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Patent 1096891 Summary

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(12) Patent: (11) CA 1096891
(21) Application Number: 261807
(54) English Title: LOW TEMPERATURE OXYDEHYDROGENATION OF ETHANE TO ETHYLENE
(54) French Title: DESOXYHYDROGENATION DE L'ETHANE EN ETHYLENE
Status: Expired
Bibliographic Data
(52) Canadian Patent Classification (CPC):
  • 260/705.2
(51) International Patent Classification (IPC):
  • C07C 11/04 (2006.01)
  • B01J 23/24 (2006.01)
  • B01J 23/34 (2006.01)
  • B01J 23/88 (2006.01)
  • B01J 27/186 (2006.01)
  • C07C 5/48 (2006.01)
(72) Inventors :
  • YOUNG, FRANK G. (United States of America)
  • THORSTEINSON ERLIND M. (United States of America)
(73) Owners :
  • UNION CARBIDE CORPORATION (United States of America)
(71) Applicants :
(74) Agent: HOPLEY, WILLIAM G.
(74) Associate agent:
(45) Issued: 1981-03-03
(22) Filed Date: 1976-09-22
Availability of licence: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): No

(30) Application Priority Data:
Application No. Country/Territory Date
618,836 United States of America 1975-10-01

Abstracts

English Abstract



10516

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.


Claims

Note: Claims are shown in the official language in which they were submitted.


10516

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.

10516

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.

10516

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.

Description

Note: Descriptions are shown in the official language in which they were submitted.


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.


10516
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 .




,. .

893
10516

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


10516
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 ~

10516
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.

10516
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.

10516
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.

10516
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~.

10516

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,

10516
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.
EXAMPLE 1
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.
EXAMPLE 2
Mo Mn or Mo Mn
16 16
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%.
EXAMPLE 4
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.



- 24

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%.
EXAMPLE 5
; ~ 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.






EXAMPLE 6
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
10516

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%.
EXAMPLE 8
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%.
EXAMPLE 9
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.
EXAMPLE 10
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

28

10516
~ ~ 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.
EXAMPLE 11
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~.
EXAMPLE 12
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~
10516


ambient atmosphere of nitxogen. The amount of
unsupported catalyst is 2027 grams. The catalyst was
reduced to 25-mesh.
EXAMPLE 14
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


EXAMPLE 15
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
10516


EXAMPLE 16
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 ~
10516


EXAMPLE 17
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 ~
10516

EXAMPLE 18

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.

10516


EXAMPLE 19
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.

10516

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.
EXAMPLE 20
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.
.

10516


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~
10516

EXAMPLE 22
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.
EXAMPLE 23
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.


EXAMPLES 24-28
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.

42

6 89 i
10516


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.
EXAMPLE 25
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.

391
10516


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.
EXAMPLE 26
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.
EXAMPLE 27

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


EXAMPLE 28
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.

10516
~68~L



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P: ooU~ ~ ~ ~ o ~ ,` ~ o
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_ ~o oooooooooC~
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X ~ ~ ~ ~ ~ ~ I~ o~ ~ o ~.
~a


47 .,

10516
89~


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O~ ~ o ~ o co oo ~ r~
\t


o o~ u~ o o
x o o~1 oo ~ a~ o ~Q o
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o ~ oo ~O a~ u~ ~ o ~ o ~ o
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x æ x x x x x ~
.




48,

9~
10516


EXAMPLES 29-46
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.
EXAMPLE 29
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
10516


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.
EXAMPLE 30
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.

10516


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%.
EXAMPLE 32
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
10516

(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.
EXAMPLE 33
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.
EXAMPLE 34
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.
EXAMPLE 35
-
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.

10516

EXAMPLE 36
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.
EXAMPLE 37 -
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%.
EXAMPLE 38
; 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%.
EXAMPLE 39

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
10516

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%.
EXAMPLE 40
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~.
EXAMPLE 41
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~
10516

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~
EXAMPLE 42

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.
EXAMPLE 43
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


600


9 ~
10516

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%.
EXAMPLE 45
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.

10516
~ q~8~1
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.-1 ~ o oo ~ ~ o o o
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65 .

10516

1~96891

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~ ~ . ~ o o o o o ~ o o o o o oo o o o o o o o
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66 .

lO ~ 6 8 9 ~ 10516


EXAMPLES 47-58
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%.
EXAMPLE 49
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
EXAMPLE S0

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%.
EXAMPLE 51
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~/

EXAMPLE 52

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%.
EXAMPLE 53
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
EXAMPLE 54
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%.
EXAMPLE 55
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
10516

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%.
EXAMPLE 58
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.

10516



6~391


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EXAMPLES 59-61
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.

10516



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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.

Representative Drawing

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Administrative Status

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Administrative Status

Title Date
Forecasted Issue Date 1981-03-03
(22) Filed 1976-09-22
(45) Issued 1981-03-03
Expired 1998-03-03

Abandonment History

There is no abandonment history.

Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Application Fee $0.00 1976-09-22
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
UNION CARBIDE CORPORATION
Past Owners on Record
None
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Number of pages   Size of Image (KB) 
Drawings 1994-03-09 1 15
Claims 1994-03-09 5 133
Abstract 1994-03-09 1 18
Cover Page 1994-03-09 1 13
Description 1994-03-09 82 2,869