U.S. patent application number 13/189563 was filed with the patent office on 2012-07-26 for catalyst for production of synthesis gas.
This patent application is currently assigned to UNIVERSITY OF SASKATCHEWAN. Invention is credited to Ajay Kumar Dalai, Hui Wang, Jianguo Zhang.
Application Number | 20120190539 13/189563 |
Document ID | / |
Family ID | 41430272 |
Filed Date | 2012-07-26 |
United States Patent
Application |
20120190539 |
Kind Code |
A1 |
Zhang; Jianguo ; et
al. |
July 26, 2012 |
CATALYST FOR PRODUCTION OF SYNTHESIS GAS
Abstract
The present invention relates to a novel composite metal oxide
catalyst, a method of making the catalyst, and a process for
producing synthesis gas using the catalyst. The catalyst may be a
nickel and cobalt based dual-active component composite metal oxide
catalyst. The catalyst may be used to produce synthesis gas by the
carbon dioxide reforming reaction of methane. The catalyst on an
anhydrous basis after calcinations has the empirical formula: M a m
+ N b n + Al c 3 + Mg d 2 + O ( am 2 + bn 2 + 3 2 c + d )
##EQU00001## M.sup.m+ and N.sup.n+ are two transition metals
serving as dual-active components and selected from the group
consisting of Ni, Co, Fe, Mn, Mo, Cu, Zn or mixtures thereof,
a+b+c+d=1, and 0.001.ltoreq.a.ltoreq.0.8,
0.001.ltoreq.b.ltoreq.0.8, 0.1.ltoreq.c.ltoreq.0.99,
0.01.ltoreq.d.ltoreq.0.99.
Inventors: |
Zhang; Jianguo; (Saskatoon,
CA) ; Wang; Hui; (Saskatoon, CA) ; Dalai; Ajay
Kumar; (Saskatoon, CA) |
Assignee: |
UNIVERSITY OF SASKATCHEWAN
Saskatoon
CA
|
Family ID: |
41430272 |
Appl. No.: |
13/189563 |
Filed: |
July 25, 2011 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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12142517 |
Jun 19, 2008 |
7985710 |
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13189563 |
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Current U.S.
Class: |
502/306 ;
502/324; 502/328; 502/329 |
Current CPC
Class: |
C01B 2203/1076 20130101;
C01B 2203/1058 20130101; B01J 35/0053 20130101; C01G 53/66
20130101; B01J 35/0066 20130101; C01B 2203/1041 20130101; B01J
2523/00 20130101; B01J 23/80 20130101; C01P 2006/14 20130101; B01J
35/1014 20130101; Y02P 20/52 20151101; C01P 2006/80 20130101; C01B
2203/1052 20130101; B01J 37/03 20130101; Y02P 20/142 20151101; C01P
2004/04 20130101; B01J 23/883 20130101; B01J 23/8892 20130101; B01J
35/1038 20130101; B01J 23/002 20130101; C01F 7/002 20130101; B01J
23/755 20130101; C01B 3/40 20130101; C01P 2004/60 20130101; B01J
35/0006 20130101; B01J 35/1061 20130101; C01P 2006/16 20130101;
B01J 37/18 20130101; Y02P 20/141 20151101; C01B 2203/1241 20130101;
C01P 2006/12 20130101; B01J 35/0073 20130101; C01B 2203/0238
20130101; B01J 35/006 20130101; B01J 2523/00 20130101; B01J 2523/22
20130101; B01J 2523/31 20130101; B01J 2523/72 20130101; B01J
2523/847 20130101; B01J 2523/00 20130101; B01J 2523/17 20130101;
B01J 2523/22 20130101; B01J 2523/31 20130101; B01J 2523/847
20130101; B01J 2523/00 20130101; B01J 2523/22 20130101; B01J
2523/31 20130101; B01J 2523/845 20130101; B01J 2523/847
20130101 |
Class at
Publication: |
502/306 ;
502/328; 502/324; 502/329 |
International
Class: |
B01J 21/10 20060101
B01J021/10 |
Claims
1. A catalyst composition comprising a dual-active component
composite metal oxide for production of synthesis gas having a
chemical composition on an anhydrous basis after calcination
expressed by the empirical formula: Ni _ a m + N b n + Al c 3 + Mg
d 2 + O ( am 2 + bn 2 + 3 2 c + d ) ##EQU00007## wherein Ni.sup.m+
and N.sup.n+ are two transition metals serving as dual-active
components and N.sup.n+ is selected from the group consisting of
Ni, Co, Fe, Mn, Mo, Cu, Zn and mixtures thereof; m and n are the
valences of Ni and N respectively and equivalent to 2 or 3; a, b, c
and d are mole fractions wherein a+b+c+d=1 and
0.001.ltoreq.a.ltoreq.068, 0.001.ltoreq.b.ltoreq.0.8,
0.1.ltoreq.c.ltoreq.0.99, 0.01.ltoreq.d.ltoreq.0.99; the
dual-active component composite metal oxide is prepared by
co-precipitation; and the dual-active component composite metal
oxide produces synthesis gas by CO.sub.2 reformation of
hydrocarbon.
2-23. (canceled)
Description
FIELD OF THE INVENTION
[0001] The present invention relates generally to catalysts for
producing synthesis gas, and more particularly to catalysts for
producing synthesis gas by carbon dioxide reforming of
hydrocarbons.
BACKGROUND OF THE INVENTION
[0002] Synthesis gas is a mixture of gases including varying
amounts of carbon monoxide and hydrogen. Synthesis gas may be used,
for example, as an intermediate in the production of synthetic
natural gas, synthetic petroleum, ammonia and methanol. Synthesis
gas may be produced by carbon dioxide reforming reactions of
hydrocarbons, particularly light hydrocarbons such as methane.
[0003] Synthesis gas may be produced by carbon dioxide reforming of
methane according to the following reaction:
CH.sub.4+CO.sub.2=2CO+2H, 247 kJmol.sup.-1
[0004] This reaction is highly endothermic and generally requires
temperatures in the range of 600 to 1100.degree. to drive the
reaction forward. Reforming catalysts such as Ni/Al.sub.2O.sub.3,
Ni/MgO/Al.sub.2O.sub.3 and the like may be used to catalyze the
reaction. Reforming catalysts used in the above reaction are
generally Group VIII metals held on various supports.
[0005] Problems with known reforming catalysts include severe and
rapid deactivation as a result of coking, or carbon deposition on
the catalyst. Often, known catalysts are expensive to produce (e.g.
some noble metal catalysts) and/or have low selectivity for target
products such as hydrogen and carbon monoxide. Carbon dioxide
reforming of methane to produce synthesis gas has therefore yet to
be established on a commercial scale.
[0006] It is desirable to provide a stable, inexpensive reforming
catalyst with high catalytic activity and high selectivity for
products such as hydrogen and carbon monoxide.
SUMMARY OF THE INVENTION
[0007] One aspect of the present invention provides a catalyst
composition having a dual-active component composite metal oxide
for production of synthesis gas. The dual-active component
composite metal oxide has a chemical composition on an anhydrous
basis after calcination expressed by the empirical formula:
M a m + N b n + Al c 3 + Mg d 2 + O ( am 2 + bn 2 + 3 2 c + d )
##EQU00002##
wherein M.sup.m+ and N.sup.n+ are two transition metals serving as
dual-active components and selected from the group consisting of
Ni, Co, Fe, Mn, Mo, Cu, Zn or mixtures thereof, m and n are the
valences of M and N respectively and equivalent to 2 or 3. a, b, c
and d are mole fractions with the proviso that a+b+c+d=1 and
0.001.ltoreq.a.ltoreq.0.8, 0.001.ltoreq.b.ltoreq.0.8,
0.1.ltoreq.c.ltoreq.0.99, 0.01.ltoreq.d.ltoreq.0.99.
[0008] Another aspect of the present invention provides a process
for preparing a catalyst composition having a dual-active component
composite metal oxide for production of synthesis gas. The
dual-active component composite metal oxide has a chemical
composition on an anhydrous basis after calcination expressed by
the empirical formula:
M a m + N b n + Al c 3 + Mg d 2 + O ( am 2 + bn 2 + 3 2 c + d )
##EQU00003##
wherein M.sup.m+ and N.sup.n+ are two transition metals serving as
dual-active components and selected from the group consisting of
Ni, Co, Fe, Mn, Mo, Cu, Zn or mixtures thereof, m and n are the
valences of M and N respectively and equivalent to 2 or 3, a, b, c
and d are mole fractions with the proviso that a+b/c+d=1 and
0.001.ltoreq.a.ltoreq.0.8, 0.001.ltoreq.b.ltoreq.0.8,
0.1.ltoreq.c.ltoreq.0.99, 0.01.ltoreq.d.ltoreq.0.99. The process
includes the steps of: [0009] (a) dissolving water soluble metal
salts comprising inorganic or organic salts of Mg. Al and two
transition metals selected from the group consisting of Ni, Co, Fe,
Mn, Mo, Cu, Zn and mixtures thereof; [0010] (b) adding a basic
solution of a precipitation reagent into an acidic solution of the
metal salts of step to generate a precipitate; [0011] (c) washing
the precipitate; [0012] (d) drying the precipitate; [0013] (e)
calcining the precipitate; and [0014] (f) activating the catalyst
composition before reaction in a flow stream comprising
[0015] A further aspect of the present invention provides a process
for producing synthesis gas using a catalyst composition for
reforming a hydrocarbon or biogas with an oxidant. The catalyst
composition has a dual-active component composite metal oxide for
production of synthesis gas. The dual-active component composite
metal oxide has a chemical composition on an anhydrous basis after
calcination expressed by the empirical formula:
M a m + N b n + Al c 3 + Mg d 2 + O ( am 2 + bn 2 + 3 2 c + d )
##EQU00004##
wherein M.sup.m+ and N.sup.n+are two transition metals serving as
dual-active components and selected from the group consisting of
Ni, Co, Fe, Mn, Mo, Cu, Zn or mixtures thereof, m and n are the
valences of M and N respectively and equivalent to 2 or 3, a, b, c
and d are mole fractions with the proviso that a+b+c+d=1 and
0.001.ltoreq.a.ltoreq.0.8, 0.001.ltoreq.b.ltoreq.0.8,
0.1.ltoreq.c.ltoreq.0.99, 0.01.ltoreq.d.ltoreq.0.99.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Further features and advantages of the invention will be
shown by the following detailed description of the preferred
embodiments of the present invention combined with the drawings in
which:
[0017] FIG. 1 is a graph showing CH.sub.4 conversion as a function
of time-on-stream (TOS) for a 28-h activity and stability test of
certain embodiments of the present invention.
[0018] FIG. 2 is a graph showing relative FI, and CO production as
a function of TOS for a 28-h activity and stability test of certain
embodiments of the present invention;
[0019] FIG. 3 is a graph showing average carbon deposition rate for
a 28-h activity and stability test of certain embodiments of the
present invention;
[0020] FIG. 4 is a graph showing carbon deposition and CH.sub.4
conversion as a function of TOS for 20, 200 and 2000-h activity and
stability tests of a certain embodiment of the present
invention;
[0021] FIG. 5 is a graph showing Hi/CO formation as a function of
TOS for 20, 200 and 2000-h activity and stability tests of certain
embodiments of the present invention;
[0022] FIG. 6 is a graph showing CH.sub.4 conversion as a function
of TOS for a 250-h activity and stability tests of certain
embodiments of the present invention;
[0023] FIGS. 7(a) and (b) are graphs, for a 250-h activity and
stability tests of certain embodiments of the present invention,
(a) showing thermo-gravimetric (TG) profiles of spent catalysts;
and (b) showing differential thermo-gravimetric (DTG) profiles of
spent catalysts
[0024] FIGS. 8(a) to (d) are transmission electron microscopy (TEM)
micrographs of catalysts before and after a 250-h testing period
for a 250-h activity and stability test of certain embodiments of
the present invention, namely (a) Catalyst 5 before reaction; (b)
Catalyst 1 before reaction; (c) Catalyst 5 after reaction; and (d)
Catalyst 1 after reaction;
[0025] FIG. 9 is a graph showing temperature-programmed reduction
(TPR) profiles of certain embodiments of the present invention;
[0026] FIG. 10 is a graph showing X-ray powder diffraction (XRD)
profiles of certain embodiments of the present invention;
[0027] FIGS. 11(a) and (b) are X-ray photoelectron spectroscopy
(XPS) Ni 2p.sub.3/2 and Co 2p.sub.3/2 spectra of certain
embodiments of the present invention;
[0028] FIG. 12 is a graph showing CH.sub.4 conversion as a function
of TOS in solid lines and CO.sub.2 conversion as a function of TOS
in dotted lines for a 28-h activity and stability tests of certain
embodiments of the present invention;
[0029] FIG. 13 is a graph showing CH.sub.4 conversion and CO.sub.2
conversion as functions of gas hourly space velocity (GHSV) for
activity and stability tests of a certain embodiment of the present
invention;
[0030] FIG. 14 is a graph showing CH.sub.4 conversion and CO,
conversion as functions of reaction temperature for activity and
stability tests of a certain embodiment of the present
invention;
[0031] FIG. 15 is a graph showing CH.sub.4 conversion as a function
of TOS for a2000-h activity and stability test of a certain
embodiment of the present invention;
[0032] FIG. 16 is a graph showing CO.sub.2 conversion as a function
of TOS for a 2000-h activity and stability test of a certain
embodiment of the present invention;
[0033] FIG. 17 is a graphshowing CO selectivity as a function of
TOS for a 2000-h activity and stability test of a certain
embodiment of the present invention;
[0034] FIG. 18 is a graph showing H.sub.2 selectivity as a function
of TOS for a 2000-h activity and stability test of a certain
embodiment of the present invention;
[0035] FIG. 19 is a graph showing variation of the BET surface area
with (Ni+Co)/(Al+Mg) ratio for certain embodiments of the present
invention;
[0036] FIG. 20 is a graph showing XRD profiles of certain
embodiments of the present invention (.smallcircle. denoting
spinel-like structures and .quadrature. denoting solid
solutions);
[0037] FIG. 21 is a graph showing TPR profiles of certain
embodiments of the present invention;
[0038] FIG. 22 is a graph showing pore size distribution of certain
embodiments of the present invention;
[0039] FIGS. 23(a) to (d) are pre-reaction TEM micrographs and
particle size distribution graphs of certain embodiments of the
present invention as defined in Example 7 of the following
description, namely (a) Catalyst 18; (b) Catalyst 17; (c) Catalyst
16; and (d) Catalyst 15;
[0040] FIG. 24 is a graph showing CH.sub.4 conversion as a function
of TOS for a 250-h activity and stability test of certain
embodiments of the present invention;
[0041] FIGS. 25(a) and (b) are graphs, for a 250-h activity and
stability tests of certain embodiments of the present invention,
showing: (a) TG profiles of spent catalysts; and (b) DTG profiles
of spent catalysts; and
[0042] FIGS. 26(a) to (d) are post-reaction TEM micrographs of
certain embodiments of the present invention, namely (a) Catalyst
18; (b) Catalyst 17; (c) Catalyst 16; and (d) Catalyst 15.
DETAILED DESCRIPTION OF THE INVENTION
[0043] Throughout the following description specific details are
set forth in order to provide a more thorough understanding to
persons skilled in the art. However, well known elements may not
have been shown or described in detail to avoid unnecessarily
obscuring the disclosure. Accordingly, the description and drawings
are to be regarded in an illustrative, rather than a restrictive,
sense.
[0044] In contrast to problems associated with known reforming
catalysts, the present invention provides a catalyst having high
activity, high stability, and high yield of synthesis gas. The term
synthesis gas, as used in this specification, includes carbon
monoxide, hydrogen and gas mixtures containing carbon monoxide and
hydrogen.
[0045] In particular, the present invention relates to a
dual-active component composite metal oxide catalyst for reforming
reactions of hydrocarbons, a method of preparing the catalyst, and
a process for producing synthesis gas using the catalyst.
Preparation and use of the catalyst is inexpensive and simple. The
terms dual-active component composite metal oxide catalyst and
bimetallic catalyst are used interchangeably in this
specification.
[0046] The catalyst according to one embodiment of the present
invention has a chemical composition on an anhydrous basis after
calcination expressed by the empirical formula:
M a m + N b n + Al c 3 + Mg d 2 + O ( am 2 + bn 2 + 3 2 c + d )
##EQU00005##
where M and N are two transition metals selected from Ni, Co, Fe,
Mn, Mo, Cu, Zn or mixtures thereof
[0047] The letters "m" and "n" represent the valence of M and N,
respectively, and are equivalent to 2 or 3 depending on the
transition metals selected. The letters "a" "b", "c" and "d"
represent mole fractions of M, N, Al and Mg, respectively, with the
provisos that a+b+c+d=1.
[0048] The mole fraction of M is 0.001.ltoreq.a.ltoreq.0.8,
preferably 0.005.ltoreq.a.ltoreq.0.5, and even more preferably
0.01.ltoreq.a.ltoreq.0.1. The mole fraction of N is
0.001.ltoreq.b.ltoreq.0.8, preferably 0.005.ltoreq.b.ltoreq.0.5,
and even more preferably 0.01.ltoreq.b.ltoreq.0.1.
[0049] M combines with N resulting in two active components in the
catalyst composition. The interaction between M and N has been
discovered to improve the selectivity of the catalyst and
suppresses coking. These interactions may include strong
metal-support interaction (SMSI) and formation of stable solid
solutions. M and N, particularly at lower molar fractions, also
have a smaller metal particle size and higher dispersion to improve
catalytic performance and reduce coking or carbon deposition. M may
be Ni and N may be Co in certain embodiments.
[0050] The overall mole fraction of M and N is
0.001.ltoreq.(a+b).ltoreq.0.8, preferably
0.005.ltoreq.(a+b).ltoreq.0.5, and even more preferably
0.01.ltoreq.(a+b).ltoreq.0.5. When the overall mole fraction of M
and N is less than 0.005, the activity of the catalyst decreases,
and when the overall mole fraction of M and N exceeds 0.8, the
stability of the catalyst decreases due to coking and
sintering.
[0051] The mole fraction of Al is 0.01.ltoreq.c.ltoreq.0.99,
preferably 0.05.ltoreq.c.ltoreq.0.95, and even more preferably
0.05.ltoreq.c.ltoreq.0.9. Aluminium increases the specific area and
improves the pore structure and distribution of the catalyst.
[0052] The mole fraction of Mg is 0.01.ltoreq.d.ltoreq.0.99,
preferably 0.05.ltoreq.d.ltoreq.0.95, and even more preferably
0.1.ltoreq.d.ltoreq.0.95. The high melting point of MgO which forms
during the process of calcination significantly increases the
resistance of catalyst to sintering greatly. The basicity of MgO
may also play a role in depressing coking.
[0053] The overall mole fraction of Mg and Al is
0.1.ltoreq.(c+d).ltoreq.0.99. preferably
0.15.ltoreq.(c+d).ltoreq.0.90, and even more preferably
0.2.ltoreq.(c+d).ltoreq.0.90. The combination of Al and Mg results
in the formation of spinel MeAl.sub.2O.sub.4 and periclase MgO
after calcination in air, and serves as a support for the
dual-active components M and N of the catalyst. When the overall
mole fraction of magnesium and aluminium is less than 0.1, the
catalyst is unstable due to severe coking and sintering. Activity
of the catalyst is also poor when the overall mole fraction of
magnesium and aluminium exceeds 0.99. The combination of magnesium
and aluminium has two important effects on the stability and
activity of the catalyst: increasing resistance to sintering at
high temperature and keeping a relatively high and stable specific
area and pore structure of the catalyst to increase the contact
area of reaction.
[0054] Any suitable method may be used to prepare the catalyst of
the present invention, including co-precipitation, impregnation,
homogenous precipitation, and sol-gel. Co-precipitation and
impregnation are preferred methods.
[0055] When using a co-precipitating method, one or more water
soluble salts selected from nickel, cobalt, manganese, iron,
molybdenum, copper, and zinc, one water soluble magnesium salt and
one water soluble aluminium salt are together dissolved in water.
Water soluble salts can include inorganic salts, for example,
nitrates, and organic salts, for example acetates.
[0056] A precipitate is generated by adding a precipitation reagent
to above mixed aqueous solution while stirring at 15 to 90.degree.
C. The precipitation reagent may be selected from NH.sup.4+,
OH.sup.-, and CO.sub.3.sup.2-. Sodium carbonate, sodium
bicarbonate, sodium oxalate, sodium hydroxide, potassium carbonate,
potassium bicarbonate, potassium oxalate, potassium hydroxide,
ammonium carbonate, ammonium bicarbonate, ammonia and the like
might be used as the precipitation reagent. Aqueous ammonia
solution is a preferred precipitation reagent.
[0057] With the addition of a precipitation reagent, a precipitate
is formed comprising the above metal components in the form of
hydroxides. After precipitation, and before drying the precipitate,
other unnecessary ions introduced with the precipitation reagent,
such as Na.sup.+, K.sup.+, and Cl.sup.-, are removed from the
precipitate by filtering and washing with distilled water.
[0058] The precipitate is then dried at 70 to 150.degree. C.
overnight. Next, the dried precipitate is calcined for 2 to 20
hours at 300 to 1300.degree. C. in air. It is preferable to
calcinate for 4 to 12 hours at 600 to 1000.degree. C. The catalyst
is a composite metal oxide at this point.
[0059] The catalyst may be crushed to 20 to 70 mesh for use. Prior
to using for producing synthesis gas, the catalyst should be
activated at 200 to 1000.degree. C., preferably 500 to 900.degree.
C. for 0.5 to 50 hours in a flow stream of 5 to 70% hydrogen. The
activation of the catalyst can be carried out in the reactor in
which the reaction to produce synthesis gas will be performed.
[0060] The catalyst may be used to produce synthesis gas by
reacting a hydrocarbon, such as methane, natural gas, petroleum
gas, naphtha, heavy oil, crude oil, biogas, or the like, and their
mixtures with an oxidant, for example steam, carbon dioxide or
oxygen. For example, the catalyst may be used for carbon dioxide
reforming of methane or natural gas.
[0061] The molar ratio between oxidant and hydrocarbon is in, the
range of 0.5 to 10, preferably 1.0 to 6.0, and even more preferably
1.0 to 3.0. It is not necessary to use a large molar ratio of
oxidant to hydrocarbon when using the catalyst of the present
invention. Inert gas such as nitrogen may be employed as reference
gas for calculation of conversion and selectivity. The molar
fraction of inert gas in feed gas is in the range of 10 to 80%.
[0062] The gas hourly space velocity (GHSV, here defined as the
volume flow rate at standard conditions divided by the mass of
catalyst) is 2,000 to 2.000,000 mL/g.sub.cat-h, preferably 10,000
to 1,000,000 mL/g.sub.cat-h, and even more preferably 40,000 to
400, 000 mL/g.sub.cat-h.
[0063] The reaction temperature is in the range of 300 to
1300.degree. C., preferably 500 to 1100.degree. C., and even more
preferably 600 to 1000.degree. C. The reaction pressure is in the
range of 0.1 to 20 atm, preferably 1 to 10 atm, and even more
preferably 1 to 5 atm.
[0064] The type of reactor that can be used can be any suitable
reactor including conventional fixed bed reactors and fluidized bed
reactors.
[0065] The catalyst of the present invention is suitable primarily
for dry reforming of light hydrocarbons and biogas, but may be used
for other purposes such as wet reforming. For the purposes of
synthesis gas production, dry reforming is preferred over wet
reforming. The present invention may also be used in other contexts
such as reduction of carbon dioxide emissions into the
atmosphere.
[0066] The present invention is demonstrated by the specific
examples below, but the invention is not limited in scope
thereto.
EXAMPLE 1
Catalyst Preparation, Characterization and Testing
[0067] The catalysts described in Examples 2-7 were prepared,
characterized and tested according to the procedures described in
this Example 1 below.
Catalyst preparation
[0068] Bimetallic catalysts having an Al--Mg--O framework were
prepared by co-precipitating a common aqueous solution of nickel
nitrate (98% purity, Lancaster Synthesis Inc.), cobalt nitrate (99%
purity, Aldrich Chemical Company), magnesium nitrate (EMD Chemicals
Inc.) and aluminium nitrate (EMD Chemicals Inc.). Other bimetallic
catalysts were prepared by replacing cobalt nitrate with iron (III)
nitrate (99% purity, Lancaster Synthesis Inc.), manganese nitrate
(99.98% purity, Lancaster Synthesis Inc.), or copper (II) nitrate
(99% purity, Aldrich Chemical Company). Yet other bimetallic
catalysts were prepared by replacing nickel nitrate with manganese
nitrate. Monometallic catalysts were prepared by coprecipitating a
common aqueous solution of either nickel nitrate or cobalt nitrate
with magnesium nitrate and aluminium nitrate.
[0069] The precipitations were conducted at room temperature at pH
8.5-9.5 adjusted by titrating with aqueous ammonia solution.
Precipitates were filtered and washed with de-ionized water, dried
in air at 120.degree. C. overnight, calcined at 900.degree. C. in
air for 3 to10 h. and crushed to 20-70 mesh size.
Catalyst Characterization
[0070] Bulk metal compositions was measured by inductively coupled
plasma mass spectrometry (ICP-MS).
[0071] Surface metal composition was measured by X-ray
photoelectron spectroscopy (XPS).
[0072] Brunauer Emmett Teller (BET) surface area, pore measurements
(volume, diameter and size distribution) were measured using
N.sub.2 adsorption at -196t using a Micromeritics Accelerated
Surface Area and Porosimetry (ASAP) 2000 analyzer. About 0.2 g of
catalyst was used for each analysis. Before analysis, samples were
evacuated at 200.degree. C. and 500 .mu.mHg (66.6 Pa) to remove
moisture and other adsorbed gases from the catalyst surface. Sample
were then evacuated at 20 .mu.mHg (2.67 Pa) before N2 adsorption.
Pore measurements were derived from the adsorpotion branch of the
N2 isotherm by the Barret-Joyner-Halenda method.
[0073] Metal dispersion and metal surface area were determined by
CO-chemisorption using a Micromeritics ASAP 2000 analyzer. Samples
were first reduced with H.sub.2 at 850 to 900.degree. C. for 4 h.
Reduced samples were transferred to the sample holder of the
analyzer under protection of an inert gas (He). Three steps were
then carried out before CO-chemisorption: (1) evacuating the sample
for 30 min. at 120.degree. C.; (2) reducing the sample again at
450.degree. C. for 30 min. using H.sub.2; and (3) evacuating the
sample again for another 30 min. at 120.degree. C. CO-chemisorption
was performed at 35.degree. C.
[0074] X-ray powder diffraction (XRD) analysis was conducted using
a Rigaku/Rotaflex Cu rotating anode X-ray diffraction instrument
equipped with a generator voltage of 40 kV and tube current of 40
mA. Samples were powdered and mixed with methanol to form a mud
which was loaded on the coarse side of a glass plate and placed
under ambient drying conditions. Dried sample plates were loaded
into the analysis chamber and scanned at a rate of 4.degree./min.,
with 2.theta. varying from 2.theta. to 80.degree..
[0075] Reducibility was studied using temperature-programmed
reduction (TPR) in a ChemBET-3000 chemisorpotion analyzer. Samples
of about 0.1 g were heated from room temperature to 1000.degree. C.
using 3%11.sub.2/N, at a flow rate of 30 mL/min. and a ramp rate of
5.degree. C./min.
[0076] Carbon deposition was measured by a Perkin-Elmer Pyris
Diamond Thermo-Gravimetric and Differential Thermo-Gravimetric
(TG/DTG) analyzer.
[0077] Spent catalyst samples were heated in a platinum sample
holder from room temperature to 850 to1000.degree. C. at a ramp
rate of 5.degree. C./min.
[0078] A JEOL-JEM-1200EX transmission electron microscope (TEM)
operating at 100 kV was used to investigate morphology of carbon
deposition on spent catalysts and metal particle size distribution
of fresh catalysts.
Catalyst Testing
[0079] Catalyst were tested in a benchtop fixed-bed quartz
microreactor with an inner diameter of 6 mm. Reactant feed gas
consisting of an equimolar mixture of CH.sub.4 (99.2%, Praxair
Canada Inc.), CO.sub.2 (99.9%, Praxair Canada Inc.) and N.sub.2
(99.9%, Praxair Canada Inc.) was introduced into the reactor at
atmospheric pressure. Before testing, catalysts were activated
(reduced) by an H.sub.2 (99.9%, Praxair Canada Inc.) and N.sub.2
mixture with a molar ratio of 1:4 to 1:9 at to 800 to 900.degree.
C. for 4 h.
[0080] Gases produced by the carbon dioxide reforming of methane
were analyzed by an online Agilent 6890 GC gas chromatography
equipped with thermal conductivity detection (TCD) and a GS-GASPRO
capillary column (J&W Scientific Inc.) of 60 m in length and
0.32 mm in inner diameter. Helium (ultra-high purity, Praxair
Canada Inc.) was used as the carrier gas. The gas chromatography
oven temperature was initially held at -60.degree. C. for 3 min.
and then increased to 30.degree. C. at a ramp rate of 25.degree.
C./min.
[0081] The conversion rate of methane, selectivity of carbon
monoxide, and selectivity of hydrogen are calculated according to
the following equations:
C CH 4 = F CH 4 i - F N 2 i .times. X CH 4 X N 2 F CH 4 i .times.
100 % ##EQU00006## S CO = F N 2 i .times. X CO X N 2 ( F CH 4 i - F
N 2 i .times. X CH 4 X N 2 ) + ( F CO 2 i - F N 2 i .times. X CO 2
X N 2 ) .times. 100 % ##EQU00006.2## S H 2 = F N 2 i .times. X H 2
X N 2 2 .times. ( F CH 4 i - F N 2 i .times. X CH 4 X N 2 ) .times.
100 % ##EQU00006.3##
where, C.sub.CH4 is the overall conversion of methane, S.sub.co,
selectivity of carbon monoxide, S.sub.H2 selectivity of hydrogen,
F.sup.i.sub.CH4 initial volume flow rate of methane,
F.sup.i.sub.CO2, initial volume flow rate of carbon dioxide,
F.sup.i.sub.N2 initial volume flow rate of nitrogen, X.sub.CH4
molar fraction of methane in the product. X.sub.N2 molar fraction
of nitrogen in the product, X.sub.CO molar fraction of carbon
monoxide in the product, X.sub.H2 molar fraction of hydrogen in the
product.
EXAMPLE 2
28 h Test of Catalysts 1-4
[0082] Bimetallic catalysts containing Ni and one of Co, Mn, Fe and
Cu were prepared by coprecipitation and designated Catalysts 1-4
respectively. Bulk metal composition, BET surface area, pore volume
and average pore diameter are shown in Table 1. Catalysts 2-4
(Ni--Mn, Ni--Fe and Ni--Cu) had similar levels of BET surface area
at 14-18 m.sup.2/g, while Catalyst 1 (Ni--Co) had a significantly
higher BET surface area at 53.5 m.sup.2/g. Pore volume followed the
order Ni--Co>>Ni--Cu>Ni--Mn>Ni--Fe while the average
pore diameter followed the order
Ni--Co<Ni--Fe<Ni--Mn<Ni--Cu.
TABLE-US-00001 TABLE 1 Bulk metal composition, BET surface area,
pore volume and average pore diameter of Catalysts 1-4 Average Bulk
Metal Composition BET surface Pore pore (mol %) area volume
diameter No. Catalyst Ni Co Mn Fe Cu Al Mg (m.sup.2/g) (mL/g) (nm)
1 Ni--Co 6.1 9.3 -- -- -- 28.2 56.4 53.5 0.160 10.4 2 Ni--Mn 6.0 --
9.0 -- -- 27.8 57.1 17.2 0.073 16.9 3 Ni--Fe 6.5 -- -- 7.9 -- 29.0
56.6 17.8 0.056 12.0 4 Ni--Cu 6.8 -- -- -- 6.9 28.6 57.7 14.7 0.088
19.6
[0083] To screen different bimetallic combinations, activity and
stability of Catalysts 1-4 over a 28-h period was investigated.
Samples were prepared by diluting 0.05 g of catalyst with 0.450 g
quartz sand. Tests were run at 750.degree. C., 1 atm, F=5.5 L/h,
GHSV=110,000 mL/g.sub.cat-h and CH.sub.4/CO.sub.2/N.sub.2=1/1/1.
CH.sub.4 conversion rate as function of time-on-stream (TOS) is
shown in FIG. 1. Catalyst 1 (Ni--Co) had a high initial activity
(91.4% CH.sub.4 conversion rate) and remained at this level
throughout the 28-h testing period. Catalyst 2 (Ni--Mn) and
Catalyst 3 (Ni--Fe) also had high initial activities, with CH.sub.4
conversion rates of 85 and 53%, respectively; however, the
conversion dropped to 63 and 18%, respectively, at the end of the
28-h testing period. Catalyst 4 (Ni--Cu) showed low but relatively
stable activity, with a CH.sub.4 conversion rate of<16%. Thus,
initial activity followed the order
Ni--Co>Ni--Mn>Ni--Fe>Ni--Cu, which is consistent with the
order of BET surface area, pore volume and average pore diameter
(Table 1). The ratio of H.sub.2 to CO selectivity, shown in FIG. 2,
reflects no obvious difference in the relative amounts of H.sub.2
and CO produced when using the different bimetallic catalysts.
[0084] After the 28-h testing period, the amount of carbon
deposited on the spent catalysts was analyzed. Average rates of
carbon deposition are shown in FIG. 3. Catalyst 3 (Ni--Fe) had a
high carbon deposition rate of 0.02104 g.sub.c/g.sub.cat-h and
corresponding high activity decay of 67% (calculated on the basis
of initial and final CH.sub.4 conversion rates). Catalyst 2
(Ni--Mn) also had a relatively high carbon deposition rate of
0.00543 g.sub.c/g.sub.cat-h and corresponding activity decay of
26%. Catalyst 4 (Ni--Cu) had a lower carbon deposition rate of
0.00222 g.sub.c/g.sub.cat-h and an activity decay of 22%. Catalyst
1 (Ni--Co) had the lowest deposition rate, at 0.00204
g.sub.c/g.sub.cat-h and no activity decay over the 28-h testing
period. Activity decay followed the same order as carbon deposition
rate: Ni--Fe>>Ni--Mn>Ni--Cu>Ni--Co.
EXAMPLE 3
20, 200 and 2000 h Tests of Catalyst 1
[0085] To investigate stability and carbon deposition over a longer
term, Catalyst 1 (Ni--Co) was tested for 20, 200 and 2000 h,
respectively. Again, samples were prepared by diluting 0.05 g of
catalyst with 0.450 g quartz sand. Tests were run at 750.degree.
C., 1 atm, F=5.5 L/h, and CH.sub.4/CO.sub.2/N.sub.2=1/1/1. CH.sub.4
conversion rates and carbon deposition are shown in FIG. 4.
[0086] In the 20-h test, the CH.sub.4 conversion rate was
maintained at about 0.000415 mol/g.sub.cat-s, but the amount of
carbon deposited was 0.0408 g.sub.c/g.sub.cat. In the 200-h test,
the CH.sub.4 conversion rate was maintained at about 0.000416
mol/g.sub.cat-s for 100 h but dropped to 0.000409 mol/g.sub.cat-s
at 200 h. Over the 200-h test, 0.2374 g.sub.c/g.sub.cat was formed.
In the 2000-h test, the CH.sub.4 conversion rate again began to
drop at 100 h from the initial 0.000415 to 0.000398 mol/g.sub.cat-s
at about 300 h, fluctuated between 0.000395 and 0.000407
mol/g.sub.cat-s until 700 h, and staved stable at 0.000404
mol/g.sub.cat-s for the last 1300 h. The amount of carbon deposited
was 0.435.g.sub.c/g.sub.cat over the 2000-h period.
[0087] Carbon deposition on Catalyst I slowed with increasing TOS.
The average carbon deposition rate was 0.00204, 0.00119, and
0.000218 g.sub.c/g.sub.cat-h for the 20, 200 and 2000-h tests,
respectively. Further calculations relating to the 2000-h test
showed the average carbon deposition rate was 0.00204
g.sub.c/g.sub.cat-h for first 20 period of TOS, 0.00109
g.sub.c/g.sub.carh for the following 180 h period and 0.000109
g.sub.c/g.sub.cat-h for the last 1800 h. Overall, decline of
catalytic activity for Catalyst 1 was remarkably low at less than
3% over the 2000-h testing period.
[0088] The molar ratio of H.sub.2/CO as a function of TOS is shown
in FIG. 5. Reverse water-gas shift reaction (RWSR) is typically a
significant reaction and reduces the H.sub.2/CO ratio in dry
reforming of methane; however, the average H.sub.2/CO ratio over
the 2000-h testing period for Catalyst 1 was about 0.965,
indicating the occurrence of some RWSR but of less significance
than expected. The molar ratio of H.sub.2 to CO oscillated between
0.9 and 1.1 during the reaction period, suggesting a periodic cycle
of carbon deposition and elimination on the catalyst surface
leading to stable catalytic performance.
EXAMPLE 4
250 h Test of Catalysts 1 and 5
[0089] A Ni--Co bimetallic catalyst containing about half of the Ni
and Co loading of Catalyst 1 was prepared by coprecipitation. This
catalyst was designated Catalyst 5. The bulk metal composition of
Catalyst 5 (and Catalyst 1 for comparison) is shown in Table 2.
TABLE-US-00002 TABLE 2 Bulk metal composition and surface metal
composition of Catalysts 1 and 5. Bulk Metal Composition (mol %)
No. Catalyst Ni Co Al Mg 1 Ni--Co 6.1 9.3 28.2 56.4 5 Ni--Co 3.6
4.9 30.0 61.5
[0090] Activity and stability of Catalysts 1 and 5 over a 250-h
period was investigated. Samples were prepared by diluting 0.03 g
of catalyst with 0.470 g of quartz sand. Tests were run at
750.degree. C., 1 atm, F=5.5 L/h, and
CH.sub.4/CO.sub.2/N.sub.2=1/1/1. CH.sub.4 conversion rate as
function of TOS is shown in FIG. 6. The initial CH.sub.4 conversion
rate of Catalyst 5 was slightly lower than that of Catalyst 1.
However, the CH.sub.4 conversion rate of Catalyst 5 surpassed that
of Catalyst 1 at an early point and remained at a high level to the
end of the 250-h testing period.
[0091] Thermo-gravimetric (TG) and differential thermo-gravimetric
(DTG) analysis on the spent Catalysts 1 and 5 detected no carbon
deposition on Catalyst 5 but some carbon deposition on Catalyst 1
(FIG. 7(a) and FIG. 7(b)). TEM analysis (FIG. 8(a)) further
confirmed that no carbon formed on spent Catalyst 5. FIG. 7(b)
shows that there were two kinds of carbon formed on Catalyst 1; one
oxidizable in air at 500.degree. C. and another oxidizble in air at
600.degree. C. Corresponding FIG. 8(d) shows filamentous carbons of
nanotubes with two very different diameters formed on Catalyst 1.
The nanotubes of different diameters may be responsible for the two
DTG peaks.
[0092] FIG. 8(a) and FIG. 8(b) show that particle size is smaller
on Catalyst 5 compared to Catalyst 1. Metallic surface area and
metal dispersion of Catalysts 1 and 5 are shown in Table 3. For
Catalyst 1, metallic surface area was 4.1 m.sup.2/g and metal
dispersion was 7.5%. Catalyst 5 had a lower metallic surface area
of 2.9 m.sup.2/g but higher metal dispersion of 8.8%. The higher
metallic surface of Catalyst 1 likely accounted for the higher
initial activity (FIG. 6). However, its lower metal dispersion and
thus larger ensembles may have resulted in relatively rapid carbon
deposition and hence activity decay (FIG. 6 and FIG. 7). Carbon
resistance of Catalyst 5 may be due to its higher metal dispersion
and smaller metal ensembles.
TABLE-US-00003 TABLE 3 BET surface area, average pore diameter,
metallic surface area and metal dispersion of Catalysts 1, and 5-7
BET Average Metallic Metal surface area pore diameter surface area
dispersion No. Catalyst (m.sup.2/g) (nm) (m.sup.2/g) (%) 1 Ni--Co
54 10.4 4.1 7.5 5 Ni--Co 56 8.5 2.9 8.8 6 Ni 45 9.0 1.2 2.9 7 Co 24
10.5 1.5 2.1
EXAMPLE 5
28 h Test of Catalysts 5-7
[0093] Comparative investigations were carried out on Ni and Co
monometallic catalysts and a Ni--Co bimetallic catalyst,
specifically Catalyst 5. In the monometallic catalysts, Ni content
or Co content was at roughly the same level as the overall Ni and
Co content in Catalyst 5 so that the comparison of catalytic
performance could be made on the basis of similar total active
metal content. The Ni monometallic catalyst was designated Catalyst
6 and the Co monometallic catalyst was designated Catalyst 7.
[0094] Bulk metal composition and surface metal composition of
Catalysts 5-7 are shown in Table 4. Comparison of surface
composition and bulk composition indicated that
Ni.sub.surface/Ni.sub.bulk was 1.10 in monometallic Catalyst 6 and
1.19 in bimetallic Catalyst 5. CO.sub.surface/CO.sub.bulk was 0.80
and 1.27 in monometallic Catalyst 7 and bimetallic Catalyst 5.
respectively. Surface enrichment of Ni and Co (particularly Co) was
therefore evident in bimetallic Catalyst 5.
TABLE-US-00004 TABLE 4 Bulk metal composition and surface metal
composition of Catalysts 5-7 Bulk Metal Composition Surface Metal
Composition (mol %) (mol %) No. Catalyst Ni Co Al Mg Ni Co Al Mg 5
Ni--Co 3.6 4.9 30.0 61.5 4.3 6.1 29.3 60.2 6 Ni 6.8 -- 27.8 65.4
7.1 -- 28.9 64.0 7 Co -- 9.7 30.0 61.5 -- 7.8 31.2 61.0
[0095] TPR profiles of the reducibility of Catalysts 5-7 (unreduced
calcine precipitates) are shown in FIG. 9. The reduction peaks in
the range of 750 to 950.degree. C. and for monometallic Catalyst 6
may indicate reduction of Ni in a mixed spinel phase
Ni.sub.xMg.sub.1-xAl.sub.2O.sub.4. The reduction peaks in the range
of 700 to 950.degree. C. for monometallic Catalyst 7 may indicate
reduction of Co in a mixed spinel phase
Co.sub.xMg.sub.1-xAl.sub.2O.sub.4. The reduction peak in bimetallic
Catalyst 5 in the range of 700 to 940.degree. C. may have resulted
from the reduction of Ni and Co in a complex quaternary spinel-like
phase. In the high-temperature calcination process, Ni and Co may
form a continuous row of Ni.sub.xCo.sub.3-xO.sub.4 spinels, x>0.
The reduction peak maximum of bimetallic Catalyst 5 was at a
temperature (850.degree. C.) lower than those for Ni monometallic
Catalyst 6 (868.degree. C.) and Co monometallic Catalyst 7
(896.degree. C.). This may be attributable to the surface
enrichment of Ni and Co in Catalyst 5 because of the greater
accessibility of Ni or Co on the catalyst surface. Also, the
reduction of Catalyst 5 appeared as a single reduction peak, which
may indicate the formation of the Ni--Co alloy during
reduction.
[0096] XRD analyses of the phase structure of Catalysts 5-7
(unreduced calcined precipitates) are shown in FIG. 10. No apparent
difference was revealed between the XRD patterns of Catalysts 5-7.
Spinel-like phases and solid solution phases were observed in all
three samples. In particular, spinel-like phases with
characteristic diffraction peaks at 2.theta. of 30.7.degree.,
36.8.degree., 44.4.degree., 59.8.degree., and 65.2.degree., and
solid solution phase peaks at 2.theta. of 41.5.degree. and
61.2.degree., were observed in all samples. The spinel-like phases
may be Ni.sub.xMg.sub.1-xAl.sub.2O.sub.4,
Co.sub.xMg.sub.1-xAl.sub.2O.sub.4, or their composites, which are
indistinguishable in XRD due to their similar morphology. The solid
solutions may be Ni--Mg--O and Co--Mg--O. XRD analyses showed that
all the high-temperature calcined samples were
well-crystallized.
[0097] XPS analyses of the oxidation states of surface Ni and Co in
Catalysts 5-7 are shown in FIG. 11(a) and FIG. 11(b). Ni.sup.2+
(854 eV and 860 eV) was predominant in the Ni monometallic Catalyst
6 while Co.sup.3+ (777 eV) was predominant in the Co monometallic
Catalyst 7. Other oxidation states for both metals such as
Ni.sup.3+ and Co.sup.2+ were increased in bimetallic Catalyst 5.
Notably, part of the Ni shifted from a lower to a higher oxidation
state and part of the Co shifted from a higher to a lower oxidation
state. This indicates electron transfer between Ni and Co in
bimetallic Catalyst 5, which suggests these metals are protected
from oxidation during the reaction. It further confirms the
near-distance interaction between Ni and Co atoms, which may easily
form Ni--Co alloy on the bimetallic catalyst surface during
reduction.
[0098] Table 5 and FIG. 12 show the test results of monometallic
Catalysts 6 and 7 and bimetallic Catalyst 5 over a 28-h period.
Samples were prepared by diluting 0.025 g of catalyst with 0.475 g
quartz sand. Tests were run at 750.degree. C., 1 atm, F=5.5 L/h,
and CH.sub.4/CO.sub.2/N.sub.2=1/1/1. Catalyst activity in terms of
CH.sub.4 conversion rate (solid line) and CO.sub.2 conversion rate
(dotted line) as functions of TOS is shown in FIG. 12. Significant
difference did not appear in either activity or carbon deposition
of monometallic Catalysts 6 and 7. Bimetallic Catalyst 5, on the
other hand, had significantly higher activity and no detectable
carbon deposition.
TABLE-US-00005 TABLE 5 Activity and carbon deposition rate of
Catalysts 5-7 Initial Final conversion Average carbon conversion
(%) (%) deposition rate No. Catalyst CH.sub.4 CO.sub.2 CH.sub.4
CO.sub.2 (g.sub.c/g.sub.cat-h) 5 Ni--Co 83.8 87.0 83.9 87.1 0 6 Ni
62.9 73.4 58.0 69.5 0.003186 7 Co 67.6 77.0 58.3 71.2 0.003973
EXAMPLE 6
2000 h Test of Catalyst 8 and 1 h Test of Catalysts 9-14
[0099] Ni--Co, Ni--Mn, Ni--Cu and Co--Mn bimetallic catalysts were
prepared by coprecipitation and designated Catalysts 8-14
respectively. Bulk metal compositions of the catalysts are shown in
Table 6.
[0100] Activity of Catalyst 8 (same as Catalyst 1 in terms of
composition) was tested over a 2000-h period, and Catalysts 9-14
were tested over a 1-h period. Catalyst 12 was the same as Catalyst
2 in terms of composition. Samples were prepared by diluting
catalyst with quartz sand. Tests were run at 750.degree. C., 1 atm,
F=5.5 L/h, and CH.sub.4/CO.sub.2/N.sub.2=1/1/1. Initial CH.sub.4
conversion, initial H.sub.2 selectivity and initial CO selectivity,
all determined at t=0.5 h, are shown in Table 6.
TABLE-US-00006 TABLE 6 Bulk metal composition, conversion of
CH.sub.4, H.sub.2 selectivity and CO selectivity of Catalysts 8-14
Bulk Metal Composition Initial conversion Initial H.sub.2 Initial
CO (mol %) of CH.sub.4 selectivity selectivity No. Catalyst Ni Co
Mn Cu Al Mg (%) (%) (%) 8 Ni--Co 6 9 -- -- 28 57 91.5 97.1 99.8 9
Ni--Co 4 5 -- -- 30 61 91.9 96.6 99.7 10 Ni--Co 25 9 -- -- 26 40
92.9 96.0 98.0 11 Ni--Co 6 27 -- -- 26 31 90.1 95.0 95.0 12 Ni--Mn
6 -- 9 -- 28 57 85.0 92.8 97.5 13 Ni--Cu 6 -- -- 6 30 58 53.9 82.5
92.5 14 Co--Mn 9 -- 9 -- 26 56 35.5 81.1 97.2
[0101] FIG. 13 shows the activity of Catalyst 8 in terms of the
CH.sub.4 conversion and CO.sub.2 conversion as a function of GHSV.
FIG. 14 shows the activity of Catalyst 8 in terms of the CH.sub.4
conversion and CO.sub.2 conversion as a function of reaction
temperature. FIGS. 15 and 16 show the high stability of Catalyst 8
in terms of the CH.sub.4 conversion and CO.sub.2 conversion,
respectively, as a function of TOS. FIGS. 17 and 18 show the CO
selectivity and H.sub.2 selectivity of Catalyst 8 as functions of
TOS. As shown in Table 6, the selectivity of these target products
is 95% or greater for all four Ni--Co containing catalysts
(Catalysts 8-11).
Example 7
250 h Test of Catalysts 15-18
[0102] Ni--Co bimetallic catalysts with varying Ni and Co content
was prepared by coprecipitation. The catalysts were designated
Catalysts 15-18. Bulk metal compositions, BET surface area and
metal dispersion of Catalysts 15-18 are shown in Table 7. Surface
area was inversely related to Ni and Co content (Table 7 and FIG.
19). The decrease of BET surface area with the decrease of Al--Mg
content provides evidence of the stabilizing role of Al and Mg in
the catalysts. Metal dispersion was also inversely related to Ni
and Co content.
TABLE-US-00007 TABLE 7 Bulk metal composition and BET surface area
of Catalysts 15-18 Bulk Metal Composition Metal (mol %) BET surface
dispersion No. Catalyst Ni Co Al Mg area (m.sup.2/g) (%) 15 Ni--Co
2 3 32 63 70 11.6 16 Ni--Co 4 5 30 61 56 10.9 17 Ni--Co 6 9 28 57
45 9.7 18 Ni--Co 18 16 26 40 27 9.4
[0103] XRD analyses of the phase structure of unreduced Catalysts
15-18 are shown in FIG. 20. As in Example 5, spinel-like phases
with characteristic diffraction peaks at 2.theta. of 30.7.degree.,
36.8.degree., 44.4.degree., 59.8.degree., and 65.2.degree. were
observed in all samples. As Ni and Co content increased, increases
in peak intensity were observed for the peaks of 20=41.5.degree.
and 61.2.degree., suggesting an increase in the amount of Ni--Mg--O
solid solution and Co--Mg--O solid solution. Again, all the samples
under calcination at 900.degree. C. were well-crystallized. It can
also be seen from the XRD patterns that the bulk phases of the
catalysts were not altered significantly with varying Ni and Co
content.
[0104] TPR profiles indicating the reducibility of Catalysts 15-18
(unreduced calcine precipitates) are shown in FIG. 21. FIG. 21
shows a single broad reduction peak for all samples. As discussed
in Example 5, after high temperature calcination, Ni and Co may
exist in a complex structure leading to single-stage reduction with
a broad peak. Such a structure may involve alloying of Ni and Co.
Owing to the relatively low Ni--Co content, no reduction of
separate Ni oxide or Co oxide was observed. Even for the highest
Ni--Co content sample, Catalyst 18, no reduction of metal oxide was
observed. This is consistent with the XRD analyses which did not
show Ni and Co oxide phases. Catalyst 18 exhibited a lower
temperature, broader reduction peak (650-900.degree. C.) compared
to Catalyst 15-18 having lower Co and Ni content. The shift of peak
maximum to higher temperatures for the lower Ni--Co content samples
may be ascribed to the increase of the metal-support interaction
resulting from better dispersion of Ni and Co in the solid
structures.
[0105] Pore size distributions of Catalysts 15-18 are shown in FIG.
22. Pore volume peaks with pores having a diameter of about 30
.ANG.. As Ni--Co content increases, the small pores, typically
having a diameter of less than 100 .ANG., drops significantly from
about 0.045 cm.sup.3/g.sub.cat of Catalyst 15 to about 0.0075
cm.sup.3/g.sub.cat of Catalyst 18.
[0106] The metal particle morphology and size distribution were
investigated using TEM and the results are shown in FIG. 23(a)-(d).
It is evident that Catalyst 18 has the broadest distribution of
metal particles with about 20% particles larger than 10 nm (FIG.
23(a)). As the Ni and Co content decreased, the amount of the large
metal particles decreased significantly. All metal particles were
smaller than 10 nm for Catalysts 15 and 16 (FIG. 23(d) and (c)).
The proportion of smaller metal particles was increased with the
decrease in the Ni--Co content. From Catalyst 18 to Catalyst 15,
the proportion portion of metal particles between 1 and 5 nm
increased from 52% to 76%. Also, in the cases of Catalysts 15 and
16, the boundaries between metals and support became indistinct in
comparison to the boundaries observed with higher Ni--Co content
catalysts.
[0107] Activity and stability of Catalysts 15-18 was investigated
over a 250-h period. Samples were prepared by diluting 0.03 g of
catalyst with 0.470 g quartz sand. Tests were run at 750.degree.
C., 1 atm, GHSV=180,000 mL/g.sub.cat-h and
CH.sub.4/CO.sub.2/N.sub.2=1/1/1. Catalyst activity in terms of
CH.sub.4 conversion rate as function of TOS is shown in FIG. 24.
Both activity and stability were inversely correlated to Co and Ni
content.
[0108] No deactivation was observed for Catalyst 15 during the
250-h testing period. Catalyst 15 maintained a stable CH.sub.4
conversion rate at about 0.680 mmol/g.sub.cat-s. For Catalyst 16,
the activity increased gradually with time in the first 30 h and
then remained at a stable CH.sub.4 conversion rate of about 0.621
mmol/g.sub.cat-s. Increasing conversion rate during the initial
period was ascribed to the formation of new active sites when the
catalyst was exposed to the reaction mixture. Deactivation was
observed for Catalysts 17 and 18. During the 250 h TOS, the
conversion rates of CH.sub.4 for Catalysts 17 and 18 dropped from
0.629 mmol/g.sub.cat-s to 0.481 mmol/g.sub.cat-s and from 0.516
mmol/g.sub.cat-s to 0.376 mmol/g.sub.cat-s, respectively.
[0109] TG and DTG analysis on the spent catalysts indicated that
Catalysts 15 and 16 had no detectable carbon deposition while
Catalysts 17 and 18 had carbon deposition of up to 0.30 and 0.46
g.sub.c/g.sub.cat, respectively (Table 8, FIGS. 25(a) and (b)). The
very slight weight loss in Catalysts 15 and 16 occurring at around
100.degree. C. (FIG. 25(a)) probably resulted from the evaporation
of moisture. Carbon deposits on Catalysts 17 and 18 were oxidized
at around 420-650.degree. C. (FIGS. 25(a) and (b)). TEM analysis
revealed no detectable carbon deposits on spent Catalysts 15 and 16
(FIGS. 26(c) and (d)), but clear filamentous carbon was found on
spent Catalysts 17 and 18 (FIGS. 26(a) and (b)).
TABLE-US-00008 TABLE 8 Carbon deposition on Catalysts 15-18 No.
Catalyst Carbon deposition at 250 h (g.sub.c/g.sub.cat) 15 Ni--Co 0
16 Ni--Co 0 17 Ni--Co 0.300 18 Ni--Co 0.446
[0110] While a number of exemplary aspects and embodiments have
been discussed above, those of skill in the art will recognize
certain modifications, permutations, additions and sub-combinations
thereof. It is therefore intended that the following appended
claims and claims hereafter introduced are interpreted to include
all such modifications, permutations, additions and
sub-combinations as are within the spirit and scope of the
invention.
* * * * *