at a temperature of 120 for a period of 16 hours.
The dried material was then transferred to a tray fabricated from l-mesh stainless steel wire screen and calcined in a muffle furnace for 8 hours àt 350 in a~
ambient atmosphere of air. The amount of catalyst deposited Qn the support calculated from the weight increase of the catalyst obtained is 21.6%.

Mo V Fe or Mo V Fe 16 4 1 1 ~.25 0.0625 .
Seventy (70) grams of ammonium meta-vanadate (0.6 gram atoms of V) and 424 grams of ammonium paramolybdate (2.4 gram atoms of Mo) were dissolved in 2 li~ers of water while stirring at 60-80, in a stainless steel evaporating dish.
To the resulting solution was added 60 grams of ferric nitrate nonahydrate (0.15 gram atoms iron) dissolved in 100 ml water.
The resulting m~xture was heated while stirring and 1040 grams (1000 ml)qNorton silica-alumina SA5218 1/4"
sph~res were added. This was followed b~ drying by evaporation with stirring on a steam bath. Further drying was carried out at a temperature of 120 for a period of 16 hours.

27.

~ 10516 The dried material was then transferred to a tE~y f~bricated from l-mesh stainless steel wire screen and calcined in a muffle furnace for 5 hours at 400 in an am-bient atmosphere of air. The amount of catalyst deposited on the support calculated from the wei~t increase of the catalyst obtained îs 27.5%.

Mo V Mn or Mo V Mn 16 4 4 ~__ 1 0.25 0.25 Thirty-five (35) grams of ammonium meta-vanadate (0.3 gram atoms of V) and 212 grams of ammonium paramolybdate (1.2 gr~m atoms of Mo) were dissol~ed in 1 liter of water while stirring at 60-80, in a stainless steel evaporating dish.
To the resulting solution were added 75 grams of man ganous acetate tetrahydrate (0.3 gram atoms Mn) dissolved in 100 ml water.
The resulting mixture was hea~ed while stîrring.
This was followed by drying by evaporation wi~h stirring on a steam bath. Further drying was carried out at a temperature of 120 for a period of 40 hours.
The dried material was then transferred to a silica dish and calcined in a muffle furnace for 5 hours at 400 in an ~mbient atmosphere of air. The amount of unsupported catalyst obtained is 222 grams.

Mo V Nb or Mo V Nb 16 4 2 1 0.25 0.125 Eighty-two (82) grams of ammonium meta-vanadate (0.7 gram atoms of V) and 494 grams of ammonium paramolybdate (2.8 gr~m atoms of Mo) were dissolved in 2 liters of water while stirring at 60-80j in a stainless steel ~ ~ 6 8 evaporating dish.
To the resulting solution were added 550 grams of niobium oxalate sol (0.35 gram atoms Nb) and 28 grams of ammonium nitrate dissolved in 100 ml water.
The resulting mîxture was heated while stirring and 1040 grams (1000 ml) Norton silica-alumina SA5218 1/4" spheres were added. This was ~ollowed by drying by evaporation with stirring on a steam bath. Further drying was carried out at a temperature of 120 for a period of 16 hours.
The dried material was then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for S hours at 400 in an ambient atmosphere of air. The amount of catalyst deposited on the support calculated from the weight increase of the catalyst obtained is 27.7%.
The niobium oxalate sol, containing the equivalent of 95.3 gm/l of ~b20s is a product of Kawecki Berylco Industries.

Mo W Nb or Mo W Nb 16 2 4 1 0.125 0.25 Seven point eight (7.8) grams of ammonium paratungstate ~0.03 gram atoms of W) and 42.4 grams of ammonium paramolybdate (0.24 gram atoms of Mo) were dissolved in 400 ml of water while stirring at 60-80, ; in a ætainless steel evaporating dish.
To the resulting solution were added 74 ml of a solution of niobium oxalate oontaining 183.9 grams/l (0.06 gram atoms Nb).
,~ .
29.

~ ~ 6 8~ 1 The resulting mixture was heated while stirring and 87 grams (100 ml) Norton sil~ca-alumina SA5205 1/4" spheres were added. This was followed by drying by evaporation with stirring on a steam bath. Further drying was carried out at a temperature of 120 for a period of 16 hours.
The dried material was then transferred to a t~ay fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 5 hours at 400 in an ambient atmosphere of air. The amount of catalyst deposited on the support calculated from the weight increase of the catalyst obtained is 55.2~.

Mo W Pb or Mo W Pb 16 3.3 1.9 1 0.2 ~.12 One hundred seven~y-seven (177) grams of ammonium para-tungstate (0.679 gram atoms of V) and 369 grams of ammonium para-molybdate (2.087 gram atoms of Mo) were dissolved in 2 liters of water while stirring at 60-80, in a stainless steel evaporating dish.
To the resulting solution were added 83 grams of lead nitrate (0.252 gram atoms Pb) and 20 ml of nitric acid dissol~ed in 450 ml water.
The resulting mixture was heated while stirring and 770 grams (1000 ml) Norton silica-alumina SA5205 1/4"
spheres were added. Thi8 was followed by drying by evaporation with stirring on a steam bath. Further drying was carried out at a temperature of 120 for a period of 16 hours.

30.

. 10516 The dried material was then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 5 hours at 400 in an ambient atmosphere of air. The amount of catalyst deposited on the support calculated from the weight increase of the catalyst obtained is 37.2%.
E~MPLE 13 Mol6Nb4Wl.6Mn4 or MlNbO.25WO.l~nO.25 Three thousand three hundred forty-eight (3348~ ~
ml of niobium o~alate solution, containing 319.1 grams Nb20s (2.4 gram atoms of Nb) and 1696 grams of ammonium paramoly~date (9.6 gram atoms of Mo) were dissolved in 4 liters o water while stirring at 60-80, in a stainless steel evaporating dish.
To the resulting solution were added 240 grams o ammonium paratungstate (0.92 gram atoms tungsten) and 880 grams of 50.3 percent solution of ma~ganous nitrate (2.46 gram atoms manganese) dissolved in 4000 ml water.
' The resulting mixture was heated while stirring and evaporated to a paste. This was transferred to furnace trays and dried in a circulatory air current at 80-90C.
overnight. Further drying was carried out at a temperat~re ~: of 120 for a period of 64 hours.
The dried material was then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 5 hours at 360 in an 31.

8~

ambient atmosphere of nitxogen. The amount of unsupported catalyst is 2027 grams. The catalyst was reduced to 25-mesh.

Mol6v4NblMnl or MlVo.25Nbo.0625Mno.0625 Two-hundred ten (210) grams of ammonium meta-vanadate (1.8 gram atoms of V) and 1272 grams of ammonium : :
paramolybdate (7.2 gram atoms of Mo) were dissolved in

5.5 liters of water while stirring at 60-80, in a lQ stainless steel evaporating dish.
To the resulting solution were added 416 grams of niobium oxalate sol (0.45 gram atoms Nb) and 160 grams of manganous nitrate (50.3% solution), (0.45 gram atoms Mn) dissolved in 150 ml water.
The resulting m~xture was heated while stirring ant 3120 grams (3000 ml) Norton silica-alumina SAS218 1/4"
spheres were added. This was followed by drying by evaporation with stirring on a steam bath. Further drying was ca~ried out at a temperature of 120 for a period of ~:: 2016 hours.
The tried material was then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 5 hours at 400 in an ambient atmosphere of air. The amount of catalyst deposited on the support calculated from the weight increase of the catalys~ obtained is 27 . 8%.

32 .

~ . . - .

~ g 6 89 ~ 105~6 Mol6V4Ta2Fel or MlVo.25Tao.l25Feo.o625 Seventy (70) grams of ammonium meta-vanadate (0.6 gram atoms of V) and 424 grams of ammonium para-molybdate (2.4 gram atoms of Mo) were dissolved in tws l~ters of water while stirring at 60-80C., in a stainless steel beaker.
To the resulting solution were added 66 grams of tantalum oxalate solution ~containing 0.3 gram atoms Ta) and 6 0 grams of ferric nitrate Fe(N03)3 9H20 (0.15 gram atoms Fe) dissolved in 100 ml water.
The resulting mixture was heated while stirring and approximately 60 per cent of the water was evaporated off.
The resulting concentrated slurry was transferred to a s~ainless steel evaporating dish and 1040 gxams (1000 ml) Norton silica-alumina (~o. SA-5218) 1/4" spheres were added. This was followed by drying by evaporation with stirring on a steam bath. Further drying was carried out at a temperature of 120C. for a period of 16 hours.
The dried material was then transferred to a tray abricated from 10-mesh stainless s~eel wire screen and calcined in a muffle furnace for 5 hours at 400C. in an ambient at:mosphere of air.
T~e amouIlt of catalyst depo~ited on the support calculated from the weight increase of the catalyst obtained is 19 . 2 weight per cent .

33.

lQ~6891 Mol6V4Ta2Mnl or MolVo 2sTao 125Mn0 0625 Two hundred eighty (280~ grams of ammonium meta-vanadate (2.4 gram atoms of V) and 1696 grams of ammonium paramolybdate (9.6 gram atoms of Mo) were dissolved i~
7.5 ~iters of water while stirring at 60-80, in a stainless steel evaporating dish.
To the resulting solution were added 1584 grams of tantalum oxalate sol (1.2 gram atoms Ta) and 216 grams of a 50.3% solution of manganous nitrate (0.6 gram atoms) dissol~ed ~n 200 ml water.
The resulting mixture was heated while stirring and 4160 grams (4000 ml) Norton silica-alumina SA 5218 1/4" spheres were added. This was followed by dry~ng by evaporation with stirring on a steam bath. Further drying was carried out at a temperature of 120 for a period of 16 hours.
The dried material was then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 5 hours at 40~ in an ambient atmosphere of air. The amount of catalyst deposited on the support calculated from the weight increase of the catalyst obtained is 19.2/~.
Tantalwm oxalate sol, containing the equivalent of 218.6 gm/l of Ta205 is a product of Kawecki Berylco Industries.

34.

9 ~

Mol6V4Ti2~1 or MlVo.2ST~o.l25~o.o62s Seventy grams of ammonium meta-vanadate (0.6 gram atoms of V) and 424 grams of ammonium paramolybda~e (2.4 gram atoms of Mo) were dissolved in two liters of water while stirring at 60~80C., ~n a stainless steel beaker.
To the resulting solution was added 175 grams of titanium ammonium lactate (chelate) solution (containing 0.3 gram atoms Ti) and 54 grams of 50.3% manganese nitrate solution (0.15 gram atoms Mn~ dissolved in 100-ml water.
The resulting mixture was heated while stirring and approx~mately 60 per cent of the water was evaporated off.
The resulting concentrated slurry was transferred to a stainless steel evaporating dish and 1040 grams (1000 ml) Norton s~lica-alumina (No. ~A-5218) 1/4" spheres were added. This was followed by drying by evaporation with stirring on a steam bath. Further drying was carried out at a temperature of 120C. for a perlod of 16 hours.
The dried material was then transferred to a tray ~abricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 5 hours at 400C. in an ambient atmosphere of air, The amount of catalyst deposi~ed on the support calculated from ~he weight increase o~ ~he catalyst obtained is 27.8 weight %.

35.

9 ~

Mol6V4W1 6Mn4 or MlVo.25Wo.lMnO.25 Three-hundred fifty (350) grams of ammonium meta-vanadate (3 gram atoms of V) and 2120 grams of ammonium paramolybdate (12 gram atoms of Mo) were dissolved in 10 liters of water while st;rr~ng at 60-80, ~n stainless steel evaporating dish.
To the resulting solution were added 313 grams of ammonium paratungstate (1.13 gram atoms W) and 750 grams of manganous acetate tetrahydrate (3.06 gram atoms Mn) dissolved i~ 6000 ml water.
The resulting mixture was heated while stirring and was followed by drying by evaporation with stirring on a steam bath. Further drying was carried out at a temperature of 120 for a period of 24 hours~
The dried material was then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 5 hours at 400 in an ambient a~mosphere of air. The amount of unsupported catalyst thus obtained was 1453 grams. 2720 grams of dried material was obtained a~ter the 120C. drying step.
1636 grams of this dried material was calcined in the 400C. calcination step to produce 1453 grams of calcined catalyst.

36.

M0l6Bil 3Til 3Mn2 6Si2,6 or MlBio.08Tio.08Mn0~l6 0-16 .
Four-hundred fifty-seven (457) grams of ammonium paramolybdate (2.6 gram atoms of Mo) were dissolved in 0.7 liters of water while stirring at 60-80, in a stainless steel evaporating dish.
To the resulting solution were added 249 grams of titanium lactate solution, "TYZOR LA" (0.21g atoms Ti) and 104 grams of bismuth nitrate pe~tahydrate (0.21 gram atoms) dissolved in 110 ml water, containing 25 ml of concentrated nitric acid a~d 153 grams of a 50.3 percent solution o~ manganous nitrate (0.43 gram atoms of Mn), and then 86 grams of colloidal silica solution, LUDOX LS.(~
The resulting mixture was heated while stirring and 770 grams (1000 ml)~Norton silica-alumina SA5205 1/4"
spheres were added. ThiB was followed by drying by evaporation with stirring on a steam bath. Further drying was carried out at a temperature of 120 for a period of 16 hours.
The dried material was ~hen transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a mufle furnace for 5 hours at 400 in an ambient atmosphere of air. The amount of catalyst deposited on the support calculated from the weight increase of the catalyst obtained is 32.5%.

37.

TYZOR LA (T.M.) is a colloidal titanium lactate sol made by E. I. duPont de Nemours and Co. L~DOX LS
(T .M. ) is a colloidal silica solution made by E. I.
duPont de Nemours and Co.

MO16V4Tal 33Fe0 67Sil 33 or MlV0.25 0.083 0.042 0.083 Thirty-five point one (35.1) grams of ammonium meta-vanadate (0.3 gram atoms of V) and 212 grams of ammonium paramolybdate (1.2 gram atoms of Mo) were dissolved in 1.1 liters of water while stirring at 60-80, in a stainless steel evaporating dish.
To the resulting solution were added 126 grams of tantalum oxalate sol (containing the equivalent of 228 g Ta205/liter tO.l gram atoms Ta) and 20.2 grams of ferric nitrate nonahydrate (0.05 gram atoms Fe) and 20 grams of LUDOX AS-30 (0.1 g atom Si) dissolved in 197 ml water. ~ .
The resulting mixture was heated while stirring :: and 770 grams (970 ml) Norton silica-alumina SA5205 1/4' spheres were added. This was followed by drying by evaporation with stirring on a steam bath. Further drying was carried out at a temperature of 120 for a period of 16 hours.
The dried material was then transferred to a tray fabricatet from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 5 hours at 400 in an 38.
.

ambient atmosphere of air. The amount of catalyst deposited on the support calculated from the weight increase of the catalyst obtained is 22.5%
EX~PLE 21 Mol6V4Til 3Nbo 67Mnl or MolV0 2sTio.o8Nbo.o42Mno~o625 Two hundred ten (210) grams of ammonium meta-vanadate ~1.8 gram atoms of V) and 1272 grams of ammonium paramolybdate (7.2 gram atoms of ~o) were dissolved in 5.5 liters of water while stirring at 60-80, in a stainless steel evaporating dish.
To the resulting solution were added 351 grams of titanium ammonium lactate, "TYZOR LA" (0.6 gram atoms Ti) and 216 grams of niobium oxalate sol (0.3 gram atoms Nb) and 160 grams of a 50.3 percent solution of manganous nitrate (0.45 gram atoms Mn) dissolved in 200 ml water.
The resulting mixture was heated while stirring and 3120 grams (3000 ml) ~orton silica-alumina SA5218 1/4" spheres were added. This was followed by drying by evaporation with stirring on a steam bath. Further drying was carried out at a temperature of 120 for a period of 16 hours.
The dried material was then transferred to a tray fabricated from a 10-mesh stainless steel wire screen and calcined in a muffle furnace for 5 hours at 400 in an ambient atmosphere of air. The amount of catalyst deposited on the support calculated from the weight increase of the catalyst obtained is 37.8%.

39.

~q~8~

Mol6Bil, 3Fel . 3Tlo, sNi7 . 3Col . 3Mgl . 3M~2 . lPo .13Sil9 . 6 ~r LO,~ e0.o~ o3Nio.456coo~o8Mgo.o8Mno~l3lpo~s~ 23 zero point twenty-nine (0.29) grams of 85 per-cent phosphoric acid (0.0025 gram atoms of P~ and 53 grams of ammonium paramolybdate (0.3 gram atoms ~f Mo) were dissolved in 0.3 liters of water while stirri~g at 60-80, in a porcelain evaporating dish. Sixty-seven (67) ml of a silica sol, LUDOX AS was then added and 50 ml conc.
ammonium hydroxide.
To the resulting solution were added 10.1 grams of ferric nitrate nonahydrate ~0.025 gram a~oms Fe) 39.99 gram~ of nickel nitrate hexahydrate (0.1375 gram atoms Ni),

6.41 grams of magnesium nitrate hexahydrate (0.025 g atoms Mg~, 7.25 grams of cobalt nitrate hexahydrate (0.025 g stoms Co), 14.27 grams of a 50.3 percent solution of ~ -manganous nitrate ~0.025 g atoms Mn), 4.0 grams of ~thallium nitrate trihydrate (0.015 g atoms Tl) dissolved in 250 ml water.
20~ ~ The resulting mixture was heated while stirring and 12.i3 grams of bismuth nitrate (0.025 g atoms Bi) disso~ved in 30 ml water and 4 ml concentrated nitric acid were added. This was followed by drying by evaporation with stirring on a steam bath. Further drying was carried out at a temperature of 120~ or a period of 16 hours.

40.

1~ q 6 ~9 1 10516 The dried material was then transferred to a silica dish and calcined in a muffle urnace for 6 hours at 525 in an ambient atmosphere of air. The amount of unsupported catalyst obtained is 90 grams.

Mol6v4Nb2cul or Molvo.2sNbo.l25cuo.o625 Forty-two (42) grams of ammonium meta-vanadate (0.36 græm atoms of V) and 254 grams of ammonium para-molybdate (1.44 gram atoms of Mo) were dissolved in 1.2 li~ers of ~ater while stirring at 60-80, in a stainless steel evaporating dish.
To the resulting solution were added 158 grams of niobium oxalate (0.18 gram atoms Nb) and 22 grams of cuprlc nitrate (0.09 gram atoms Cu) dissolved in 60 ml water.
The resulting mixture was heated while stirring and 1040 grams (1000 ml) Norton silica-alumina SA5218 1/4" spheres were added. This w~s followed by drying by evaporation with st~rring on a steam bath. Further drying was carried out at a temperat~re of 120 for a period of 16 hours.
The dried material was then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 5 hours at 400 in an ambient atmosphere of air. The amount of catalyst :

41.

~ 9 6 89 1 10516 deposited on ~he ~upport calculated from the weight increase of the catalyst obtained is 15.9%.
The catalyst of Example 23 was evaluated in Test Procedure B, and the ~est resuLts are shown in Table I.

The catalysts of Examples 24-28 are outside the scope of the pre~ent in~en~îon, These catalysts were prepared as disclosed beIow, and tested in Catalyst Test Procedure A. When so tested they showed little or no selectivity for the purposes of converting ethane to ethylene. The ca~alyst~ of Exam~les 24-26 contained exce~s amounts of Fe and/or Co, i.e., ~ 8 gram atoms of Fe and/or Co per 16 gram ato~s of Mo, and the catalysts of Examples 27-28 did not contain any Mo.
EX~LE 24 Mol6Col~ Mn2 or MalC0.875MnO,125 One thousand five hundred fifty-six C1556) grams of ammonium paramoly~date C8.82 gram atoms of Mo~ were dissolved in 4.16 liters of water while stirring at 60-80, in a stainless steel evaporating dish.
To the resulting solution were added 178.4 grams of ~anganese sulfa~e Cl,a6 gram atoms ~ and 2328 grams of co~altous ni~rate ~8 g~am a~oms Co~ dissolved in 1760 ml water.
The resul~ing mixture was heated while stirring and 633 grams of titanium h~drate pulp was added. The slurry was neutralizPd with 677 grams of aqueous ammonium dissolved in 1243 ml of water. This was followed by drying by evaporation wi~h stirring on a steam bath.
Further drying was carried out at a temperature of 120 for a period of 16 hours.

6 89 i The dried material was then transferred to an evaporating desk and calcined in a muffle furnace for 8 hours at 400 in an ambient atmosphere of air. The catalyst was pelletized and then roasted 12 hours at 550C. Catalyst test results for this material by Procedure A showed no sele~tivity to ethylene, but complete combustion starting at 210C.

Mol6Fel.6co6~4w3.2Bil.6si2.l6Ko.l or MolFeO lCro~4W0~2BiO~lSiO~135K0~006 Six hundred forty-eight (648) grams of ammonium paratungstate (2.483 gram atoms of W) and 2124 grams of ammonium paramolybdate (l2.03 gram atoms of Mo) were dissolved in 3 liters of water while stirri~g at 60-80, in a stainless steel evaporating dish.
To the resulting solution were added 1400 grams of cobaltous nitrate hexahydrate (4.81 gram atoms of Co), 486 græms of ferric nitrate nonahydrate (1.203 gram atoms of Fe), and 584 grams of bismuth nitrate pentahydrate ~1.204 g atoms of Bi), and 300 ml of a 1.35 percen~
potassium hydroxide solution (0.072 g atoms of K), dissolved in 1400 ml water.
The resulting mixture was heated while s~irring and 320 grams of Ludox, a 30.5% colloidal silica sol were added. This was followed by drying by evaporation with stirring on a steam bath. Further drying was carried 43.

out at a temperature of 120 for a period of 16 hours.
The dried material was then transferred to a tray abricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 5 hours at 400 in an ambient atmosphere of air. The catalyst was mixed with 10 percent of its weight of naphthalene and pelleted into S/16~ x 5/16" cylindersO The pellets were roasted 6 hours at 450C. Catalys~ test results for this material by Procedure A showed no selectivity to ethylene on oxidation of ethane at 366C.

Mol6Feg or MlFeO.5 -Thirty-Five point three (35.3) grams of ammo~ium paramolybdate (0.2 gram atoms of Mo~ were dissolved in 200 milliliters of water while stirring at 60-80, in a stainless steel evaporating dish. To the resulting solutio~ were added 35 grams of ferric nitrate hexahydrate (0.1 gram atoms of Fe) dissolved in 200 ml water.
The resulting mixture was heated while stirring and thcn flltered. This was followed by drying at a temperature o 120 for a period of 16 hours.
The dried material was then transferred to a silica dish and calcined in a muffle furnace for 4 hours at 400 in a~ ambient atmosphere o pure o~ygen. The am~unt of catalyst obtained i~ 34 grams. Catalyst test 44.

~ 68~1 10516 results for this material by Procedure A showed a reaction beginning at 276C " but no selectivity for the production of ethylene.

V3Sbl2Cel Eight point seven (8.7) grams of vanadium pentoxide (0.096 gram atoms of V) was dissolved in 350 ~C) ~o~o~hlorJc D ml conc (16N)~acid and 200 ml ethanol while stirring at 55, in a glass evaporating dish.
lQ To the resulting solution were added 114.4 grams of antimony pentachlor~de (0.383 gram atoms Sb) dissolved in 80 ml conc HCl and 13.847 grams of cerium nitrate hexahydrate (0.032 gram atoms Ce) dissolved in 100 ml ethanol.
The resulti~g mixture was neutralized with 440 ml conc ammonium hydroxide dissol~ed in 700 ml of water.
The precipitate was filtered and washed on the filter with 1000 ml water. This was followed by drying at a temper-ature of 120 for a period of 16 hours.
: ~ 20 The dried material was then transferred to a tray fabricated from 10-mesh stainless steel ~ire screen and calcined in a muffle furnace for 12 hours at 750 in an ambient atmosphere of air. Catalyst test results for this material by Procedure A showed activity to burn ethane at 262C., but no selectivity for the formation of ethylen~.

45.

i 10516 Sb5VlNblBi5 Twenty-eight (28) grams of ammonium meta-vanadate (0.2404 gram atoms of V) were dissol~ed in 700 ml of water while stirring at 60-80, in a stainless steel evaporating dish.
To the resulting solution were added 583 grams of bismNth nitrate pentahydrate (1.202 gram a~oms Bi) and 180 grams of antimony trioxide (1.202 gram atoms Sb~ and 219 gram~ (172 ml) of niobium oxalate sol (0.2404 g atoms Nb) dissolved in 720 ml of 3N ~itric acid.
The resulting mixture was heated whila stirring and 770 grams (1000 ml) Norton silica-alumina SA5205 l/41' spheres were added. This was followed by drying by evaporation with stirring on a steam bath. Further drying was carried out at a temperature of 120 for a period of 16 hours.
The dried material was then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 5 hours at 400 in an ambient atmosphere of air. The amount of catalyst deposited on the support calculated from the weight increase of the catalyst obtained is 36 ~ l~/oo When tested in Catalyst Test Procedure A, the catalyst of Example 28 showed initial activity at 525C.
However, the % selectivity of ethane to ethylene at this temperature was only 26~.

46.

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Catalysts 29-46 were prepared as disclosed below, and evaluated in Catalyst Test Procedure B. Each of the catalysts of Examples Z9-31 contain the elements Mo and V, and the catalysts of Examples 32-46 contain the elements Mo and V and one other X or Y element. The composition of each catalyst is given at the headings of the respec~ive Examples, and the test results are given in Table II below.
Each catalyst of Examples 29-46 was evaluated at one or two different hot spot temperature~ be~ween 300 and 400C~ to determine the % conversion and % efficiency results at each such temperature for oxydehydrogenat~ng ethane to ethylene.

Mol6V4 or MlV0 25 .
40.9 Grams of ammonium meta-vanadate (0.35 gram atoms of V) was dissolved in 1 liter of water while stirring at 85-95, in a stalnless s~eel steam jacketed evaporating dish.

To the resulting solution were added 40.9 grams of oxalic acid (0.454 mols) in 400 ml water and 247 grams of ammonium paramolybdate (1.4 gram atoms Mo) dissolved in 800 ml water.
The resulting mixture was heated while stirring and dried by evaporation with stirring. F~rther drying 49.

9 6 ~ 1 was carried out at a temperature of 120 for a period of 16 hours.

The dried material was broken to 4 x 8 mesh then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace or 4 hours at 400 in an ambient atmosphere of air. This was a neat catalyst; no support was added.

Mol6V6 7 or MlV0 42 .
57 Grams of ammonium meta-~anadate (0.487 gram atoms of V) was dissolved in 1.5 liters of water (90);
added 66 grams of glycerol and 216 grams of ammonium paramolybdate dissolved in 220 ml water (1.22 gram atoms of Mo) while stirring at 60-80, in a stainless steel evaporating dish.
The resulting mixture was heated while stirring and 1000 grams (1000 ml)'Norton silica-alumina #S218 1/4" spheres were added. This was foll~wed by drying by evaporation with stirring on a steam bath. Further drying was carried out at a temperature of 1~0 for a perlod of 16 hours.
The dried material was then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 4 hours at 400 in an ambient atmosphere or air. The a~ount of catalyst deposited on the support calculated from the weight increase of the catalyst obtained is 18.5%.

50.

EXAMæLE 31 =~ ~
Mol6Vg or MlV0.5 16 Grams of ammonium meta-vanadate (0.136 gram atoms of V) and 48.1 grams of ammonium paramolybdate ~0.272 gram atoms of Mo) were dis~olved in.5 liters of water while stirring at 85-95, in a stainless steel steam jacketed evaporating dish.
To the resulting solution were added 4.8 grams of ammonium oxalate, [(NH4)2C204-H20] (.034 mol5) in 50 ml water.

The resulting mixture was heated while stirring and 140 græms Norton silicæ-alumina #521~ 4 x 8 mesh (irregular shapes) were added. This was followed by drying by evaporation with stirring. Further drying was carried out at a temperature of 120 for a period of 16 hours.

The dried material was then transferred to a tray fabricated from 10-mesh stainless s~eel wire screen and calcined in a muffle furnace for 4 hours at 400 in an ambient atmosphere of air. The amount of catalyst deposited on the support calculated from the weight increase of the catalyst obtained is 22%.

Mol6VgFel or MlV0.5FeO.0625 15.9 Grams of ammonium meta-vanadate (0.136 gram atoms of V) and 48.1 grams of ammonium paramolybdate 51.

96~gl (0.272 gram atoms of Mo) were dissolved in .3 liters of water while stirring a~ 85-95, in a ~tainless steel steam jacketed evaporating dish.
To the resulting solution were added 4.8 grams of ferric sulfate (Fe2~S04]3~9H20) (0.017 gram atom~ of Fe) in 400 ml water.
The resulting mixture was heated while stirring and 130 gramg Norton silica-alumina ~5218 4 x 8 mesh (irregular shapes) were added. This was followed by drying by evaporation with stirring. Further drying was carried out at a temperature of 120 for a period of 16 hours.
The dried material was then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a mNffle furnace for 4 hours at 400 in an ambient atmosphere of air. The amount of catalyst deposi~ed on the support calculated from the weight increase of the catalyst obtained is 27.4%. Catalyst test results for this material are given in Table II.

Mol6V2Nb2 or Ml~0.125NbO.125 ; ~ 16 Grams of ammonium meta-vanadate (0.136 gram atoms of V) and 192.4 grams of ammonium paramo~ybdate (1.09 gram atoms of Mo) were dissolved in .8 liters of water while stirring at 85-95, in a stainless steel steam Jacketed evaporating dish.

: 52.

1~ ~ 6 ~9 ~ 10516 To the resulting solution were added 124 grams of niobium oxalate solution (14.6% Nb205) in 100 ml w~ter (0.136 gram atoms of Nb).
The resulting mixture was heated while stirring and dried by evaporation with stirring. Further drying was carried out at room temperature under total vacuum for a period of 3 days.
The dried material was broken to 4 x 8 mesh and then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muf~le furnace for 4 hours at 400 in an ambient atmosphere of air. This was a neat catalyst; no support was added.

M16V4~b2 or Molvo.2sNbo.l25 40.9 Grams of ammonium meta-vanadate (0.350 gr G atoms of V) was dissolved in 1.0 liters of water while stirring at 85-95QC., in a stainless steel steam jacketed evaporating dish.
To the resulting solution were added 159.2 grams of niobium oxalate solution (14.6% Nb20s) diluted with 100 ml water (0.175 gram atoms of Nb) and 247 grams of ammonium paramolybdate (1.399 gram atoms of Mo) dissolved in 800 ml water.
The resulting mixture was heated and dried by ; evaporation with stirring. Further drying was carried out at a temperature of 120 for a period of 16 hours.

53.

1~ q ~ 10516 The dried material was broken to 4 x 8 mesh and then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 4 hours at 400 in an ambient atmosphere of air. m is was a neat catalyst; no support was added.

-Mol6V4 6Nb0.6 or MlVo.288Nb0.0375 81.8 Grams of ammonium meta-vanadate (0.7 gram atoms of V) and 494 grams of ammonium par~molybdate (2.8 gram atoms of Mo) were dissolved in 1.5 liters of water while stirring at 85-95, in a stainless steel steam jacketet evaporating dish.
To the resulting solution were added 318.4 grams of ~iobium oxalate solution (14.6% Nb20s) in 200 ml water (0.35 gram atoms Nb). The resultant slurry was filtered;
the filtrate allowed to stand at room temperature for 3 days. More crystals formed and were filtered out. The final filtrate was evaporated to dryness, with stirring, in the stainless steel evaporator. Further drying was carried out at a temperature of 120 for a period of 16 hours.
The dried material was broken to 4 x 8 mesh and hen transferred ~o a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 4 hours at 400 in an ambient atmosphere of air. This was a neat catalyst; no support was added.
Analysis indicates the compos~tion Mol6V4 6Nb0 6.

54.

Mol6V6Nb2 or MlV0.375NbO.125 61.4 Grams of ammonium meta-vanadate (0.525 gram atoms of V) was dissolved in 1.0 liters of water while stirring at 85-95QC, in a stainless steel ste~m jacketed evapora~ing dish.
To the resulting sol~tion were added 275 grams of niobium oxalate solution (8.45% Nb20s)(0c175 gram atoms Nb) and 247 grams of ammonium paramolybdate (1.399 gram atoms Mo) dissolved in 800 ml wa~er.
The resulting mixture was heated and dried by evaporation with stirring. Further drying was carried out at a temperature of 120 for a period of 16 hours.
The dried material was broken to 4 x 8 mesh and then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 4 hours at 400 in an ambient a~mosphere of air. This was a neat catalyst; no support was added.

Mol6VgNbo 5 or MlV0.5NbO.031 , 16 Grams o~ ammonium meta-vanadate (0.136 gram atoms of V) a~d 48.1 grams of ammonium paramolybdate (0.272 gram atoms of Mo) were dissolved in .5 liters of wàter while stirring at 85-95, in a stainless steel steam ~acketed evaporati~g dish.

~. ' ~' .

6~1 10516 To the resulting solution was added 7. 75 grams of niobium oxalate æolutlon (14~6~/o Nb205) (0~0085 gram atoms Nb).
The resulting mixture was heated while stirring and 140 grams Norton silica-alumina #5218 4 x 8 mesh tirregular shapes) were added. This was followed by drying by evaporation with stirring. Further drying was carried out at a temperature of 120 for a period of 16 hours.
The dried material was then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 4 hours at 400 in an ambient atmosphere of air. The amount of catalyst deposited on the support calculated ~rom the weight increase of the catalyst obtai~ed is 23.2%.

; M~16V8Nb2 or MO1VO.5Nbo 125 15.9 Grams of ammonium meta-vanada~e (0.136 gram atoms of V) and 48.1 grams of ammonium paramolybdate (0.272 gram atoms of Mo) were dissolved in .5 liters of water while stirring at 85-95C., in a stainless steel .
steam jacketed evaporating dish.
To the resulting solution was added 31.0 grams ~ ~ :
: of nlobium oxalate solution (14.6% Nb205) (0.034 gram atomæ Nb).
~ ::

~ 9 6 ~ 1 10516 The resulting mixture was heated while stirring and 145 grams Norton silica-alumina #5218 4 x 8 mesh (irregular shapes) were added. This was followed by drying by evaporation with stirring. Further drying was carried out at a temperature of 120 for a period of 16 hours.
The dried material was then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace ~or 4 hours at 400 in an ambient atmosphere of air. The amount of catalyst deposited on the support calculated from the weight increase o~ the catalyst obtained is 19.7%.

M16V12.9NblO.l_ or MlVO.806NbO.63 22.5 grams of ammonium meta-vanadate (0.192 gram atoms of V) and 42.1 grams of ammonium paramoly~date (0.238 gram atoms of Mo) were dissolved in .5 liters of water while 8tirring a~ 85-95, in a stainless steel steam 3acketed evaporating dish.
~ To the resulting ~olution were added 137.7 grzms of niobi~m oxalate solution (14.6% Nb205) (O.lSl gram atoms Nb) and 12.6 grams of ammonium nitrate (~H4N03) (0.157 mols).
The resulting mixture was heated while stirring - ant 160 grams Norton silica-alumina #5218 4 x 8 mesh (irregular shapes) were added. This was followed by : 57.

:' ' 3~Q968~1 drying by evaporation with stirring. Further drying was carried out at a temperature of 120 for a period of 16 hours.
The dried material was then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 4 hours at 400 in an ambient atmosphere of air. The amount of catalyst deposited on the support calculated from the weight increase of the catalyst obtained is 20.3%.

M16V21 3~b3.7 or Molvl~33Nbo~23 42.4 Grams of ammonium meta-vanadate (0.362 gram atoms of V) and 48.1 grams of ammonium paræmolybdate (Q.272 gram atoms of Mo) were dissolved in .5 liters of water while stirrlng at 85-95~ in a stainless steel steam jacketed evaporating dish.
To the resulting solution were added 57.4 grams of niobium oxalate solution (14~6% Nb205) (0~063 gram atoms Nb) and 5.0 grams of ammonium nitrate ~NH4N03) (0.062 mols) dissolved in 30 ml water.

The resulting mixture was heated while stirring and 160 grams"Norton'silica-alumina ~5218 4 x 8 mesh (irregular shapes) were added. This was followed by drying by evaporation with stirring. Further drying was carried out at a temperature of 120 for a period of 16 hours.

58.

1~ 9 6 8 ~ 1 10516 The dried material was then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calclned in a muffle furnace for 4 hours at 400 ~n an ambient atmosphere of air. The amount of catalyst deposited on the support calculated from the weight increase of the catalyst obtained is 24.2~.

Mol6V4Sb2 or MlV0.25SbO.125 70 Grams of ammonium meta-vanadate (0.6 gram atoms of V) and 424 grams of ammonium paramolybdate (2.4 gram atoms of Mo) were dissolved in 2.0 liters of water while stirring at 60-80, in a stainless steel evaporating dish.
To the resulting solution were added 95 grams of o~alic acid (in 500 ml water) (0.75 mols H2C204) and 370 grams of colloidal antimony 02ide (lOV/o Sb) (0.3 gram atoms Sb).
The resulting mi~ture was heated while ~tirring and 1040 grams (1000 ml)~Norton silica-alumina #5218 l/47' spheres we~e added. This was followed by drying by evaporation with stirring on a steam bath. Further drying was carried out at a temperature of 120 for a period of 16 hours.
The dried material was then transferred to a tray fabrica~ed from 10-mesh stainless steel wire screen and calcined in a muffle urnace for 4 hours at 400 in a~

59.

68~

ambient atrnosphere of air. The amount of catalyst deposited on the support calculated from the weight increase o~ the catalyst obtained is 16~8~/o~

M16V4Si32 or MolV0 25Si2 23.9 Græms of ammonium meta-vanadate (0.204 gram atoms of V) and 144.3 grams of ammonium paramolybdate (0.817 gram atoms of Mo) were dissolved in .5 liters of water while stirring at 85-95, in a stainless steel steam jacketed evaporating dish.
To the result~ng solution were added 326 grams of "Ludo~ AS" (30.1% SiO2) (1.633 gram atoms Si).
The resulting mixture was heated while stirring and dried by evaporation with stirring. Further dryi~g was carried out at a temperature of 120~ for a period of 16 hours.
The dried material was broken to 4 x 8 mesh and then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnaee for 4 hours at 400 in an ambie~t atmosphere of air. This was a neat catalyst; no support was added.

Mol6VgSn2 or MlV0.5SnO.125 16.0 Erams of ammonium meta-va~adate (0.137 gram atoms of V) and 48.1 grams of ammonium paramolybdate (0.272 græm atoms of Mo) were dissolved in .5 liters of 9 ~

water while stirring at 85-95, in a stainless steel steam jacketed evaporating dish.
To the resulting solution were added 7.7 grams of stannous chloride (SnC12~2H20) (0.034 gram atoms Sn~
in 120 ml water and 5 ml concentrated hydrochloric acid.
The resulting mixture was heated while stirring and 140 grams"Norton silica-alumina #5218 4 x 8 mesh (irregular shapes) were added. This was followed by drying by evaporation with stirring. Further drying was carried out at a temperature of 120 for a per~od of 16 hours.
The dried material was then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 4 hours at 400 in an ambient atmosphere of air. The amount of catalyst deposited on the support calculated from the weight increase of the catalyst o~tained is 23.1%.

Mol6V8Ta2 or MlV0,5TaO.125 16.0 Grams of ammonium meta-vanadate (0.137 .
gram atoms of V) and 48.1 grams of ammonium paramolybdate (0.272 gram atoms of Mo) were dissolved in .5 liters of ~; water while stirring at 85-95, in a s~ainless steel steam jacketed evaporating dish.
To the resulting solution was added 43.3 grams of tantalum oxalate ~olution ~17.38% Ta20s) diluted with 61.

lO a 6 ~9 1 10516 100 ml water (0.034 gram atoms Ta).

The resulting mixture was heated while stirring and 140 grams Norton silica-alumina #5218 4 x 8 mesh (irregular shapes) were added. This was followed b~
drying by evaporation with stirring. Further drying was carried out at a temperature of 120 for a period of 16 hours.

The dried material was then transferred to a tray fabricated from 10-mesh sta~nless steel wire screen and calcined in a mNffle furnace for 4 hours at 400 in - an ambient atmosphere of air. The amount of catalyst deposited on the support calculated from the weight increase of the catalyst obtained is 23,4%.

Mol6V4Ti2 or MlVQ.2sTiO.125 82 Grams of ammonium meta-vanadate (0.7 gram atoms of V) and 494 grams of ammonium paramolybdate (2.8 gram atoms o~ Mo) were dissolved in 2.0 liters of water while stirring at 60-80a, in a stainless steel evaporating dish.

To th~ resulting solution were added 204 grams of '7TYZoR" LA (titanium lactate) 8.2% Ti (0.35 gram atoms Ti) and 28 grams of ammonium nitrate (0.35 mols NH4N03) dissolved in 100 ml water.
The resulting mixture was heated while stirring and 1040 græms (1000 ml) Norton silica-alumina ~5218 62.

~ 10516 1/4" spheres were added. This was followed by drying by evaporation with stirring on a steam bath. Further drying was carried out at a temperature of 120 for a period o~ 16 hours.
The dried material was then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a mNffle furnace for 4 hours at 400 in an smbient atmosphere of air. The amount of catalyst deposited on the support calculated from the weight increase of the catalyst obtained is 30.4%.
,EXAMPIE 46 Mol6V8W2 or M~V0.5W0.125 15.9 Grams of ammonium meta-vanadate (0.136 græm atoms of V) and 48.1 grams of ammonium paramolybdate e~s (0.272 gram atoms of Mo) were dissolved in 500 ~ eE~ of water while stirring at 85-95, in a stainless steel steam ~acketed evaporating dish.
To the resulting solution were added 8.6 græms of ammonium metatungst~te 92% W03 (in 100 ml water) (0.034 gram atom W).
The resulting mixture was heated while stirring and 145 grams Norton silica-alumina #5218 4 x 8 mesh (irregular shapes) were added. This was followed by drying by evaporation with stirring. Further drying was carried out at a temperature of 120 for a period of 16 hours.

63.

~6B~ 10516 The dried material was then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a mu~fle furnace for 4 hours a~ 400 in an ambient atmosphere of air. The amount of catalyst deposited on the support calculated from the weight increase of the catalyst obtained is 26.1%.

64.

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lO ~ 6 8 9 ~ 10516 Catalysts 47-58 were prepared as disclosed below, and evaluated in Catalyst Test Procedure B. ~ach of the catalysts of Examples 47-57 contain the elements Mo, V and Nb and one other X or Y element. The catalyst of Example 58 contains the elements Mo and V, and W and Mn. The composition of each catalyst is given at the heading o the respective Examples, and the test results are given in Table III below.
Each catalyst of Examples 47-58 was evaluated at two hot spot temperatures between 300 and 400C. to determine the % conver~ion and % efficiency results at each such temperature for oxydehydrogenating ethane to ethylene.
EX~MPLE 47 Mol6~4Nb2Ko.s or MlV0.25NbO.125K0 031 8.0 Grams of ammonium meta-vanadate (0.068 gram atoms of V) and 48.1 grams of ammonium paramolybdate (0.272 gram atoms of Mo) were dissolved in .5 liters of water while stirring at 85-95, in a stainless steel steam jacketed evaporating dish.
To the resulting solution were added 0.85 ~rams of potassium nitrate (KN03) (0.0084 gram atoms K) and 31 grams of niobium oxalate solution (14.6% Nb20~) 0.034 ~' gram atoms Nb) and 2.8 grams ammonium nitrate (NH4N03) (0.035 mols).

67.

~0 9 6 8 9 ~ 10516 The resulting mixture was heated while stirring and 150 grams Norton silica-alumina #5218 4 x 8 mesh (irregular shapes) were added. This was followed by drying by evaporation with stirring. Further drying was carried out at a temperature of 120 for a period of 16 hours.
The dried material was then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 4 hours at 400 in an ambient atmosphere of air. The amount of catalyst deposited on the support calculated from the weight increase of the catalyst obtained is 17.9%.

Mol6V4Nb4P~ or Molvo.2sNbo.25po-25 8 Grams of ammonium meta-vanadate (0.068 gram atoms of V) and 48.1 grams of ammonium paramolybdate (0.272 gram atoms of Mo) were dissolved in .5 liters of water while stirring at 85-95, in a stainless steel steam jacketed evaporating dish.
To the resulting solution were added 7.8 grams of phosphoric acid (85.6V/o H3P04) (0.068 gram atoms P) and 62 grams of niobium oxalate solution (14.6% Nb20s) (0.068 gram atoms Nb) and 5.6 grams ammonium nitrate (0.07 mols NH4N03).
The resulting mixture was heated while stirring and 150 grams Norton'silica-alumina #5218 4 x 8 mesh 68.

~ g S 8g ~ 10516 (irregular shapes) were added. This was ~ollowed by drying by evaporation with stirring. Further drying was carried out at a temperature of 120 for a period of 16 hours.
The dried material was then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 4 hours at 400 in an ambient atmosphere of air. The amount of ~atalyst deposited on the support calculated from ~he weight increase of the catalyst obtained is 25.3%.

Mol6v8Nb2ce2 or MolV0 sNb0.l2sCeO.125 15.9 Grams of ammonium me~a-vanadate (0.136 gram atoms of V) and 48.1 grams of ammonium p æ amolybdate (0.272 gram atoms of Mo) were dissolved in .5 liters of weter while stirring at 85-95, in a stainless steel steam ~acketed evaporating dish.
To the resulting solution were added 31 grams of niobium oxalate solution (14.6% Nb205) in 100 ml water ~- 20 (0.034 gram atoms Nb) and 14 grams of cerium nitrate (41.8% CeO2) (0.034 gram atoms Ce) dissolved in 150 ml water.
The resulting mixture was heated while stirring and 150 grams Norton silica-alumina #5218 4 x 8 mesh (irregular shapes) were added. This was followed by drying by evaporation with stirring. Further drying was 6g-~Q~ 6 8~ 1 10516 carried out at a temperature of 120 for a period of 16 hours.
The dried material was then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 4 hours at 400 in an ambient atmosphere of air. The amount of eatalyst deposited on the support calculated from the weight increase of the catalyst ob~ained is ~8 Mol6v8Nb2co2 or MlV0.5NbO.125C0.125 .
15.9 Grams of ammonium meta-vanadate (0.136 gram atoms of V) and 48.1 grams of = onium paramoiybdate (0.272 gram atoms of Mo) were dissolved in .5 liters of water while stirring at 85-95, in a stainless steel steam jacketed evapora~ing dish.
To the resulting solution were added 31 grams of niobium oxalate solution (14.6% Nb205) in 100 ml water (0.034 gram atoms Nb) and 8.5 grams of cobalt acetate, lCo(CH3C00)2 4H20] (0.034 gram atoms Co) dissolved i~
150 ml water.
The resulting mixture was heated while stirring and 150 grams Norton silica-alumina #5218 4 x 8 mesh (irregular shapes) were added. This was followed by drying by evaporation with stirring. Further drying was carried out at a temperature of 120 for a period of 16 hours.

70.

1~ ~ 6 ~ 1 10516 The dried material was then transferred to a tray fabricated from 10-mesh stainless steel wire scree~
and calcined in a muffle furnace for 4 hours at 400 in an ambient atmosphere of air. The amount of catalyst deposited on the suppor~ calculated from the weigh~
increase of the catalyst obtained is 26.3%.

Mol6VgNb2Cr2 or MlV0.5NbO.125CrO.125 .
15.9 Grams of ammonium meta-vanadate (0.136 gr2m atoms of V) and 48.1 grams of ammonium paramolybdate tO.272 gram atoms of Mo) were dissolved in .6 liters of water while stirring at 85-95a, in a stainless steel steam ~acketed e~aporating dish.
To the resulting solution were added 31 grams of n~obium oxalate solution (14.6% Nb20s) in 100 ml water (0.034 gram atoms Nb) and 8.4 grams of chromium acetate, [Cr(C2H302)3 H20] (0.034 gram atoms Cr) dissolved in 150 ml water.
The resulting mixture was heated while stirring and 150 grams Norton silica-alumina #5218 4 x 8 mesh (irregular shapes) were added. This was followed by drying by evaporation with stirring. Further drying was carried out at a temperature of 120 for a period of 16 hours.
The dried material was then transferred to a tray fabricated from 10-mesh stainless steel wire screen 1~6891 ~ 10516 and calcined in a muffle f~rnace for 4 hours at 400 in an ambient atmosphere of air. The amount of catalyst deposited on the support calculated from the weight increase of the catalyst obtained is 24~2~/

Mol6V8Nb2CU2 or MlV0.5NbO.125CU0.125 15.9 Grams of ammonium meta-vanadate (0.136 gram atoms of V) and 48.1 grams of ammonium paramolybdate (0.272 gram atoms of Mo) were dissolved in .5 liters of water while st~rring at 85-95, in a stainless steel steam jacketed evaporating dish.

To the resulting solution were added 31 grams of nlobium oxalate solution (14.6% Nb205) in lO0 ml water (0.034 gram atoms Nb) and 6.8 grams of cupric acetate, 1(CH3COO)2CU-H2O] (0.034 gram atoms Cu) dissolved in 150 ml water.
The resulting mixture was heated while stirring and 150 grams Norton silica-alumina #5218 4 x-8 mesh (irregular shapes) were added. This was followed by drying by evaporation with stirring. Further drying was carried out at a temperature of 120 for a period of L~
hours~
The dried ma~erial was then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace or ~ hours at 400 in an ambient atmosphere of air. The amount of catalyst 72.

1~68~1 10516 deposited on the support calculated from the weight increase of the catalyst obtained is 25.1%.

Mol6V8Nb2Fe2 or MlV0.5NbO,125FeO.125 . . .
15.9 Grams of ammonium meta-vanadate (0.136 gram atoms of V) and 48.1 grams of ammonium paramolybdate (0.272 gram atcms of Mo) were dissolved in .5 liters of water while ætirring at 85-95, in a stainless steel steam jacketed evaporating dish.
To the resulting solution were added 31 grams of niobium oxalate solution (14.6% ~b20s) in 100 ml water (0.034 gram atoms Nb) and 6.4 grams of ferric oxalate, [Fe2(C204)3l (0.034 gram atoms Fe) dissolved in 150 ml water plus 4.4 grams of oxalic acid.
The result~ng mixture was heated while st~rring and 150 grams ~orton silica-alumina #5218 4 x 8 mesh (irregular shapes) were added. This was followed by drying by evaporation with stirring. Further drying was carried out at a temperature of 120 for a period of 16 hours.
The dried material was then transferred to a tray ~abricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 4 hours at 400 in an ambient atmosphere of air. The amount of catalyst deposited on the support calculated from the weight increase of the catalyst obtained is 23%.

10 ~ 6 8g ~ 10516 Mol6VgNb2Mn2 or MolVo sNb0.l25MnO.l25 .
15.9 Grams of ammonium meta-vanadate (0.136 grzm atoms of V) and 48.1 grams of ammonium paxamoly~date (0.272 gram atoms of Mo) were dissolved in .4 liters of water while stirring at 85-95C, in a stainless steel steam jacketed evaporating dish.
To the resulting solution were added 31 grams of niobium oxalate solution (14.6% Nb205) (0.034 gram atoms Nb) and 8.4 grams of manganese acetate, (0.034 gram atoms Mn) dissolved in 100 ml water, The resulting mixture was heated while stirring and 140 grams tNorton'silica-alumina ~5218 4 x 8 mesh (irregular shapes) were added. This was followed by drying by evaporation with stirring. Further drying was carried out at a temperature of 120 for a period of 16 hours.
The dried material was then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined i~ a muffle furnace for 4 hours at 400 i~ an ambient atmosphere of air. The amount of catalyst deposited on the support calculated from the weight increase of the catalyst obtained is 25.4%.

Mol6VgNb2Ni2 or MlV0.5NbO.125NiO.125 , 15.9 Grams of ammonium meta-va~adate (0.136 græm atoms of V) and 48.1 grams of ammon~um paramolybdate 74.

109~8~1 10516 (0.272 gram atoms of Mo) were dissolved in .5 liters of water while stirring at 85-95, in a st~inless steel steam jacketed evaporating dish.

To the resulting solution were added 31 grams of niobium oxalate solution (14.6% Nb205) in 100 ml water (0.034 gram atoms Nb) and 8.5 grams of nickelous acetate (~i(C2H302~-4H20)~ (0.034 gram atoms Ni) dissolved in 150 ml water.
The resulting mixture was heated while st~rr:ing and 150 grams Norton silica-alumina #5218 4 x 8 mesh (irregular shapes) were added. This was followed by drying by evaporation with stirring. Further trying was carried out at a temperature of 120 for a period of 16 hours.
The dried material was then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 4 hours at 400 in an ambient a~mosphere of air. The amount of catalyst deposited on the support calculated from the weight increase of the ~ ~ 20 catalyst obtained is 26.4%.
- ~ EXAMPLE 56 Mol6VgNb2Si32 or MlVO.sNbO.125Si2 35.9 Græms of ammonium meta-vanadate (0.307 grams atoms of V) and 10~.0 grams of ammonium paramolybdate (0.612 gram atoms of Mo) were dissolved in .5 li~ers of water while stirring at 85-95, in a stainless steel steam ~acketéd evaporating dish.

~Q~68~1 10516 ~ To the resulting solution were added 69.6 grams of niqbium oxalate solution (14.6% Nb205), (0.076 gram atoms Nb) and 244.2 grams of "Ludox AS" colloidal silica sQ~ ~30~1~/o SiO2)~ (1,223 gram atoms Si).
The resulting mixture was heated while stirring and dried by evaporation with stirring. Further drying was carried ou~ at a temperat~re of 120 for a period of 16 hours.
m e dried material was broke~ to 4 x 8 mesh and was ~hen transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle ~ : :
furnace for 4 hours at 400 in an ambient atmosphere of air. This was a neat catalyst, no support was added.
~ . EXAMPLE 57 ; Mol6V8Nb2Ul or MlV0.5NbO.125U0.0625 .
15~9 Grams of ammonium meta-vanadate (0.136 græm atoms of V) and 48.1 grams of ammonium paramolybdate (0.272 gram atoms of Mo) were dissolved ~n .35 liters of : water while stirring at 85-95C~ in a stainless steel steam ~acketed evaporating dish.

: ; To the resulting solution were added 31 græms , of niabium oxalate solution (14~6% Nb205) (0.034 gram ~; atoms Nb) and 7.2 grams of uranyl ac2tate, [(CH3C00)2U02-2H20] (0.017 gram atoms U).

:
76.

3L~q6~1 The resulting mixture was heated while stirring and 140 grams'Norton silica-alumina #5218 4 x 8 mesh ~irregular shapes) were added. This was followed by drying by evaporation with stirring. Further drying was carried out at a temperature of 120~ for a period of 16 hours.
The dried material was then transferred to a tray fabricated from lO-mesh stainless steel wire screen and calcined in a muffle furnace for 4 hours at 400 in an ambient atmosphere of air. The amount of catalyst deposited on the support calculated from the weight increase of the catalyst obtained is 27%.

Mol6V4W1 6Mn4 or MlV0.25WO.lM~0.25 350 grams of ammonium meta-vanadate (3 gram atoms of V) and 2120 grams of ammonium paramolybdate (12.0 gram atoms of Mo) were dissolved in 10 liters of wat~r while stirring at 60-80, in a stainless steel evaporating dish.
To the resulting solution were added 313 grams of ammonium paratungstate dissol~ed in 5 liters water (1.13 gram atoms W) and 750 grams of manganese acetate 4H20 (3.06 gram atoms Mn) dissolved in 1 liter water.
The resulting mixture was heated while stirring and dried by evaporation with stirring. Further drying was carried out at a temperature of 120 for a period of 16 hours.

~q~ 0516 The dried material was broken to 4 x 8 mesh and then transferred to a tray fabricated from 10-mesh stainless steel wire screen and calcined in a muffle furnace for 5 hours at 400 in an ambient atmosphere of air. This was a neat catalystO

78.

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80, lO 9 6 ~9 10516 The catalyst of Example 35 ~M16V4.6NbO.6) was used in three experiments (Examples 59-61) ~n the oxydehydrogenation of ethane to ethylene, in the absence or presence o~ added water, to demonstrate the ability of such catalyst to prepare acetic acid under such conditions. No water was added in Examples 59-60.
Water was added in Example 61. The reaction conditions employed (pressure, temperature, inlet gas composition, inlet water rate and outlet water rate), and the test results (% selectivity, productivity and % conversion) for these examples are shown below in Table IV. The catàlyst was evaluated in Examples 59-61 by Catalyst Test Procedure C.

81.

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.~
~ l ¢ h ~ J ~ ~ ~ ~ U~
,1 a~
a) o o a) ~ ~
¢ ~0~ ~
O m ~ ~d O ~ ~ ~ o ao ~ ~rl o ~ ~) .
h oo O t~
4 ~ O O cr~ S~
o a~ ~d tn. . . ~, S~ ~ ~ a~ o o o P~ ~ ~
3 H 0~ O ^

O ~ :C C`3 00 o~ ~g ~ oo oo * ~ ~1 0 00 ~I CO ~ ~1 U~ ~ ~ . . . 4~ ~
. ~ o m ~ O u~ ~m O ~rl C~l 00 tQ
.,, C~
. ~ o ~> ~D H O¦c~J o U-) ^
~1 C~ C`l c~
O O
~ ~ ~ ~rl .. .. .
~ ~ ~ ~ ~ ~ 1 0 ¢ a~ c~
E~ Sc~ ~
O U~
~ O h rn C~O h O~ IJ IhC~l t~
C~ I~C`3C~l E~~d ~ c~ ~ Oo~
rC ~ ~ ~ O

E~ ~ oo ~ r~

.~ ~
~n I
. ~
O ~ ^ O
a~ ~ rl ~ ~ u~
n ~0 E~ ~ ~ ~ 5~ c~ ~ 1` ;
q . ~ ~
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C~
o 5~
~ a) ~

82 .

~Q96~1 10516 It is believed that two groups of catalysts which are exemplified in various of the examples disclosed above are novel compositions of matter, ~upported and unsupported.
These catalysts comprise the following compositions:

Novel Catalyst I

MhViNbjAk wherein A is Ce, K, P, Ni, and/or U, h is 16, i is 1 to 16, and preferably 1 to 8, j is 1 to 10, and preferably 0.2 to 10, k is > 0 to 32, and preferably 0.1 ~o 5.
Novel Catalyst II
MolWmlh wherein L is Nb and/or Pb, 1 is 16, m is 1 to 16, and preferably 1 to 8, n is 1 to 10, and preferably 0.2 to 10.
In the catalyst evaluation ~ests conducted in Examples 1-23 and 29-61 the effluent gas streams did notcontain any hydrogen, methane or higher alkanes produced by the process.
The products formed in all cases were ethylene, a~etic acid, water 7 CO and COz-83.

Claims (36)

WHAT IS CLAIMED IS:
1. A low temperature process for converting ethane to ethylene which comprises catalytically oxydehydrogenating ethane exothermically at a temperature of < 450°C in the gas phase, wherein the oxydehydrogena-tion catalyst is a calcined composition containing the elements Mo, X and Y in the ratio MoaXbYc wherein X is selected from the group consisting of Cr, Mn, Nb, Ta, Ti, V and/or W, Y is selected from the group consisting of Bi, Ce, Co, Cu, Fe, K, Mg, Ni, P, Pb, Sb, Si, Sn, Tl and/or U, a is 1 b is 0 to 2 and c is O to 2, with the proviso that the total value of c for Fe, Co and/or Ni is < 0.5
2. A process as in claim 1 in which b is 0.05 to 1Ø
3. A process as in claim 1 in which c is 0.05 to 1Ø
4. A process as in claim in which X comprises V.
5. A process as in claim 4 in which X comprises V and Nb.
6. A process as in claim 5 in which X comprises V, Nb and Mn.

84.
7. A process as in claim 1 in which X comprises W.
8. A process as in claim 7 in which X comprises W and V.
9. A process as in claim 7 in which X comprises W and Nb.
10. A process as in claim 3 in which said calcined composition comprises the elements Mo, V and at least one of Fe, Mn, Nb, Sb, Si, Sn, Ta, Ti, and W.
11. A process as in claim 10 in which said cal-cined composition comprises the elements Mo, V and Nb.
12. A process as in claim 10 in which said calcined composition comprises the elements Mo, V and Mn.
13. A process as in claim 3 in which said calcined composition comprises the elements Mo, V, Nb and at least one of Ce, Co, Cr, Cu, Fe, K, Mn, Ni, P, Si and U.
14. A process as in claim 13 in which said cal-cined composition comprises the elements Mo, V, Nb and Ce.
15. A process as in claim 13 in which said cal-cined composition comprises the elements Mo, V, Nb and Cu.
16. A process as in claim 13 in which said cal-cined composition comprises the elements Mo, V, Nb and Fe.
17. A process as in claim 13 in which said cal-cined composition comprises the elements Mo, V, Nb and Mn.

85.
18. A process as in claim 13 in which said calcined composition comprises the elements Mo, V, Nb and Si.
19. A process as in claim 13 in which said cal-cined composition comprises the elements Mo, V, Nb and U.
20. A process as in claim l which is conducted in the presence of added water.
21. A low temperature process for converting ethane to ethylene which comprises catalytically oxyde-hydrogenating ethane exothermically at a temperature of 450°C. or less in the gas phase in which the catalyst is a calcined composition containing the elements of Mo, X, and Y in the ratio:
MoaXbYc wherein X is at least one of the groups V, Nb and Mn;
V and W, V and Mn; or W and Nb.
Y is selected from the group consisting of Bi, CE, Co, Cu, Fe, K, Mg, Ni, P, Pb, Sb, Si, Sn, Tl and/or U, a is 1 b is 0.05 to 1 c is 0 to 2 with the proviso that the total value of c for Fe, Co and/or Ni is less than 0.5.
22. A process as in claim 21 in which X in said calcined composition also comprises the elements Ta and/or Ti; Y comprises the elements Fe, Sb, Si, and Sn, and b and c are 0.05 to 1; with the proviso that the total value of c for Fe is less than 0.5.

86.
23. A process for the catalytic oxydehydrogena-tion of ethane to ethylene exothermically in the gas phase at a temperature of 550°C. or less by contacting the ethane under such conditions with a calcined catalyst comprising Mo, V, Nb and one additional element of the group Cu, Ce, Mn and U.
24. A process as in claim 3 in which the said catalyst contains the elements Mo, V, and Nb and Mn in the ratio:
ModVeNbfMng d is 16 e is 1 to 8 f is 0.2 to 10 g is 0.1 to 5
25. A process for the catalytic oxydehydrogena-tion of ethane to ethylene exothermically in the gas phase at a temperature of 550°C. or less by contacting the ethane under such conditions with a calcined catalyst comprising Mo, V, Nb and X.
26. A process as in claim 21 in which X comprises V, Nb and Mn.
27. A process as in claim 21 in which X com-prises W and V.
28. A process as in claim 21 in which said calcined composition comprises the elements Mo, V and Mn.
29. A process as in claim 21 in which said 87.

calcined composition comprises the elements Mo, V, Nb and Ce.
30. A process as in claim 21 in which said calcined composition comprises the elements Mo, V, Bn and Cu.
31. A process as in claim 21 in which said calcined composition comprises the elements Mo, V, Nb and Mn.
32. A process as in claim 21 in which said cal-cined composition comprises the elements Mo, V, Nb and U.
33. A process as in claim 23 in which said catalyst comprises the elements Mo, V, Nb and Ce.
34. A process as in claim 23 in which said catalyst comprises the elements Mo, V, Nb and Cu.
35. A process as in claim 23 in which said catalyst comprises the elements Mo, V, Nb and U.
36. A process as in claim 23 in which said catalyst comprises the elements Mo, V, Nb and Mn.

88.
CA 261807 1975-10-01 1976-09-22 Low temperature oxydehydrogenation of ethane to ethylene Expired CA1096891A (en)

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DE2849637A1 (en) * 1978-11-16 1980-05-29 Hoechst Ag Traegerkatalysator and process for its manufacture
JPS56109282A (en) * 1980-02-01 1981-08-29 Chugai Ro Kogyo Kaisha Ltd Thermal decomposition apparatus for wastes such as waste vinyl chloride
FR2511671A1 (en) * 1981-08-18 1983-02-25 Davy Mckee Ag Process for dehydrogenation
DE3208571A1 (en) * 1982-03-10 1983-09-22 Basf Ag Oxidation catalyst, in particular for the production of methacrylic acid by gas-phase oxidation of methacrolein
JPS5995144U (en) * 1983-11-24 1984-06-28
US4524236A (en) * 1984-06-28 1985-06-18 Union Carbide Corporation Process for oxydehydrogenation of ethane to ethylene
US4596787A (en) * 1985-04-11 1986-06-24 Union Carbide Corporation Process for preparing a supported catalyst for the oxydehydrogenation of ethane to ethylene
JPS62202925A (en) * 1986-03-03 1987-09-07 Kawasaki Heavy Ind Ltd Fluidized bed furnace
US5162578A (en) * 1987-06-12 1992-11-10 Union Carbide Chemicals & Plastics Technology Corporation Acetic acid from ethane, ethylene and oxygen
US5260250A (en) * 1989-07-05 1993-11-09 Bp Chemicals Limited Catalyst for the production of ethylene and acetic acid
US5210293A (en) * 1989-07-05 1993-05-11 Bp Chemicals Limited Process and catalyst for the production of ethylene and acetic acid
WO2001005913A1 (en) 1999-07-16 2001-01-25 Reatech Phosphor addition in gasification
JP2001330774A (en) 2000-03-14 2001-11-30 Nikon Corp Zoom lens
US7402719B2 (en) * 2002-06-13 2008-07-22 Velocys Catalytic oxidative dehydrogenation, and microchannel reactors for catalytic oxidative dehydrogenation
DE102006018885A1 (en) * 2006-04-18 2007-10-25 Leibnitz-Institut für Katalyse e.V. an der Universität Rostock A process for the production of olefins, aldehydes and carboxylic acids through oxidation of alkanes
DE102008017308B4 (en) * 2008-04-04 2014-09-25 Süd-Chemie Ip Gmbh & Co. Kg A process for preparing nanocrystalline bismuth Molybdänmischoxidkatalysatoren
DE102008017311A1 (en) 2008-04-04 2009-10-08 Süd-Chemie AG A process for preparing a nanocrystalline Molybdänmischoxidkatalysators

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US3119883A (en) * 1960-08-08 1964-01-28 Du Pont Dehydrogenation of ethane
NL282561A (en) * 1961-09-14
US3320331A (en) * 1966-01-27 1967-05-16 Exxon Research Engineering Co Oxidative dehydrogenation of aliphatic hydrocarbons over aluminum phosphate supported molybdenum and vanadium
FR1590081A (en) * 1968-01-10 1970-04-13
DE1800063B2 (en) * 1968-10-01 1976-11-11 A process for the preparation of mono- and diolefins
BE787078A (en) * 1971-08-02 1973-02-02 Tsailingold Anatoly L Method for obtaining alkenes and alkadienes
US3933933A (en) * 1972-04-19 1976-01-20 Phillips Petroleum Company Oxidative dehydrogenation processes
JPS5331121B2 (en) * 1972-08-16 1978-08-31

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