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Patent 1204788 Summary

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(12) Patent: (11) CA 1204788
(21) Application Number: 435442
(54) English Title: METHANE CONVERSION
(54) French Title: CONVERSION DU METHANE
Status: Expired
Bibliographic Data
(52) Canadian Patent Classification (CPC):
  • 260/688
  • 260/705.1
  • 260/712.8
(51) International Patent Classification (IPC):
  • C07C 9/02 (2006.01)
  • C07C 11/02 (2006.01)
  • C07C 15/02 (2006.01)
(72) Inventors :
  • JONES, C. ANDREW (United States of America)
  • LEONARD, JOHN J. (United States of America)
  • SOFRANKO, JOHN A. (United States of America)
(73) Owners :
  • ATLANTIC RICHFIELD COMPANY (United States of America)
(71) Applicants :
(74) Agent: OSLER, HOSKIN & HARCOURT LLP
(74) Associate agent:
(45) Issued: 1986-05-20
(22) Filed Date: 1983-08-26
Availability of licence: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): No

(30) Application Priority Data:
Application No. Country/Territory Date
522,938 United States of America 1983-08-12
412,650 United States of America 1982-08-30
412,649 United States of America 1982-08-30
412,666 United States of America 1982-08-30
412,665 United States of America 1982-08-30
412,664 United States of America 1982-08-30
412,663 United States of America 1982-08-30
412,662 United States of America 1982-08-30
412,655 United States of America 1982-08-30
412,667 United States of America 1982-08-30
522,935 United States of America 1983-08-12
522,906 United States of America 1983-08-12
522,876 United States of America 1983-08-12
522,877 United States of America 1983-08-12
522,905 United States of America 1983-08-12
522,942 United States of America 1983-08-12
522,944 United States of America 1983-08-12
522,925 United States of America 1983-08-12

Abstracts

English Abstract






ABSTRACT OF THE DISCLOSURE

A method for synthesizing hydrocarbons from a
methane source which comprises contacting methane with an
oxide of Mn, Sn, In, Ge, Pb, Sb, or Bi at a temperature of
about 500 to 1000°C. The oxide is reduced by the contact
and coproduct water is formed. A reducible oxide is
regenerated by oxidizing the reduced composition with
molecular oxygen. A preferred mode of operation comprises
recirculating solids comprising the reducible oxides
between two physically separate zones: a methane contact
zone and an oxygen contact zone.


Claims

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






The embodiments of the invention in which an exclusive
property or privilege is claimed are defined as follows:


1. A method for converting methane to higher
hydrocarbon products which comprises contacting a gas
comprising methane and an oxidative synthesizing agent
comprising a reducible oxide of at least one metal selected
from the group consisting of manganese, tin, indium,
germanium, lead, antimony, and bismuth at a temperature
selected within the range of about 500 to 1000°C, provided
that when said oxidative synthesizing agent comprises a
reducible oxide of manganese or indium, said contacting is
carried out in the substantial absence of catalytically
effective Ni, Rh, Pd, Ag, Os, Ir, Pt, Au and compounds
thereof.
2. The method of Claim 1 wherein the gas
contains about 40 to 100 vol. % methane.
3. The method of Claim 1 wherein the gas
contains about 80 to 100 vol. % methane.
4. The method of Claim 1 wherein the gas
contains about 90 to 100 vol. % methane.
5. The method of Claim 1 wherein the gas compri-
sing methane is natural gas.
6. The method of Claim 1 wherein the gas compri-
sing methane is processed natural gas.
7. The method of Claim 1 wherein a gas consis-
ting essentially of methane is contacted with the said
reducible oxide.
8. A method for synthesizing hydrocarbons from a
methane source which comprises:
(a) contacting a gas comprising methane with
a solid comprising a reducible oxide of

- 56 -





at least one metal selected from the
group consisting of manganese, tin,
indium, germanium, lead, antimony and
bismuth at a temperature selected within
the range of about 500 to 1000°C to form
C2+ hydrocarbons, coproduct water and
solids comprising a reduced metal oxide,
provided that when said solid comprises
a reducible oxide of manganese or indium,
said contacting is carried out in the
substantial absence of catalytically
effective Ni, Rh, Pd, Ag, Os, Ir, Pt, Au
and compounds thereof;
(b) recovering C2+ hydrocarbons;
(c) at least periodically contacting the
solids comprising a reduced metal oxide
with an oxygen-containing gas to produce
solid comprising a reducible metal
oxide; and
(d) contacting a gas comprising methane with
the solids produced in step (c) as recited
in step (a).
9. The method of Claim 8 wherein the temperature
of step (c) is selected within the range of about 300 to
1200°C.
10. A method for converting methane to higher
hydrocarbon products which comprises contacting a gas
comprising methane and a reducible oxide of manganese at a
temperature within the range of about 500 to 1000°C, said
contacting being carried out in the substantial absence of


- 57 -





catalytically effective Ni, Rh, Pd, Ag, Os, In, Pt, Au and
compounds thereof.
11. The method of Claim 10 wherein the reducible
oxide of manganese is contacted with a gas comprising
methane at a temperature within the range of about 600 to
900°C.
12. The method of Claim 10 wherein the gas
contains about 40 to 100 vol. % methane.
13. The method of Claim 10 wherein the gas
contains about 80 to 100 vol. % methane.
14. The method of Claim 10 wherein the gas
contains about 90 to 100 vol. % methane.
15. The method of Claim 10 wherein the gas
comprising methane is natural gas.
16. The method of Claim 10 wherein the gas
comprising methane is processed natural gas.
17. The method of Claim 10 wherein a gas consis-
ting essentially of methane is contacted with the said
reducible oxide.
18. The method of Claim 10 wherein the reducible
oxide of manganese comprises Mn3O4.
19. The method of Claim 10 wherein the oxide of
manganese is associated with a support material.
20. The method of Claim 18 wherein the oxide of
manganese is associated with a support material.
21. The method of Claim 19 wherein the support
material is silica.
22. The method of Claim 20 wherein the support
material is silica.
23. A method for synthesizing hydrocarbons from a

- 58 -





methane source which comprises:
(a) contacting a gas comprising methane with
a solid comprising a reducible oxide of
manganese at a temperature within the
range of about 500 to 1000°C to form C2+
hydrocarbons, coproduct water, and
solids comprising a reduced oxide of
manganese, said contacting being carried
out in the substantial absence of catalyt-
ically effective Ni, Rh, Pd, Ag, Os, Ir,
Pt, Au and compounds thereof;
(b) recovering C2+ hydrocarbons;
(c) at least periodically contacting the
solids comprising the reduced oxide of
manganese with an oxygen containing gas
to produce a solid comprising a reducible
oxide of manganese; and
(d) contacting a gas comprising methane with
the solids produced in step (c) as
recited in step (a).
24. The method of Claim 23 wherein the temperature
of step (c) is within the range of about 300 to 1200°C.
25. The method of Claim 23 wherein the tempera-
ture of step (c) is within the range of about 700 to 1200°C.
26. The method of Claim 23 wherein the tempera-
ture of step (c) is within the range from about 900 to
1200°C.
27. The method of Claim 26 wherein the reducible
oxide of manganese comprises Mn3O4.
28. The method of Claim 25 wherein the said solid

- 59 -





of step (a) comprises Mn3O4 on a silica support.
29. The method of Claim 23 wherein the tempera-
ture of step (a) is within the range of about 600 to 900°C.
30. The method of Claim 29 wherein the tempera-
ture of step (c) is within the range of about 700 to 1200°C.
31. A method for converting methane to higher
hydrocarbon products which comprises contacting a gas
comprising methane and a reducible oxide of tin at a
temperature within the range of about 500 to 1000°C.
32. A method for converting methane to higher
hydrocarbon products which comprises contacting a gas
comprising methane and a reducible oxide of indium at a
temperature within the range of about 500 to 850°C, said
contacting being carried out in the substantial absence of
catalytically effective Ni, Rh, Pd, Ag, Os, Ir, Pt, Au and
compounds thereof.
33. A method for converting methane to higher
hydrocarbon products which comprises contacting a gas
comprising methane and a reducible oxide of germanium at
a temperature within the range of about 500 to 800°C.
34. A method for converting methane to higher
hydrocarbon products which comprises contacting a gas
comprising methane and a reducible oxide of lead at a
temperature within the range of about 500 to 1000°C.
35. A method for converting methane to higher
hydrocarbon products which comprises contacting a gas
comprising methane and a reducible oxide of antimony at a
temperature within the range of about 500 to 1000°C.
36. A method for converting methane to higher
hydrocarbon products which comprises contacting a gas

- 60 -





comprising methane and a reducible oxide of bismuth at a
temperature within the range of about 500 to 850°C.
37. A method for converting methane to higher
hydrocarbon products by contacting methane with an oxida-
tive synthesizing agent which agent comprises at least one
reducible oxide of at least one metal which oxides when
contacted with methane at synthesizing conditions are
reduced and produce higher hydrocarbon products and water;
which method comprises contacting a gas comprising methane
and an oxidative synthesizing agent under elevated pressure.
38. The method of claim 37 wherein the pressure
is within the range of about 2 to 100 atmospheres.
39. The method of claim 37 wherein the pressure
is within the range of about 3 to 30 atmospheres.
40. A method for converting methane to higher
hydrocarbon products by contacting methane with an oxida-
tive synthesizing agent comprising at least one reducible
oxide of at least one metal selected from the group consis-
ting of Mn, Sn, In, Ge, Pb, Sb and Bi, which method
comprises contacting a gas comprising methane and said
oxidative synthesizing agent under elevated pressure.
41. The method of Claim 40 wherein the pressure
is within the range of about 2 to 100 atmospheres.
42. The method of Claim 40 wherein the pressure
is within the range of about 3 to 30 atmospheres.
43. The method of Claim 41 wherein the tempera-
ture of said contact is selected within the range of about
500 to 1000°C.
44. The method of Claim 43 wherein the metal
selected is Mn.

- 61 -





45. The method of Claim 44 wherein the said
contacting is carried out in the substantial absence of
catalytically effective Ni, Rh, Pd, Ag, Os, Ir, Pt, Au and
compounds thereof.
46, A method for converting methane to higher
hydrocarbon products by contacting methane with an oxida-
tive synthesizing agent which agent comprises at least one
reducible oxide of at least one metal which oxides when
contacted with methane under synthesizing conditions are
reduced and produce higher hydrocarbon products and water;
which method comprises:
(a) continuously introducing and contacting
a gas comprising methane and particles
comprising an oxidative synthesizing
agent under synthesizing conditions in a
first contact zone to form C2+ hydro-
carbons, coproduct water, and particles
comprising a reduced metal oxide;
(b) continuously removing particles compri-
sing a reduced metal oxide from the
first zone and contacting the particles
with an oxygen-containing gas in a
second zone to produce particles compri-
sing an oxidative synthesizing agent;
and
(c) returning particles formed in the second
zone to the first zone.
47. A method for converting methane to higher
hydrocarbon products which comprises:
(a) continuously introducing and contacting


- 62 -





a gas comprising methane and particles
comprising an oxidative synthesizing
agent, which agent comprises at least
one reducible oxide of at least one
metal selected from the group consisting
of Mn, Sn, In, Ge, Pb, Sb and Bi, under
synthesis conditions in a first contact
zone to form C2+ hydrocarbons, coproduct
water, and particles comprising reduced
synthesizing agent; and
(b) continuously removing particles compri-
sing reduced synthesizing agent from the
first zone and contacting the said
reduced particles with an oxygen-
containing gas in a second zone to
produce particles comprising an oxida-
tive synthesizing agent; and
(c) returning particles formed in the second
zone to the first zone.
48. The method of Claim 47 wherein particles are
maintained in the first zone as a fluidized bed of solids.
49. The method of Claim 48 wherein particles are
maintained in the first zone as a fluidized bed of solids.
50. The method of Claim 48 wherein the average
residence time of particles in the first zone is within the
range of about 0.04 to 30 minutes.
51. The method of Claim 48 wherein the average
residence time of particles in the first zone is within the
range of about 0.04 to 4 minutes.
52. The method of Claim 50 wherein the residence

- 63 -





time of methane feedstock in the first zone is within the
range of about 0.1 to 100 seconds.
53. The method of Claim 50 wherein the residence
time of methane feedstock in the first zone is within the
range of about 1 to 20 seconds.
54. The method of Claim 47 wherein the tempera-
ture of the first zone is selected within the range of
about 500 to 1000°C.
55. The method of Claim 47 wherein the said
reducible oxide is associated with a support material.
56. The method of Claim 55 wherein the support
material is silica.
57. The method of Claim 47 wherein the metal
selected is Mn.
58. The method of Claim 57 wherein said contact-
ing in the first zone is carried out in the substantial
absence of catalytically effective Ni, Rh, Pd, Ag, Os Ir,
Pt, Au and compounds thereof.
59. The method of Claim 57 wherein the tempera-
ture of the first zone is within the range of about 500 to
1000°C.
60. The method of Claim 47 wherein the metal
selected is Sn and the temperature of the first zone is
within the range of about 500 to 1000°C.
61. The method of Claim 47 wherein the metal
selected is In and the temperature of the first zone is
within the range of about 500 to 850°C.
62. The method of Claim 61 wherein the contact-
ing in the first zone is carried out in the substantial
absence of catalytically effective Ni, Rh, Pd, Ag, Os, Ir,
Pt, Au and compounds thereof.

- 64 -





63. The method of Claim 47 wherein the metal
selected is Ge and the temperature of the first zone is
within the range of about 500 to 800°C.
64. The method of Claim 47 wherein the metal
selected is Pb and the temperature of the first zone is
within the range of about 500 to 1000°C.
65. The method of Claim 47 wherein the metal
selected is Sb and the temperature of the first zone is
within the range of about 500 to 1000°C.
66. The method of Claim 47 wherein the metal
selected is Bi and the temperature of the first zone is
within the range of about 500 to 850°C.


- 65 -

Description

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


88


PF 50-55-OlllA


METHANE CONVERSION


BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
This invention relates to synthesis of hydro-
carbons from a methane source. A particular application of
this invention is a method for converting natural gas to
more readily transportable material.
ESCRIPTION OF THE PRIOR ART
A major source of methane is natural gas. Other
sources of methane have been considered for fuel supply,
e~g., the methane present in coal deposits or formed during
mining operations. Relatively small amount of methane are
also produced in various petroleum processes.
The composition of natural gas at the wellhead
varies but the major hydrocarbon present is methane. For
example the methane content of natural gas may vary within
the range of from about 40 to 95 vol. ~. Other constitu-

ents of natural gas may include ethane, propane, butanes,pentane (and heavier hydrocarbons)~ hydrogen sulfide,
carbon dioxide, helium and nitrogen.
Natural gas is classified as dry or wet depending
upon the amount of condensable hydrocarbons contained in it.
Condensable hydrocarbons generally comprise C3-~ hydrocarbons
although some ethane may be included. Gas conditioning is





~2~


required to alter the composition of wellhead gas, process-
ing facilities usually being located in or near the produc-
tion fields. Conventional processing of wellhead natural
gas yields processed natural gas containing at least a
major amount of methane.
Large-scale use of natural gas often requires a
sophisticated and extensive pipeline system. Liquefaction
has also been employed as a transportation means, but
processes for liquefying, transporting, and revaporizing
natual gas are complex, energy-intensive, and require
extensive safety precautions. Transport of natural gas has
been a continuing problem in the exploitation of natural
gas resources. It would be extremely valuable to be able
to con~ert methane (e.g., natural gas) to more easily
handleable, or transportable, products. Moreover, direct
conversion to olefins such as ethylene or propylene would
be extremely valuable to the chemical industry.
In addition to its use as fuel~ methane is used
for the production of halogenated products (e.g., methyl
chloride, methylene chloride, chloroform and carbon tetra-
chloride). Methane has also been used as a feedstock for
producing acetylene by electric-arc or partial-oxidation
processes. Electric-arc processes are operated commer-
cially in Europe. In partial-oxidation processes, a feed
mixture of oxygen and methane (the methane may contain
other, additional hydrocarbons) are preheated to about
540C and ignited in a burner. Representative processes of
this type are disclosed in U.5. Patent NOs. 2,679,544;
2,234,300; and 3,244,765. Partial oxidation produces
significant quantities of CO, CO2 and H2, yielding a diulte

20~7~8 :
` :
acetylene-containing gas and thereby making acetylene
recovery difficult.
The largest, non-fuel use of methane is in the
production of ammonia and methanol ~and formaldehyde)~ The
first; methane conversion, step of these processes is the
production of a synthesis gas ~CO + H2) by reforming of
methane in the presence of steam overr for example, a
nlckel catalyst. Typlcal reformers are tubular furnances
; heated with natural gas, the temperature being maintained
at 900C and the pressure at about 225 atmospheresO
Pyrolytic or dehydrogenataive conversion of
methane or natural gas to C2+ hydrocarbons has previously
` been proposed. The conversion required high temperatures
`~ (greater than about 1000C.) and is characterized by the
,~ formation of by~product hydrogen. ~he patent literature
contains a number of proposals to catalyze pyrolytic
l reactions, allowing conversion at lower temperatures. See,
1~ for example, U.S. Patent Nos. 1,656l813; 1,687,890;
~` 1,851,726 1,863,212; 1,922,960; 1~958,648; 1,986,238 and
1,988,873. U.S. Patent 2,436,595 discloses and claims a
: `
catalytic, dehydrogenative methane-conversion process
which employs fluidized beds of heterogeneous catalysts
comprising an oxide or other compound of the metals of
group VI or VIII.
Including oxygen in a methane feed for conversion
over metal oxide catalysts has been proposed. Margolis, L.
Ya., Adv. Catal. 14/ 429 (1963) and Andtushkevich, T.V.,
et al, Kinet. Katal 6, 860 (1965) studied oxygen-methane
cofeed over different metal oxides. ~hey report the forma-
tion of methanol, formaldehyde, carbon monoxide and carbon



-- 3 --

~2~


dioxide from methane/oxygen feeds. Higher hydrocarbons are
either not formed or are converted much faster then methane.
Fatiadi has prepared an extensive review of
reactions in which manganese dioxide is used for mild,
selective heterogeneous oxidation of numerous classes of
organic compounds. The us~ of manganese dioxide to form
higher hydrocarbon products from methane is not mentioned.
Fatiadi, A. J., "Active Manganese Dioxide In organic
Chemistry - Part I", Synthesis, 1976, ~o. 2, pp. 65, et seq.
(February, 1975); Fatiadi, A. J., "Active Manganese Dioxide
In Organic Chemistry - Part II", Synthesis, 1976, No. 3,
pp. 113, et seq. (March, 1976).
It has been reported that manganese oxide forms
manganese carbides from methane at 800~. Fisher, F., et
al, Brenstoff - Chem., 10, 261 (1929).
SUMM~RY OF THE INVENTION
It has been found that methane may be converted
to higher hydrocarbon products by contactiny a methane-
containing gas with oxides of manganese, tin, indium,
germanium, lead, antimony and/or bismuth at temperatures
selected within the range of about 500 to 1000C. Hydro-
carbons produced include lower alkanes, lower olefins and
aromatics. The oxides are reduced by the methane contact
and are easily reoxidizable by contact with an oxygen-
containing gas.
The present process is distinguished from
previously known pyrolytic methane conversion processes by
the use of the aforementioned reducible oxides to synthe-
size higher hydrocarbons from methane with coproduction of
water, rather than methane.



The present process is distinguished from
previously suggested methane conversion processes which
rely primarily on interactions between methane and at least
one of nickel and the noble metals, such as rhodium,
palladium, silver, osimum, iridium, platinum and gold. An
example of this type of process is disclosed in U.S. Patent
~,205,194. The present process does not require that
methane be contacted with one or more of nickel and such
noble metals and compounds thereof.
Moreover, in a preferred embodiment, such contac-
ting is carried out in the substantial absence of catalyt-
ically effective nickel and the noble metals and compounds
thereof to minimize the deleterious catalytic effects of
such metals and compounds thereof. For example, at the
conditions, e.g., temperatures, useful for the contacting
step of the present invention, these metals when contacted
with methane tend to promote coke formation, and the metal
oxides when contacted with methane tend to promote forma-
tion of combustion products (COx) rather than the desired
hydrocarbons. The term "catalytically effective" is used
herein to identify that qua~tity of one or more of nickel
and the noble metals and compounds thereof which when
present substantially changes the distribution of products
obtained in the contacting step of this invention relative
to such contacting in the absence of such metals and
compounds thereof.







Oxides of manganese which are reduced when
contacted with methane at a temperature of about 500-1000C.
include MnO2, Mn2O3, Mn3O4 or mixtures thereof. However,
it has been further discovered that, of these reducible
oxides of manganese, Mn3O4 is the most effective in promot-
ing high yields of hydrocarbon products. The spinel,
Mn3O4, is known to be formed by oxidation/decomposition of
manganese compounds at temperatures above about 900C. and
can be stabilized at lower temperatures, e.g., by being
supported on silica.
A preferred oxide of tin is SnO2.
A preferred oxide of indium is In2O3.
A preferred oxide of germanium is GeO2.
A preferred o~ide Gf lead is PbO.
A preferred oxide of antimony is Sb2O3.
A preferred oxide of bismuth is Bi2O3.
It has been further found that use of elevated
pressures (i.e., pressures greater than atmospheric) in the
methane contact zone of processes employing one or more of
the aforementioned reducible oxides promotes the formation
of C3+ hydrocabon products (i.e., hydrocarbons having three
or more carbon atoms per molecule). According to this
distinct embodiment of the present invention, methane
contact zone pressures are preferably within the range of
about 2 to 100 atmospheres, more preferably within the
range of about 3 to 30 atmospheres.
The conversion of methane to higher hydrocarbons
by contact with oxidative synthesizing agents involves
multiple reactions which are not clearly understood.
However, gas-(or vapor-) phase reaction products may be




generally characterized as: (1) hydrocarbon products and
(2) combustion products. Hydrocarbon products include
al~anes, olefins and aromatics. The process is distin-
guished from pyrolytic methane conversion processes by the
coproduction of water, rather than hydrogen, and by the
competing combustion reactions occurring during methane
contacting.
A further distinct embodiment of the presently
claimed invention resides in the discovery that improved
results (e.g., production of hydrocarbon products while
reducing the formation of combustion products during
methane-contacting) are obtained by employing a process
wherein solids (i.e., solid particles) are recirculated
between two physically separate zones: a methane contact
zone and an oxygen contact zone~ Desirable product distri-
butions may advantageously be obtained if particles compri-
sing an oxidative synthesizing agent and a gas comprising
methane are continuously introduced (e.g., at independently
chosen feed rates) into the methane contact zone, which
zone is maintained at selected contact temperatures.
Moreover, maintaining fluidized beds o solids in the two
contact zones enables control of average solids residence
time in each zone and promotes mixing of the two-phase
mixtures present in the zones. Average residence time of
the methane-containing feed is also controlled. This mode
of operation further improves product composition and
reduces the formation of combustion products in the methane
contact zone, especially when compared to cyclic processes
involving intermittent or pulsed flow of methane and oxygen
over solids maintained in a single contact zone or when

~2~4~


compared to processes wherein oxygen and methane are cofed
over metal oxide catalysts.
Moreover, the process of the present invention
provides the capability of producing a substantially
uniEorm stream of desirable hydrocarbon products from
relatively easily combustible material--methane--while
employing oxidative synthesizing agents which are reduced
during the methane-contacting. Such substantially uniform
hydrocarbon product streams result in, for example, more
effective and easier separation of products.
This invention is further described in the
following detailed description of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a plot of methane conversion and
hydrocarbon product selectivity vs. time for the results
reported in Example 3.
Figure 2 is a plot o methane conversion vs. time
for the results reported in Examples 2 and 5.
Figure 3 is a plot of ~ C converted and hydro-
carbon product selectivity vs. run time for the results
reported in Example 10.
Figure 4 is a plot of ~ C converted and hydro-
carbon product selectivity vs. run time Eor the results
reported in Example 11.
Figure 5 is a plot of methane conversion and
hydrocarbon product selectivity vs. time for the results
reported in Example 13.
Figure is 6 a plot of methane conversion vs. time
for the results reported in Example 13 and 14.
Figure 7 is a plot of methane conversion and

12~9~7~38

hydrocarbon product selectivity vs. time for the results
reported in Examples 16 and 17.
Figure 8 is a plot of methane conversion and
hydrocarbon product selectivity vs. time for the results
reported in Example 18.
Figure is 9 a plot of methane conversion and
hydrocarbon product selectivity vs. time for the results
reported in Examples 19.
Figure 10 is a plot of methane conversion to
gaseous products and C2+ hydrocarbon product selectivity
vs. time for the combined results of Examples 20 and 21.
Figure is 11 a plot of methane conversion to
gaseous products and ~2+ hydrocarbon product selectivity
vs. run time for the results of Example 22.
Figure 12 is a plot of methane conversion and
hydrocarbon selectivity vs. time for the results
of Examples 23 and 24.
Figure 13 is a plot of methane conversion and
hydrocarbon product selectivity vs. time for the results of
Example 25.
Fi~ure 14 is a plot of methane conversion and
hydrocarbon product selectivity vs. time ~or the results
reported in Example 26.
Figure 15 is a plot of methane conversion and
hydrocarbon product selectivity vs. run time for the
results of Example 27.
~ igure 16 is a plot of methane conversion vs.
time for the results reported in Examples 22 and 28.
Fi~ure 17 is a plot of methane conversion and
hydrocarbon product selectivity vs. time for the results of
Example 30.

_ ~ _

~2a~


Figure 18 is a plot of methane conversion vs.
time for the results of Examples 30 and 31.
Figure 19 is a plot of the ratio, ~ yield of C
hydrocarbon products/% yield of C2+ hydrocarbon products,
vs. run time for the instantaneous results obtained in
Examples 33 and 34 and Comparative Example A.
DETAILED DESCRIPTION OF THE INVENTION

_
Oxidative synthesizing agents are compositions
comprising at least one oxide of at least one metal, which
composition r when contacted with methane at a temperature
selected within the range of about 500 to 1000C, produces
C2+ hydrocarbon products, coproduct water, and a composi-
tion comprising a reduced metal oxide. The composition of
the oxidative synthesizing agent thus contains at least one
reducible oxide of at least one metal. The term "reducible"
is used to identify those oxides of metals which are
r~duced by contact with methane at tempera~ures selected
within the range of about 500 to 1000C. The term "oxide(s)
of metal(s)" includes: (1) one or more metal oxides (i.e.,
compounds described by the general formula MxOy wherein M
is a metal and the subscripts x and y designate the
relative atomic proportions of metal and oxygen in the
compound) and/or (2) one or more oxygen containing metal
compounds, provided that such oxides and compounds have the
capability of performing to produce higher hydrocarbon
products as set -forth herein. Preferred oxidative synthe-
sizing agents comprise reducible oxides of metals selected
from the group consisting of Mn, Sn, In, Ge, Pb, Sb, and
Bi, and mixtures thereof. Particularly preferred oxidative

synthesizing agents comprise a reducible oxide of manganese

-- 10 --




and mixtures of a reducible oxide of manganese with other
oxidative synthesizing agents. More preferred are oxida-
tive synthesizing agents which comprise Mn3O~. Among the
reducible oxides of manganese, those containing major
amounts of Mn2O3 and Mn3O4 are preferred~ As noted, a
particularly preferred class of oxidative synthesizing
agents are those comprising Mn3O4. Among the reducible
oxides of tin, those containing major amounts of SnO2 are
preferred. Among the reducible oxides of indium, those
containing major amounts of In2O3 are preferred. Among the
reducible oxides of germanium, those containing major
amounts of GeO2 are preferred. Among the reducible oxides
of lead, those containing major amounts of PbO are pre-
ferred. Among the reducible oxides of antimony, those
containing major amounts of Sb203 are preferred. Among the
reducible oxides of bismuth, those containing major amounts
of Bi2o3 are preerred.
Reducible oxides are preferably provided as
particles. They may be supported by, or diluted with, a
conventional support material such as silica, alumina,
titania, zirconia, and the like, and combinations thereof.
A presently preferred support is silica.
Solids may be formed in conventional manner using
techniques well known to persons skilled in the art. For
example, supported solids may be prepared by conventional
methods such as adsorption, impregnation, precipitation,
coprecipitation, or dry-mixing.
A suitable method is to impregnate the support
with solutions of a compound containing the metal. Some
examples of metal compounds are the acetate, acetyl-


~L2~

acetonate, oxide, carbide, carbonate, hydroxide, formate,
oxalate, nitrate, phosphate, sulfate, sulfide, tartrate,
fluoride, chloride, bromide or iodide. Such compounds may
be dissolved in water or other solvent and the solutions
combined with the support and then evaporated to dryness.
Preferably, aqueous solutions are employed and water-
soluble compounds are usedO In some cases, the solutions
may have acids and/or bases added to them to facilitate
dissolution of the precursors of the metal oxide. For
example, acids such as hydrochloric or nitric acid or bases
such as ammonium hydroxide may be used as desired. The
dried solids may then be screened or otherwise processed to
form the desired shape, size, or other physical form of the
finished solids. Finally, the solids are prepared for use
by calcination at high temperatures for a period of time in
accordance with conventional practice in this art. For
example, the solids are placed in an oven or kiln, or in a
tube through which oxygen (e.g., air or oxygen diluted with
other gases) is passed, at an elevated temperature selected
within the range of about 300 to 1200C. Particular calcin-
ation temperature will vary depending upon the particular
metal compound.
For solids comprising reducibl~ oxides of
manganese, the calcination temperature should be within the
range of about 500 to 1200C, preferably about 700 to
1200C, more preferably about 900 to 1200C. Use of higher
calcination temperature promotes the formation of Mn3O4 in
the finished solid.
For solids comprising reducible oxides tin, the
calcination temperature should be within the range of about

_ 12 -


300 to 1200C, preferably about 500 to 1100C.
For solids comprising reducible oxides of indium,
the calcination temperature should be within the range of
about 300 to 900C, preferably about 500 to 850C.
For solids comprising reducible oxides of
germanium, the calcination temperature should be within the
range of about 300 to 1200C, preferably about 500 to
1000C.
For solids comprising reducible oxides of lead,
the calcination temperature should be within the range of
about 300 to 1000C, preferably about 500 to g00C. Use of
higher calcination temperatures promotes the formation of
PbO in the finished solid.
For solids comprising reducible oxides of
antimony, the calcination temperature should be ~7ithin the
range of about 300 ~o 1200~C, preferably about 500 to 850.
For solids comprising reducible oxides of bismuth,
the calcination temperature should be within the range of
about 300 to 1000~C, preferaby about 500 to 850C.
The foregoing description regarding preparation
of reducible oxides of manganese, tin, indium, germanium,
lead, antimony and bismuth in a form suitable for the
synthesis of hydrocarbons from a methane source is merely
illustrative of many possible preparative methods, although
it is a particularly suitable method and is preferred.
Metal loadings on supported solids may be within
the range of about 1 to 50 wt. % (calculated as the
elemental metal(s) o the reducible oxides(s~.
In addition to methane, the feedstock employed in
the method of this invention may contain other hydrocarbon

~ 13 -



of nonhydrocarbon components, although the methane content
should be within the range of about 40 to 100 vol. %,
preferably from about ~0 to 100 vol. ~, more preferably
from about 90 to 100 vol. ~.
Operating temperatures for the contacting of
methane-containing gas and the oxidative synthesizing agent
are selected from the range of about 500 to 1000C, the
particular temperature selected depending upon the partic-
ular oxide(s) employed in the oxidative synthesizing agent.
For example, all oxidative synthesizing agents
have the capability of synthesizing higher hydrocarbons
from a methane source when the temperature of the methane-
contact are selected within the lower part of the recited
range. Reducible oxides of certain metals, however, may
require operating temperatures below the upper part of the
recited range to minimize sublimation or volatilization of
the metals (or compounds thereof) during methane contact.
Examples are: (1) reducible oxides of indium (operating
temperatures ~7ill pr~ferably not exceed about 850C); (2)
reducible oxides of germanium (operating temperatures will
preferably not exceed about 800C); and (3) reducible
oxides of bismuth (operating temperatures will preferably
not exceed about 850C).
Operating temperatures for the contacting of
methane-containing gas and a reducible oxide of manganese
are in the range of about 500 to 1000C., preferably within
the range of about 600 to 900C.
Operating temperatures for the contacting oE
methane-containing gas and a reducible oxide of tin are in
the range of about 500 to 1000C., preferably within the



range of about 600 to 900C.
Operating temperatures for the contacting of
methane-containing gas and a reducible oxide of indium are
in the range of about 500 to 850C., preferably within the
range of about 600 to 800C.
Operating temperatures for the contacting of
methane-containing gas and a reducible oxide of germanium
are in the range of about 500 to 800C., preferably within
the range of about 600 to 750C.
Operating temperatures for the contacting of
methane-containing gas and a reducible oxide of lead are in
the range of about 500 to 1000C., preferably within the
range of about 600 to ~00C.
Operating temperatures for the contacting of
methane-containing gas and a reducible oxide of antimony
are in the range of about 500 to 1000C., preferably within
the range of about 600 to 900C.
operating temperatures for the contacting of
methane-containing gas and a reducible oxide of bismuth are
in the range of about 500 to 850C., preferably within the
range of about 600 to 800C.
Operating pressures for the methane contacting
step are not critical to the broadly claimed invention.
However, both general system pressure and the partial
pressure of methane have been found to effect overall
results.
A distinct embodiment of the present invention is
a method wherein an oxidative synthesizing agent comprising
a reducible metal oxide is contacted with me-thane, the
further improvement residing in the use of elevated



pressures to promote the formation of C3+ hydrocarbon
products. Operating pressures for the methane contacting
step of this invention are preferably within the range of
about 2-100 atmospheres, more preferably about 3-30 atmos-
pheres. Elevated pressures have been found to provide
improved results, e.g., elevated pressures promote forma-
tion of C3+ hydrocarbon products.
Contacting methane and an oxidative synthesizing
agent to form higher hydrocarbons from methane also reduces
the oxidative synthesizing agent and produces coproduct
water~ The exact nature of the reduced forms of oxidative
synthesizing agents are unknown, and so are referred to
herein as "reduced synthesizing agent" or as "a reduced
metal oxide". Regeneration of a reducible oxide is readily
accomplished by contacting reduced compositions with oxygen
(e.g., an oxygen-containing gas such as air) a~ a tempera-
ture selected within the range of about 300 to 1200C., the
particular temperature selected depending on the particular
metal(s) included in the oxidative synthesizing agent. The
contact time should be sufficient to produce a reducible
oxide from at least a portion of the reduced composition.
Oxygen contacting temperatures for reduced oxides
of manganese are preferably within the range of about 300
to 1200C., more preferably within the range of about 700
to 1200C.~ still more preferably within the range of about
900 to 1200C. Higher reoxidation temperatures promote
formation of Mn3O4, the preferred reducible oxide of
manganese.
Oxygen contacting temperatures for reduced oxides
of tin are preferably within the range of about 300 to



- 16 -

~L2~


1200C., more preferably within the range of about 500 to
1100C.
Oxygen contacting temperatures for reduced oxides
of indium are preferably within the range of about 300 to
900C., more preferably within the range of about 500 to
850C. Higher reoxidation temperatures promote formation
of In2O3, the preferred reducible oxide of indium.
Oxygen con~acting temperatures for reduced oxides
of germanium are preferably within the range oE about 300
to 1200C., more preferably within the range of about 500
to 1000C.
Oxygen contacting temperatures for reduced oxides
of lead are preferably within the range of about 300 to
1000C., more preferably within the range of about 500 to
900C. Higher reoxidation temperatures promote formation
of PbO, the preferred reducible oxide of lead.
Oxygen contacting temperatures for reduced oxides
of antimony are preferably within the range of about 300 to
1200C., more preferably within the range of about 500 to
850C~
Oxygen contacting temperatures for reduced oxides
of bismuth are preferably within the range of about 300 to
1200C., more preferably within the range of about 500 to
850C.
Particles comprising a reducible oxide of Mn, Sn,
In, Ge, Pb, Sb or Bi may be contacted with methane in fixed,
moving, fluidized, ebullating, or entrained beds of solids.
Preferably, methane is contacted with a fluidized bed of
particles comprising the said reducible oxides.
Similarly, particles comprising a reduced oxide

- 17


of Mn, Sn, In, Ge, Pb, Sb~ or ~i may be contacted with
oxygen in fixed, moving, fluidized, ebullating or entrained
beds of solids. Preferably, oxygen is contacted with a
fluidized bed of particles comprising the reduced oxides.
A single reactor apparatus containing a fixed bed
of solids, for examplel may be used with intermittent or
pulsed flow of a first gas comprising methane and a second
gas comprising oxygen ~e.g., oxygen, oxygen diluted with an
inert gas, or air, preferably air).
Preferably, however, the methane contacting step
and the oxygen contacting step are performed in physically
separate zones with particles recircula~ing between the two
zones. Thus, the preferred method for synthesizing hydro-
carbons from a methane source comprises: (a) contacting in
a first zone a gas comprising methane and particles compri-
sing an oxidative synthesizing agent to form higher hydro-
carbon products, coproduct water, and reduced synthesizing
agent; (b) removing particles comprising reduced synthe-
sizing agent from the first zone and contacting the reduced
particles in a second zone with an oxygen-containing gas
to form particles comprising an oxidative synthesizing
agent; and (c) returning the particles produced in the
second zone to the first zone.
Particles comprising an oxidative synthesizing
agent which are contacted with methane may be maintained as
fluidized, ebullating, or entrained beds of solids. Prefer-
ably, methane is contacted with a 1uidized bed of solids.
Similarly, partic~es comprising reduced synthes-
izing agent which are contacted with oxygen may be main-

tained as fluidized, ebullating or entrained beds of solids.
- 18 -


Preferably, oxygen is contacted with a fluidized bed of
solids.
Thus, in a presently preferred embodiment of the
present invention, methane feedstock and particles compri-
sing an o~idative synthesiæing agent are continuously
introduced into a methane contact zone maintained at
synthesizing conditionsO Synthesizing conditions include
the temperatures and pressures described above. The
methane feedstock is introduced at sufficient velocity such
that the particles are fluidized~ Gaseous reaction
products from the methane contact zone (separated from any
~ntrained solids) are further processed--e.g., they are
passed through a fractionating system wherein the desired
hydrocarbon products are separated from unconverted methane
and combustion products. Unconverted methane is preferably
recovered and recycled to the methane contact zone.
Of considerable importance to the process of this
invention is the average residence time of particles in the
methane contact zone. Selection of a desired solids resi-

dence time is dependent on the particular reducible metaloxide(s) incorporated in the particles comprising an oxida-
tive synthesizing agent, the concentration of such active
component, the feedrate and composition of the methane
feedstock, and other operating conditions (esp. temperature
and pressure of the contact zone). Preferably, the average
residence time of particles in the fluidized bed contact
zone is within the range of about 0.04 to 30 minutes, more
preferably about 0.4 to 4 minutes. Optimum solids resi-
dence times for any particular oxidative synthesizing agent
will decrease as methane contact temperatures, gas eed

-- 19 --

~20~


rates or hydrocarbon concentrations in the feed increase.
The feed rate of methane feedstock is related to
the average residence time of particles, comprising an
oxidative synthesizing agent, in the methane contact zone.
Preferably, residence time of methane feedstock in the
methane contact zone is within the range of abou-t 0.1 to
100 seconds, more preferably about 1 to 20 seconds.
The SiZ2 of particles comprising an oxidative
synthesizing agent is preferably selected to render those
particles capable of fluidization, preferably in a dense
phase, in the methane contact zone. These particle sizes
are usual and are not peculiar to this invention.
Particles comprising reduced synthesizing agent
are contacted with molecular oxygen in an oxygen contact
zone for a time sufficient to restore or maintain the
activity of the agent by oxidizing at least a portion of
the reduced metal oxide to produce a reducible oxide and by
removing, i.e., combusting, at least a portion of any
carbonaceous deposit which may form on the particles in the
methane contact zone. The conditions of the oxygen contact
zone will preferably include a temperature selected within
the range of about 300 to 1200C, pressures up to about 30
atmospheres, and average particle contact times within the
range of about 3 to 120 minutes. Sufficient oxygen is
preferably provided to oxidize all reduced metal oxide to
produce a reducible oxide and to completely combust any
carbonaceous deposit material deposited on the particles.
At least a portion of the particles comprising an oxidative
synthesizing agent, which are produced in the oxygen
0 contact zone are returned to the methane contact zone.

- 20 ~




The rate of solids withdrawal from the methane
contact zone is desirably balanced with the rate of solids
passing from the oxygen contact zone to the methane contact
zone so as to maintain a substantiall~ constant inventory
of particles in the methane contact zone, thereby enabling
steady state operation of the synthesis systemO
The invention is further illustrated by reference
to the following examples.
Experimental results reported below include
conversions and selectivities calculated on a molar basisO
Solids productivity, reported as g/g-hr., is
grams of methane converted to C2~ hydrocarbon products/gram
of solid oxidative synthesizing agent/hour.
The supported manganese oxides employed in
Examples 1-11 were made by impregnating the appropriate
amount of manganese, as manganeous acetate, onto the
supports from water solutions. Supports used were Houdry
~SC 534 silica, Cab-O-Sil, Norton alpha-alumina and
Davison gamma-alumina. The impregnated solids were dried
at 110C for 4 hours and then calcined in air at 700C for
16 hours. Composition of the calcined solids is identified
as "wt. % Mn/(support)".
Methane-contact runs described in Examples 1-11
were made at about atmospheric pressure in a quartz tube
reactor (12 mm. inside diameter) packed with 10 ml~ of
catalyst. The reactors were brought up to temperature
under a flow of nitrogen which was switched to methane at
the start of the run. Instantaneous samples of the
effluent were taken throughout the run and analyzed by gas
chromatography and gas chromatography- mass spectroscopy.

- 21 -

8~3


A cumulative run sample was also collected.
Examples 1-4 demonstrate the effect of manganese
oxide loading on methane conversion. Total conversion is
shown to bear a distinct relationship to loading.
EXAMPLE 1
A feed of 100% methane was passed over a bed of 5
wt. % Mn/SiO2 according to the procedure described above.
Contact zone temperature was 800C and the GHSV (gas hourly
space velocity) was 600 hrs~l. Results are reported in
Table I below. No carbon formation was detected on the
solid present at the end of the run.
TABLE I


Time % _ % Selectivity
(min) conv. CH2CH2 CH~CH~ C
Instantaneous Results
1 4.00 2~.5 37i4 1.991.8 19.9 21.0
2 1.02 17.6 59.8 1.47trace 14.3
4 .243 20.5 77.3 2.05
8 .166 22.2 74~6 3.0
.134 26.8 67.9 5.2
Cumulative Results
30 .429 27.2 45.~ 2.9 g.7 9.1
EXAMPLE 2
A feed of 100% methane was passed over a bed of
10 wt. % Mn/SiO2 according to the procedure described above.
Contact zone temperature was 800C and the GHSV was 600
hrs~l. Results are reported in Table II below. No carbon
formation was detected on the solid present at the end of
the run.




- 22

~2~7~

TABLE II


Run Time % % Selectivity
(min) Conv. CH~CH2 CH3CH3 C~ C _ O~
Instantaneous Results
* 1 Z2.4 40.7 18.2 2~1 17.1 18.9
4 .85 28.g 48.6 22.4
12 .32 3~.6 36.6 26.7
30 .27 56.7 43.2
Cumulative Results
1030 1.77 24.5 23~9 24O4 26.4
* Solids Productivity (Instantaneous) = 0.145 g/g hr.
EXAMPLE 3
A feed of 100~ methane was passed over a bed of
15 wt. % Mn/SiO2 according to the procedure described above.
Contact zone temperature was 800C and the GHSV was 600
hrs~l. Results are reported in Table III below. No carbon
formation was detected on the solid present at -the end of the
run. Figure 1 is a plot of % methane conversion and
selectivity to C2+ hydrocarbon products vs. run time.


TABLE III

Run Time % % Selectivity
(min) Conv. CH2CH2 CH~CH~ C~ C4-C7 CO CO~
Instantaneous Results
-
* 1 30.1 36.5 13.9 2.15 3.56 19.5 24.2

2 12.3 42.9 27.0 17.0 12.9


12 .402 55.8 44.1

30 .308 51.8 41.8

Cumulative Results

30 2.27 31.8 23.9 15.8 28.3

* Solids Productivity at 1 min = 0.157 g/g hr.


- 23 -

~7~

EXAMPLE 4
A feed of 100% methane was passed over a bed of
50 wt. % Mn/SiO2 according to the procedure described above.
Contact zone temperature was 700C and the GHSV was 600
hrs~l. Results are reported in Table IV below. No carbon
formation was detected on the solids present at the end of
the run.
TABLE IV


P~un Time % % Selectivity
(min) Conv. CH~CH~ CH~CH~ c3 CO CO2
Instant~neous Results

_
1 22 D 8 2.3 3.46 .01 94.2
2 11.6 3.5 9.37 .05 .17 86.8
4 7.39 4.44 1~.8 .08 81O1
12 2.31 5.76 22.0 ~13 .~6 71.1
1.08 11.9 22.0 .36 65.6
Cumulative Results
-
30 4~12 4.26 12~5 .09 .36 82.6
EXAMPLE 5
This example demonstrates the recyclability of
the Mn oxide, oxidative synthesizing agent of this inven-
tion. The reduced solid remaining at the end of the run
described in Example 2 was regenerated under a flow of air
at B00C. for 30 minutes. The reactor was then flushed
with nitrogen. The regenerated, reoxidized solids were
then contacted with methane at a temperature of 800C and a
GHSV of 600 hrs.~l. Results are shown in Table V below.

No carbon oxides were ~etected during the oxidation of the
reduced solids. Comparison of the results reported in
Tables II and V indicates substantially complete recovery


- 24 -




of Mn oxide activity for the conversion of methane to
higher hydrocarbons. Figure 2 is a plot of methane conver-
sion vs. time for the combined results of Examples 2 and 5.
TABLE V


Run Time % % Selectivity
(min) Conv. CH2(::H2 CH3CH3 ~ C0
Instantaneous Results
21.1 38.9 1705 2.4 18.8 lg.9
4 1.05 26.1 ds2~3 31.5
1012 .42 40.9 26.9 29.8
30 .36 64.8 35.2
Cumulative Results
30 1.56 25~2 18.1 1.3 24.7 30.7
EXAMPLE 6
The runs of this example show the effect of
temperature on the conversion process of this invention. A
feed of 100% methane was passed over a bed of 5 wt. %
Mn/SiO2 at a GHSV of 600 hr. 1. Results obtained at
various contact temperatures are shown in Table VI below.


TABLE VI
Run A

Time % % Selectivity
TempC (min) conv. CH2CH2 CH3CH3, ~ C4-C6 C0
Instantaneous Results
650 2 1.25 2.4 19.1 trace 39.0 39.4
4 .28 503 62.1 27.5
16 .081 8~6 91.3

30 .03 15.8 84.1
Cumulative Results
3030 .223 6.7 52.0 21.5 19.7


-- 25 --



Run ~


Time % % Selectivity
TempC tmin) conv.CH2CH2 CH3CH3C3 C4-C~ CO C~2
Instantaneous Results
700 2 1.95 10.5 39.2 .9 23.0 26.1
4 .896 9.9 53.5 .08 27.5
8 .31 1370 87.1trace
16 .08713.7 86.2
.03 16.6 83.3
Cumulative Results
30 .319 14.1 67.1 9.4 9.
Run C


Temp~C (min) conv. CH2CH2 ~L3~ 5~ CO ~2_

Instantaneous Results
750 2 2.65 18.2 ~4.0 1.5 19.9 16.3
4 .5g6 15.1 81.0 1.3 2.5
8 .164 1~.6 85.3
16 .053 16O9 83.0
.041 17.0 ~3.0
Cumulative Results
30 .379 23.7 57.8 2.1 9.23 7.12
Example 1, supra, shows results of a similar run at 800C.
Initial and cumulative conversions increase with tempera-
ture over the range of temperatures studied. Selectivities
to higher, C3+, hydrocarbons tend to increase with tempera-
ture as does the ratio of olefinic (e.g., ethylene) to
paraffinic (e.g., ethane) hydrocarbon products. Formation

of C3~ hydrocarbon products is promoted by higher tempera-
tures.



- 26 -

~7~

EXAMPLE 7
Example 1 was repeated except that during prepar-
ation of the supported Mn oxide, the dried impregnated
catalyst was calcined in air at 1000C and the methane feed
contained 16 vol. % methane, the remainder being N2.
Contact temperature was 750C and GHSV was 600 hrs.-l.
Results are shown in Table VII below. X-ray diffraction
analysis of the calcined solid indicated that Mn was
present as Mn3O4.
TABLE VII

Run Time % % Selectivity
(min) Conv. CH2CH2 CH3CH3 ~_ CO C02

Instantaneous Results
1 12.7 - 15.7 17.5 .39 19.0 47.3
2 10.1 18.7 27.9 .49 21.6 31.1
4 2.59 19.7 47.7 ~77 16.5 15.26
12 1.02 12.3 49.1 .48 38.1
.289 32.8 65.4 1.73
Cumulative Results
30 2.96 17.4 13.7 .23 24.3 44.28
Example 3
This example demonstrates the effect of space
velocity on the methane conversion process of this inven-
tion. The procedure of Example 2 was repeated in the two
Runs described in Table VIII below except that the space
velocity of Run A was 1200 hrs -1 and space velocity of Run
B was 300 hrs -1.




39


- 27 -



TABLE VIII

Run A
Run Time % % Selectivity
(min) Conv. C2H4 ~2~h C3 C4-C7 CO CO~
Instantaneous Results
-
~5 5~25 22~2 ~0~3 ~15 27~0 8~8
1~0 o81 18~4 78~7 ~85 1~9
4~0 ~10 15~8 84~1
15.0 ~ 08 22 ~ 6 77 ~ 3
Cumulative Results
-
15 ~335 25~9 52~2 2~7 8~35 10~7


Run B

Run Time % % Selectivity
(min) Conv. ~2~ C2H6 ~ C4-C7 CO ~2_

Instantaneous Results

1 37~ 20~1 4~6 1~20~7 48~1 25~3

2 l9.B 24.1 18.6 2.80~4 45~2 10~7

4 3~54 35~8 34~0 1~5~5 28~2

12 2~21 34~7 55~0 1~5 0 8

1.75 30 ~ 0 68 ~ 7 1.3

Cumulative Results

_
30 3~85 33~2 19~2 1~4 ~2 35~8 10~2
Example 9
Each of the following runs were made over 10 ml.
catalyst with a 14-16 vol. ~ CH4 in N2 feed. The feed rate
(calculated at standard conditions) was 100 ml/min, equiva-
lent to a GSHV Of 600 hrs~l. In Run A, the solid contact-
ing agent was 5 wt. %Mn/gamma alumina and the contacting zone
tempe-rature was 750C~ In Run B, the solid contacting
30 agent was 5 wt. % Mn/alpha-alumina and the contacting zone


~ 28 ~

7~

temperature was 750C. In Run C, the solid contacting
agent was 5 wt. % Mn/SiO2 solids which had been subjected
to at least 10 methane contact/oxidation cycles. In the
oxidation portion of these cycles, reduced solids from the
methane-contacting portion of the cycle were regenerated
under a flow of air at 700C for 15 to 30 minutes and the
reactor was then flushed with nitrogen before starting the
next methane run. The contacting zone temperature for Run
C was 700C. The results reported in Table IX are cumula-

tive results obtained over a 30 minute contact time. X-ray
diffraction analysis of the solid contacting agent used in
Run C indicated that Mn was present as Mn3O
TABLE IX

Solids
Productivity
% ~ Selectivity x 103
Run# Conv. ~ C CO~2 (g/g-hr)
A 6.12 11.4 .48 31.754.5 1.06
B 9.64 6.56 12.9 .07 80.3 0.95
C 1.23 12.0 51.6 .85 19.615.8 1.49


Example 10
A feed of 95 vol. % methane and 5 vol. % ethane
was passed over a bed of 5 wt. ~ Mn/SiO2 according to the
procedure described above. The contact temperature was
700C and the G~SV was 860 hrs~l. Unlike the runs
described in the previous examples, a carbonaceous, coke-
like deposit was present on the solids at the end of an 11
minute run. The results for the run, reported in Table X,

below, are based on C in the feed converted to gas phase
products only and do not take coke formation into account.
The amount of carbonaceous deposit formed over the 11


- 29 -

7~


minute run was 14.8% of all feed converted. Figure 3 is a
plot of % C converted and % selectivity to C2+ hydrocarbon
products vs. run time for the results of this example.




:: - 30 -

~(9~7~




~ ~D
o ~ t~ t~
~,
;.~
v ~ In
~ o
o C~ oo

u~ a) ,~
S N O ~~1 ~ ~
~C: S:: . . . . ~ ~1
.~ o o o o o
.~ o
, U~ ~D ~ O O ~
~ 1~o o o o o o
O U
, o o o o o o
~ ,
~ . u~ ~ ~D ~ ~ Lt~
.,1 .:1 . o . . ~ .
~ C.~ o O o O o o
.~ ,
U '. "U~ o ~ ~9
C~ ~ ~ ~ ~ ,
.
u~ $ o ~ o t~
r r~ D r- t~
,~ u~ t~
. l ~
~ ~ a~ ~ ~ oo ~
~ , ~n
.,1 l ~oo ~ ~ ~ cn o
~n ~, ,~o OD ~ ~, ~ t_
~ :C ~
a) ~ ~Q ~ o o o o o
D ~ ~ 1~ 0
c.) i ~, ~n ~.

dP ~ O ~ O m ~ In 3 a~
a~ ~ 00 0 In o ~q o~
o~ ~ . . . . . a~ O
E~ ~ ~ ~
a) ~ ... ,
~ ' lR .
_ H
~ ) o ~



-- 31 --

7~8

Example 11
A feed of 95 vol. % methane and 5 vol. % ethylene
was passed over a bed of 5 wt. % Mn/SiO2 according to the
procedure described above. The contact temperature was
700C and the GHSV was 860 hrs~-l. A carbonaceous, coke-
like deposit was present on the solids at the end of an 11
minute run. The amoun-t of carbonaceous deposit formed was
35.6% of all feed C converted. A wax-like condensate was
also noted at the reactor outlet. The amount of this
condensate was 5.0% of all feed C converted, Results for
the run are tabulated in Table XI, Figure 4 is a plot of %
C converted and % selectivity to C2 + hydrocarbon products
vs. run time for this example.




- 32 -

12~




O 0~ Cl~ t~

o . . o
U ~9 o~

a3
o ~ o
~ ~1 O~1 ~ O O
~ E~
tu
a
o o
N
U~ ~::
~ Q)
m
O . C~ OD O
.~ O ~
.~
H: ~ O C~Ct~~`1~1 00
X ~( .~
.~ ~)1~') ~ ~ ~ ~D ~1
O . ~ ~ N r--l
:1 :aJ~
~ ' a~ :
E-lu~ .
, ~ CO ~ U~ D O
' dP ~
~I U 1 ~ ~n o ~ ~r
:~ . > . ~ .
~` ~ L~ o G~
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~ l~
t` ~ ~ ~ ~ ~9
~:: U~
'O ~
U~ ~ ~~ ~I` ~I r-l O
' ~ 5~ U~ . ~ , . .
~ C~ ~ r~ O O O

a) o ~ ~ co ~ ~ ~ ~
a) In
E~ H~ ~ ~ O O ~,~--1
a~ ~a
,~_ C
E~ ~ H O --1 .--~
~ ~ -1
C~

L7g~

The supported oxides of tin employed in Examples
12-15 were made by impregnation of tin ~artrate, in an
aqueous solution of 7% hydrochloric acid, on Houdry HSC 534
silica, the amount of tin provided being sufficient to
yield a solid containing 5 wt. % Sn/SiO2. The solids were
dried at 110C for 4 hours and then calcined in air at
700C for 16 hours. The solids employed in the runs
described in the examples are equilibrated solids, i.e.,
solids prepared as described above which have been
contacted at least once with methane at a temperature of
about 700C and then reoxidized by being contacted with air
at about 700C.
Runs described in Examples 12-15 were made in a
quartz tube reactor (12 mm. inside diameter) packed with
10 ml. of solids at about atmospheric pressure. The
reactors were brought up to temperature under a flow of
nitrogen which was switched to methane at ~he start of the
run. Instantaneous samples of the effluent were taken
throughout the runs and analyzed by gas chromatography and
gas chromatography mass spectroscopy.
EXAMPLE 12
A feed of 100% methane was passed over a bed of
solids as described ~bove. Contact zone temperature was
700C and the GHSV (gas hourly space velocity) was 600
hrs~l. Results are reported in Table XII below. No
carbon was detected on the solid present at the end of the
run.




- 34 -

~788


TABLE XI I
Run Time % % Selectivity
~min) conv. C2H4 ~ C~ C4-7 CO ~O~
Instantaneous Results
.5 3.18 7.2 13.7.2 .8 15.5 62.3
1.0 1.27 8.8 17.2.5 2.7 24.7 45.7
2.0 .25 34,3 52.73.6 9.2
Cumulative Results
-
15 .23 29.9 29.93.4 8.6 11.0 16.9
EXAMPLE 1 3
A feed of 100% methane was passed over a bed of
solids as described above. Contact zone temperature was
750C and the GHSV was 600 hrs~l. Results are reported in
Table XIII below. No carbon was detected on the solid
present at the end of the run. Figure 5 is a plot of %
methane conversion and % selectivity to C2 + hydrocarbon
products vs. run time.


TA13LE XI I I

Run Time % % Selectivity
(min~ conv. C~H~ fi C C4-7 CO ~2
20Instantaneous Results
-
.5 7.23 9.9 14.6 .4 .4 9.2 65.4

1.0 1.25 18.2 35.6 .7 1.0 2.3 42.2

2.0 .43 30.7 67.6 1.3 .2

Cumulative Results

.
15 .54 24.7 40~8 .9 2.5 13.0 17.8
E_AMPLE 1 4
The reduced solid remaining at the end of the run
described in Example 13 was regenerated under a flow of air
at 750C for 30 minutes. The reactor was then flushed with
nitrogen. The regenerated, reoxidized solids were then


- 35 -


contacted with methane at a temperature of 750C and GHSV
of 600 hrsO~l. Resul-ts are shown in Table XIV below. No
carbon oxides were detected during the oxidation of the
reduced solids. Figure 6 is a plot of methane conversion
vs. run time for the combined results of Examples 13 and 14.


TABLE XIV

Run Time % ~ Selectivity
(min? _ conv. ~ C2H6 C3 C4-7 CO ~2
Instantaneous Results
10.5 6.52 11.2 1~.8.3 .2 13.5 59.8
1.0 1.10 22.7 34Ø5 .7 15.7 26.3
2.0 .37 32.7 65~21.2 .2 .8
Cumulative Results
15 .48 26.2 35.31.33.~ 12.0 21.9
EXAMPLE 15
The procedure of Example 12 was repeated except
that contact zone temperature was 800C. Results are shown
in Table XV below. No carbon was detected on the solid
present at the end of the run.
TABLE XV

Run Time % ~ Selectivity
(min? conv- ~2~ C2H6C~ C4-7 CO C02
Instantaneous P~esults
.5 10.1 15.7 13.6.8 .9 11.1 57.7
1.0 3.2 26.7 21.11.71.8 18.2 30.3
2.0 2.2 20~6 19.41.2 .9 24.9 32.7
Cumulative Results
15 1.9 18.0 13.7.8 .8 27.9 38.6




- 36 -



EXAMPLE 1~
Indium nitrate (1.7 grams) was dissolved in 100
ml. water. This solution was then added to 9.5 grams of
Houdry HSC 534 silica and allowed to stand Eor 1 hour. The
mixture was slowly taken to dryness with gentle warming
followed by heating at 110C. in a drying oven for 2 hours.
The solid was then heated to 700C at 2/minute and held at
700C. for 10 hours in air to give a finished indium oxide/
silica solid containing 5 weight % indium. The finished
solid (207 grams) was charged to a quartz tube of 0.5 inch
inside diameter surrounded by a tubular furnace. The
contact zone temperature was raised to 700C. under flowing
nitrogen. Nitrogen flow was stopped and methane was intro-
- duced into the reactor at a rate of 100 ml/min. (i.e., a
gas hourly space velocity of 860 hrsO~l GHSV~. Reactor
effluent was sampled at the reactor exit and analyzed on a
gas chromatograph at a number of time intervals. In addi-
tion, all reactor effluent was collected in a sample bag
for subsequent analysis of the cumulative reaction products
Results (obtained at about atmospheric pressure) are shown
in Table XVI below,




- 37 -

7~8

TABLE XVI

% Selectivity
Time
(min.) Conversion C2~4 ~ C~ ~2
Instantaneous Results
1 0.73 10.9 21.9 0.366.9
3 0.31 22.4 51.3 0.725.6
6 0.23 26.0 73.6 0.4 0.0
11 0.12 34.0 66.0 0.0 0~0
0.10 39.4 60.6 0.0 0.0
Cumulative Results
30 0.21 28.4 47.7 0.223.7
EXAMPLE 17
After completion of the run described in Example
16, ethane Elow was stopped and the contact zone was
flushed with nitrogen for 30 minutes, and the solids were
oxidized under flowing air at 700C for 90 minutes. The
effluent produced during reoxidation was monitored for
carbon oxides, and none were found, indicating that no
carbonaceous deposit was formed during the methane-contact
run described in Example 16. The reoxidized solid was then
contacted with methane as described in Example 16. Results
are shown in Table XVI below. Figure 7 is a plot of
methane conversion and selectivity to C2-~ hydrocarbon
products vs. run time for the combined results of Examples
16 and 17.




- 38 -

7~

TABLE XVII
% Selectivity
Run Time %
(min ) Conversion C~H~ C2H6 C3 ~2
Instantaneous Results
1 0.85 12.8 26.0 0.460.8
3 0.34 21.6 48.4 ~.629.4
6 0.21 31.3 6~.1 0.6 0.0
11 0.13 32.2 67.5 0.3 0.0
0.12 29.6 70.4 0.~ 0,0
Cumulative Results
30 0.25 29.1 50.4 0.3~0.2
EXAMPLE 18
The procedure of Example 16 was repeated except
that the gas hourly space velocity was reduced to 86
hours~l. Results are shown in Table XVIII below, and a
plot of methane conversion and selectivity to C2~ hydro-
carbon products vs. run time is shown in Figure 8.
TABLE XVIII
% Selectivity
Run Time
20 (min.) Conversion ~ h ~ 2
1 5.41 7.1 4.2 0.188.6
7 1.98 20.7 13.2 0.565.6
12 1.59 21.5 15.8 0.662.1
23 1.20 27.5 20.9 1.749.9
Cumulative Results
-
30 2.20 16.3 11.5 0.571.7
EXAMPLE 19
The procedure of Example 16 was repeated again
except that the feed comprised 6 volume per cent methane in
nitrogen. Results for the run are shown in Table XIX below.

- 39 -

~2~7~19


Figure 9 is a plot of methane conversion and selectivity to
C2+ hydrocarbon products vs. run time.
TABLE XIX
% Selectivity
Run Time %
(min.) Conversion C~H4 C2Hk C~ ~2
Instantaneous Results
1 5.6~ 0.8 0.9 0.0 98.3
5 0.32 15.3 31.3 0.2 53.2
12 0.27 12.5 33.~ 0.4 53.6
1029 0.17 13.1 36.1 0.0 50.8
Cumulative Results
30 0.49 10.4 25.6 0.1 63.9
EXAMPLE 20
Germanium dioxide (0.36 gram) was dissolved in
100 ml. water over a period of 12 hours. 1Ihis solution was
added to 9.5 grams of Houdry HSC 534 silica and allowed to
stand for 1 hour. The mixture was slowly taken to dryness
with gentle warming, followed by heating at 110C. in a
drying oven for 2 hours. The dried solid was then further
heated to 700C. at a rate of 2/minute and held at 700C.
for 10 hours to give a product containing 2.5 weight %
germanium. The entire procedure was then repeated using
the solid containing 2.5 weight % germanium instead of
fresh silica, to give a final germanium oxide/silica solid
containing 5 weight % germanium. The finished solid (2.6
grams) was charged to a quartz tube of 0.5 inch inside
diameter surrounded by a tubular furnace. The reactor
temperature was raised to 700C. under flowing nitrogen.
Nitrogen flow was stopped and methane was introduced into
the reactor at a rate oE 100 ml./min. (860 hrs.~l GHSV).

-- ~10 --

7~

The reactor effluent was sampled at the reactor exit and
analyzed on a gas chromatograph at a number of time
intervals. In addition, all reactor effluent was collected
in a sample bag for subsequent analysis of the cumulative
reaction products. Results (obtained at about atmospheric
pressure and 700C.) are shown in Table XX below. The total
amount of carbon oxides formed during reoxidation of the
solids (see Example 21, infra) was used to calculate the
yield of coke (or other carbonaceous deposit) formed on the
solid during the methane run. The instantaneous results
shown in Table XX are methane conversion to gaseous products
and selectivity to these products (i.e~, % of C converted
to gas phase products). The cumulative results shown in
Table XX include solid ~ormation.
TABLE XX
% Selectivity*

Run
Time Conver- Ben-
(min.) sion C~H~ h _~ C~ zene CO Coke*
Instantaneous Results
201 0.39 10.4 26.0 1.0 0O3 0.0 62.3
3 0.18 41.3 49.6 5.8 2.5 0.8 0.0
10 0.15 53.3 33.3 6.7 4.7 2.0 0.0
30 0.13 54.2 27.2 11.4 5.4 1.8 0.0
Cumulative Results
30 0.22 31.9 25.2 6.4 3.2 1.4 6.~ 25.9

*Basis of instantaneous results is C converted to gas
phase products and does not include conversion to solid,
carbonaceous deposits.
EXAMPLE 21
After completion of the run described in Example

20, the reactor was flushed with nitroyen for 30 minutes


- 41 -

~2~4~7W

and the solid was reoxidized under flowing air at 700C.
for 90 minutes. The reoxidized solid was then contacted
with methane as described in Example 20. Results, shown in
Table XXI below, are presented in the same manner as
described in Example 20. Figure 10 is a plot of methane
conversion to gaseous products ancl C2~ hydrocarbon select-
ivity (basis: methane conversion to gaseous products) vs.
run time for the s~ombined results of Examples 20 and 21.


TABLE XII
~6 Selectivity*
Run %
Time Conver- Ben-
(min.) sion ~L C~H,~ C3 C4,szene CO Coke*
_ . .
Instantaneous Results
-
~.30 6.8 20.5 0.7 0.3 0.071.7
3 0.19 37.6 5~.6 5.3 3.0 1.5 0.0
0.17 51.3 3201 9.0 5.1 2.5 0.0
0~14 56.4 2400 12.05.4 2.2 0.0
Cumulative Results
30 0.21 34.1 21.0 6.8 3.4 1.3 8.4 25.0

20 *Basis of instantaneous results is C converted to gas phase
products and does not include conversion to solid,
carbonaceous deposits.
EXAMPLE 22
The procedure of Example 20 was repeated except
that the methane run temperature was increased to 750C.
Results are shown in Table XXII below. Figure 11 shows the
time dependence of methane conversion to all gaseous
products and to gaseous hydrocarbons.




-- 42 --

~97~38

TABLE XXII


% Selectivity*
Run %
Time Conver- Ben-
(min.)sion C2H4 ~ C4,s zene CO Coke*

Instantaneous Results
~ 7 . . _ _ _
1 1.41 38.6 24.6 3.5 2.5 1.9 2~.9
3 1.14 52.4 11.3 5O0 3.0 5.0 23.3
0.96 67.5 10.4 ~.6 4.2 7.2 ~.1
0.32 66.7 22.5 6.7 2.2 1.9 0.0
Cumulative Results
30 1.06 41.1 9.5 4.4 2.3 3.3 8.7 30.7

*Basis of instantaneous results is C converted to gas phase
products and does not include conversion to solid,
carbonaceous deposits.
EXAMPLE 23
Lead (II) acetate ~0.92 gram) was dissolved in
100 ml. of water. This solution was added to 9.5 grams of
Houdry HSC 534 silica and allowed to stand for one hour.
The mixture was slowly taken to dryness with gentle warming,
followed by heating at 110C in a drying oven for 2 hours.
The solid was then heated to 500C at a rate of 2C/minute
and held at 500C for 10 hours to give a finished solid
containing 5 wt. % lead.
The finished solid (2.8 grams) was charged to a
quartz tube (0.5 inch inside diameter) surrounded by a
tubular furnace. The reactor temperature was raised to
700C under flowing nitrogen. Nitrogen flow was stopped
and methane was introduced into the reactor at a rate of

100 ml./min. (860 hrs.-l G~SV). The reactor effluent was
sampled at the reactor exit and analy~ed on a gas chromato-

graph at a number of time intervals. In addition, all


- 43 -

~2~4~8~

reactor effluent was collected in a sample bag for subse~
quent analysis of the cumulative reaction products.
Results (obtained at about atmospheric pressure and 700C.)
are shown in Table XXIII below. The total amount of carbon
oxides formed during reoxidation of the solids (see Example
24, infra) was used to calculate the yield of coke (or
other carbonaceous deposit) formed on the solid during the
methane run. The instantaneous results shown in Table
XXIII are methane conversion to gaseous products and
10 selectivity to these products (i.e., % of C converted to
gas phase products). The cumulative results shown in Table
XXIII include solid formation.
TABI.E XXIII


% Selectivity*
Run 96
Time Conver- Ben-
(min.)sion ~2~ ~ C3 C~ zene CO ~2 Coke*
= .
Instantaneous Results

3.87 12.45.7 0,5 0.3 0.261.719.1

3 0.26 62.533.6 2.7 1.2 0.00.0 0.0

0.12 61.938.1 0.0 0.0 0.00.~ 0.0

0.08 58.341.7 0.0 0.0 0,00.0 0.0

0.08 57.542.5 0.0 0.0 0.00.0 0.0


Cumulative Results

30 0.33 23.1 14.9 0.3 0.2 0,124.07O5 29.9

*~asis of instantaneous results is C converted to gas
phase products and does not include conversion to solid,
carbonaceous deposits.




-- 44 --

9~20~7~3

EXAMPLE 24
After completion of the run described in Example
23, the reactor was flushed with nitrogen for 30 minutes
and the solid was reoxidized under flowing air at 700C.
for 90 minutes. The reoxidized solid was then contacted
with methane in the same manner described in Example 23.
Results, shown in Table XXIV below, are presented as in
Example 23. Figure 12 as a plot o:E methane conversion to
gaseous products and C2+ hydrocarbon product selectivity
(basis: methane conversion to gaseous products) vs. run
time for the combined results of Examples 23 and 24.
TABLE XXIV
% Selectivity*
.
Run %
Time Conver- Ben-
~min.) sion ~2~ C2H~ C3 C4,s zene CO ~2 Coke*

Instantaneous Results

1 3.50 14.35.2 0.2 0.1 0.162.917.2

3 0.2g 54.143O9 1.0 0.7 0.30.0 0.0

0.16 51.24~.0 0.8 0.0 0.00.0 0.0

0.11 51.448.6 0.0 0.0 0.00.0 0,0

0.10 51.0~9.0 0.0 0.0 0.00.0 0.0

Cumulative Results


30 0.31 25.3 23.1 0.5 0.3 0.119.2 7.4 25.0

*Basis of instantaneous results is C converted to gas phase
products and does not include conversion to solid,
carbonaceous deposits.
EXAMPLE 25

Example 23 was repeated except that the GHSV was

86 hrs.~l, Results are shown in Table XXV below and are

plotted as a function of run time in Figure 13.




- ~5 -


TABLE XXV
% Selectivity*
Run
Time Conver-Ben- Tol-
(min.) sion ~2~ C2H6 C3 ~ ene uene CO ~2 Coke*
Instantaneous Results
1 3.66 ~8.6 3.6 3.3 2.4 ~.9 0.8 0.0 48.4
3 3.47 43.6 4.0 3.8 2.3 2.7 0.9 0.0 42.7
2.07 43.5 4.4 3.9 2.1 107 Oq5 0.0 43.9
1.57 50.3 5.4 4.5 1.8 1.3 0.4 0.0 36.3
0.70 58.7 g.0 5.9 109 1.4 0.3 0.0 22.9
Cumulative Results
30 3.15 25~7 3.5 3.2 1.6 1.3 0.3 0.0 25.7 38,7
*Basis of instantaneous results i5 C converted to gas phase
products and does not include conversion to solid,
carbonaceous deposits.
EXAMPLE 26
Example 23 was repeated except that the contact
zone temperature was 800C. Results are shown in Table
XXVI below and are plotted as a func-tion of run time in
Figure 14.




- 46 -

~47~

TABLE XXVI
% Selectivity*

Run %
Time Conver- Ben- Tol-
(min.) sion C~H4 ~2~ C3 C4~ zene uene CO ~2 Coke*
Instantaneous Results
1 2.45 32.6 4.9 3.5 2.2 1.9 0~7 26.9 27.3
3 1 L 22 49.3 9.0 4.9 2.5 2.1 0.9 31.3 0.0
0.63 6~.3 20.3 7.2 3.0 2.5 0.7 0.~ 0.0
0.5~ 59.7 24.3 8.2 4.3 2.6 O.g 0.0 0.0
0.5~ 58.5 25.6 9.0 3.1 2.9 0.9 0.0 0.0
Cumulative Results
1.~5 38.6 12.9 4.6 2.1 1.8 0.7 4~0 1.6 33.7

*Basis of instantaneous results is C converted to gas phase
products and does not include conversion to solid,
carbonaceous deposits.
EXAMPLE 27
An aqueous solution of antimony tartrate was
added to Hourdy HSC 534 silica and allowed to stand for one
hour. The mixture was dried at 110C for 4 hours and
calcined at 700C for 16 hours. The relative amounts of
antimony tartrate and silica were sufficient to yield a
finished solid containing 5 wt.% Sb.
Finished solid (10 ml.) was charged to a quartz
tube (0.5 in. inside diameter) surrounded by a tubular
furnace. The reactor was brought up to 700C under a flow
of nitrogen which was switched to methane at the start of
the run. A feed of 100% methane was passed over the bed of
solids. Contact zone temperaturek was 700C, the pressure
was atmospheric, and the GHSV (gas hourly space velocity~
was 600 hrs.-l. Instantaneous samples were taken through-


out the run and analyzed by gas chromatography and gas


- 47 -

~478~

chromatography-mass spectroscopy. A cumulative sample was
also collected and analyzed. Results are reported in Table
XXVII below. No carbon was detected on the solid at the
end of the run. Figure 15 is a plot of methane conversion
and % selectivity to C2~ hydrocarbon products vs. run time.


TABLE XXVII

Run Time % % Selectivity
(min) _ conv. ~ 2~ C~ CO ~2
Instantaneous Results
100.5 1.2 5.6 6.2 0.3 35.552.3
1.0 0.6 2302 32.0 0.3 44.5
2.0 0.0~ 40.0 60.0
Cumulative Results
-
15 0.12 40.7 32.8 20.36.5
EXAMPLE 28
The reduced solid remaining at the end of the run
described in Example 27 was regenerated under a flow of air
at 700~C for 30 minutes. The reactor was flushed with
nitrogen. The reoxidized solids were then contacted with
20 methane as in Example 27. Figure 16 is a plot of methane
conversion vs. time for the combined results of Examples 17
and 28.
E_MPLE 29
Example 27 was repeated except that the contact
zone temperature was 800~C. Results are shown in Table
XXVIII below.




-- 4~ --

7~

TABLE XXVIII

Run Time ~ % Selectivity
(min) conv. ~ C2H~ C~ CO ~2
Instantaneous Results
.5 2.7 10.3 11.7 .04 24.553.1
1.0 1.2 32.1 29.8 0.6 3~.1
2.0 0.5 55.6 4~.2 0.2
Cumulative Results
15 ~.25 ~4.2 3~.7 0.4 8.38.4


The supported oxides of bismuth employed in
Examples 30-32 were made by impregnation of an aqueous
solution of bismuth nitrate on Houdry HSC 534 silica, the
amount of bismuth provided being sufficient to yield a
solid containing 5 wt. % Bi/SiO2. The solids were dried at
100C for 4 hours and then calcined in air at 700C for 16
hours.
Runs described in Example 30-32 were made in a
~quartz tube reactor (12 mm. inside diameter) packed with
10 ml. of solids. Pressures were about atmospheric. The
reactor was brought up to temperature under a flow of
nitrogen which was switched to methane at the start of the
run. Instantaneous samples of the effluent were taken
throughout the runs and analyzed by gas chromatography and
gas chromatography-mass spectroscropy. A cumulative
sample was also collected and analyzed.
EXAMPLE 30
A feed of 100~ methane was passed over a bed of
solids as described above. Contact zone temperature was

700C and the GHSV (gas hourly space velocity) was 600
hrs.~l. Results are reported in Table XXIX below. No

_ ~,9 _


carbon was detected on the solid at the end of the run.
Figure 17 is a plot of methane conversion and ~ selectivity
to C2~ hydrocarbon products vs. run time.
TABLE XXIX
__%_ electivity

Run
Time Conver-
~min ? sion ~ C2HfiC3 C4-c7 CO ~2
Instantaneous Results
,5 3.40 8.89 22.19.22 .74 20.29 ~7.67
101 1.98 11.01 27.36.35 1.30 28.80 30.91
2 1.07 16~11 35.53O59 2.05 45.72 0
Cumulative Results
15 .38 30.13 46.151.503.35 14.62 4.2
EXAMPLE 31
The reduced solid remaining at the end of the run
described in Example 30 was regenerated under a flow of air
at 700C for 30 minutes. The reactor was flushed wi-th
nitrogen. The reoxidized solids were then contacted with
methane at a temperature of 700C and 600 hrs -1. Results
are shown in Table XXX below. Figure 18 is a plot of
methane conversion vs. time for the combined results of
Examples 30 and 31.




- 50 -

~2~7~38

TABLE XXX

% Selectivity
Run %
Time Conver-
(min )sion C2H4 ~h C3 C4-c7 CO ~2
Instantaneous Results
.5 2.27 5.6g 12.53.11 .31 35.66 45.70
1 1.19 12.14 24.63.30 .8~ 49.35 12.75
2 .37 29.55 67.461.021.98 0 0

Cumulative Results
15 .32 20.74 49.9210042.42 20.31 5.57
EXAMPLE 32
Example 30 was repeated except that the contact
zone temperature was 800C. Results are shown in Table
XXXI below.
TABLE XXXI
% Selectivity
_ _ _
Run %
Time Conver-
(min.)sion ~ C2H~ C3 C4-C7 - CO?
Instantaneous Results
.5 29.6~ 7.71 6.68.14 .34 8.28 76.85
1 5.13 23.13 30.721.173.11 24.55 17.32
2 2.25 26.38 40.071.512.~9 29.04 0
Cumulative Results
15 1.04 30.05 44.842.152.28 15~71 4.97





~1;)47~il

EXAMPLE 33
A supported oxide of manganese was prepared by
impre~nating the appropriate amount of manganese, as mangan-
ous acetate in a water solution ! onto a Cab-O-Sil silica
support. The impregnated solids were dried at 110C for 4
hours and then calcined in air a~ 700C for 16 hours. The
composition of the calcined solids was 15 wt.% Mn/silica.
The finished solid was charged to a stainless
steel tu~e (of 3/8 inch inside diameter) surrounded by a
tubular furnace. The interior walls of the stainless steel
tube had been treated with p~tassium pyrophospha~e to
con~rol coke ~ormation cataly2ed by the reactor wall. The
contact ~one t~mperature and pressure w~re raised to 700C
and 100 psig, r~spectively, under flôwing nitrogen.
Nitrogen flow was stopped and methane was introduced into
the contact zone at a GHSV tgas hourly space velocity~ of
435 hrs.-l~ Reactor effluent was sampled at the reactor
exit and analyzed on a gas chromatograph at a number of
time interva}s~ In addition, all reactor effluent was
2Q collected in a sample bag for subsequent analysis of the
cumulative reaction products. Results are reported in
Table XXXII below. Figure 19 shows a plot of ~he ratio,
~ yield of C3~ hydrocarbon products/% yield of C2~ hydro-
carbon products, vs. run time for the instantaneous results
obtained in this run.




- 52 -

* Trade Mark

~2~9~7~1~

TABLE XXXII

% Selectivity
Run %
Time Conver-
~min.) sion ~ C~ C4-C7 CO ~2
Instantaneous Results
-
2 3~19 29.38 49.36 6.47 14.~0 0 0
4 10.44 15.57 10.17 1.84 1.56 2.75 68.11
8 2.62 6.45 18.65 1.54 0.89 13.98 58.49
16 1.23 Q 78.80 ~.73 1.55 14.93 0
Cumulative Results
30 2.~7 3.78 35.22 3.431.86 34.14 21.57
EXAMPLE 34
The procedure of Example 33 was repeated except
that the methane feed rate was increased to provide a GHSV
of 2392 hrs.-l. Figure 19 shows a plot of the ratio, %
yield of C3+ hydrocarbon products/~ yield of C2+ hydro-
carbon products vs. run time for the instantaneous results
obtained in this run.
COMPARATIVE EXAMPLE A
..
The procedure of Example 33 was repeated exc~pt
that the pressure in the contact zone during the methane run
was 0 psig. Figure 19 shows a plot of the ratio, % yield
of C3+ hydrocarbon products/% yield of C2+ hydrocarbon pro-
ducts, vs~ run time for the results obtained in this run.
EXAMPLES 35 - 36
Following the same preparative procedure described
in Example 31, a composition containing 5 wt.% Mn/SiO2 was
prepared and contacted with methane (as described in Example
33) under the operating conditions shown in Table XXXIII
below. Table XXXIII also shows instantaneous results

7~

(i.e., % methane conversion and % selectivity to C3+ hydro-
carbon products) obtained at 2.0 and 1.0 minutes, respec-
tivel~, in Examples 35 and 36.
EXAMPLE 37
A supported oxide of indium was prepared by
impregnating the appropriate amount oE indium, as indium
nitrate in a water solution, onto a silica support. The
impregnated solids were dried at 110C for 2 hours. The
dried solid was then heated to 700C at 2/minute and held
at 700C for 10 hours in air to give a finished solid
containing 5 wt.% In. This solid was contacted with
methane as described in Example 33 under the operating
conditions shown in Table XXXIII below. Table XXXIII also
show instantaneous results obtained at 2.0 minutes after
the start of ~he methane contact.
COMPARATIVE EXAMPLE B
Methane was contacted, at atmospheric pressure,
with a bed of 5 wt.% Mn/SiO2 (prepared as described in
Example 33) in a quartz tube reactor (12 mm. inside
diame~er) packed with 10 ml. of the solid. The temperature
in the contact zone was maintained at 700C and the GHSV
was 600 hrs.~l. Instantaneous results obtained at a run
time of 2 minutes are shown in Table XXXIII below.
COMPAR~TIVE EXAMPLE C
Methane was contacted, at atmospheric pressure,
with a bed of 5 wt.% In/SiO2 (prepared as described in
Example 5) in a quartz tube reactor (0.5 inch inside dia-
meter) packed with 2.7 grams of the solid. The temperature
in the contact zone was maintained at 700C and the G~SV
was 860 hrs.~l. Instantaneous results obtained at run time


of 1.0 and 3.0 minutes are shown in Table XXXIII below.
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-- 55 --

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Administrative Status

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Administrative Status

Title Date
Forecasted Issue Date 1986-05-20
(22) Filed 1983-08-26
(45) Issued 1986-05-20
Expired 2003-08-26

Abandonment History

There is no abandonment history.

Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Application Fee $0.00 1983-08-26
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
ATLANTIC RICHFIELD COMPANY
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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Description 1993-09-23 55 1,881
Drawings 1993-09-23 19 379
Claims 1993-09-23 10 347
Abstract 1993-09-23 1 17
Cover Page 1993-09-23 1 28