U.S. Environmental Protection Agency Industrial Environmental Research EPA~600/7~76~026
Office of Research and Development Laboratory
Research Triangle Park, North Carolina 27711 October 1976
PARAMETRIC STUDIES OF
CATALYSTS FOR NOX CONTROL
FROM STATIONARY POWER PLANTS
Interagency
Energy-Environment
Research and Development
Program Report
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Research reports of the Office of Research a-nd Development, U.S.
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This report has been assigned to the INTERAGENCY ENERGY-ENVIRONMENT
RESEARCH AND DEVELOPMENT series. Reports in this series result from
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EPA-600/7-76-02 6
October 1976
PARAMETRIC STUDIES OF CATALYSTS
FOR NO CONTROL
X
FROM STATIONARY POWER PLANTS
by
KenNobe, George L. Bauerle, and S. C. Wu
University of California, Los Angeles
405 Hilgard Avenue
Los Angeles, California 90024
Grant No. R803653-01
Program Element No. EHE624
EPA Project Officer: Richard D. Stern
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, NC 27711
Prepared for
U.S. ENVmONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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SUMMARY
Chemical specifications of laboratory-prepared vanadium oxide-alumina and
iron oxide-chromium oxide-alumina catalysts have been optimized for maximum ac-
tivity for reduction of NO with NH3 in simulated flue gas. Fifteen percent "V^Og load-
ing and 10$ Fe-Cr oxides with an Fe/Cr ratio of 9/1 were the optimum formulations.
A commercial 10$ V^Og-AloO- catalyst was found to be almost as active as the
15^5 laboratory-prepared catalyst; no commercial Fe or Fe-Cr catalysts were found
comparable to the prepared 9/1 Fe-Cr catalyst.
Parametric tests showed that both catalysts were selective in the presence of O0
with strong enhancement in NO conversion rates due to the presence of O9 under typi-
cal operating conditions. Neither CO nor IO affect the NO reduction in the concen-
tration ranges applicable to power plant exhaust. Both catalysts were most active
between 400 and 425°C and required excess NHg (NHL/NO ^ 0.67) for maximum activ-
ity.
Rate expressions describing the intrinsic reduction kinetics of NO with NH_ in
simulated flue gas over the V^O.- and Fe-Cr catalysts are:
o rte m3 -9650/RT 0.30 0.22 0.05, . „_, . . %
rate = 2.05 x 10° e p p p (moles NO/gm. cat. -hr).
1056 Fe-Cr (9/l)-Al0O_:
& u
oo. ,«q -10,860 0.45 0.10 0.15 . . ^, ^ u %
rate = 3.25 xlOd e p p p (moles NO/gm. cat.-hr).
3 2
Long-term durability tests in the presence of SO for periods of 648 and 1052
hours for V^O and Fe-Cr catalysts, respectively, have indicated no degradation in
catalyst performance. In fact, improvement in activity and broadening of the conver-
sion-temperature maxima were observed.
Typical conversion levels for V_O and Fe-Cr catalysts operating at 400°C in
simulated flue gas containing 1000 ppm NO, 1000 ppm NH_ and SO were about 90 and
80$, respectively, at 20,000 hr"1 space velocity.
iii
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With the Fe-Cr catalyst a sharp increase in the activity for reduction of low
concentrations of NOX (~ 500 ppm) was observed during the SO durability tests.
With 500 ppm NO and stoichiometric NHg levels, conversions close to 90$at 20,000
hr~ space velocity were typical with SOX levels of about 350 ppm. With excess NH3,
NOX conversions exceeding 90$ were observed.
Two new catalysts were prepared in an attempt to reduce the cost of the VgOg cat-
alyst by dilution with other metal oxides. A 15$Fe-V (1/1) oxade-Al2O catalyst was
prepared and preliminary tests indicate this catalyst to be more active than the
V2O , the 10$ Fe-Cr (9/1) and the 10$Fe2Og catalysts. A second new catalyst, 10$
Fe-Cr- V (18/1/1) oxide-AUO , was prepared during the last stages of this project and
tests showed it to be the most active catalyst developed in the program. A test of
about 180 hours duration of the latter catalyst in simulated flue gas containing SO at
400°C and 10, 000 hr""1 showed that 99$ removal of NO was achieved and activity clid
not deteriorate with exposure time. These preliminary results of the two catalysts
suggest that synergistfc catalytic activity has been achieved with mixtures of VgO and
other metal oxides. Parametric and long term durability tests of these two new cat-
alysts are recommended.
Although there was no deterioration of either the V2Og or the Fe-Cr catalyst in
simulated flue gas containing up to about 200 ppm SO3, which was homogeneously
formed from the injected SO2, recent reports suggest that SO3 may be the primary
cause of the rapid deterioration of certain catalysts. The SO levels or the ratio
of SO3 to SO2 may have been too low to demonstrate this effect on the UCLA catalysts.
Recent reports suggest interaction of SO» with (a) the active metal oxide and/or with
(b) the AUO carrier, respectively. Investigation of these possible interactions is of
immediate importance. In particular, the influence of the SO3/SO2 ratio at various
levels of total sulfur oxides should be studied. An SO3 reaction with A12O3 may re-
quire the development of SOQ-resistant carriers.
o
iv
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CONTENTS
SUMMARY iii
FIGURES Vii
TABLES x
1.1 Introduction 1
1.2 Conclusions 2
1.3 Recommendations 4
2 Statement of Work 5
3 Background and Description of the Problem 6
4 Experimental 12
4.1 Catalyst preparation 12
4.2 Bench-scale apparatus 14
4.3 Analytical equipment and procedure 14
4.4 Standard flue gas composition and flow rate 16
4.5 Test procedure 17
4.6 Data reduction 17
4.7 Literature acquisition 19
5 Results 20
5.1 Optimization of composition and development of chemical
specifications of vanadia and iron-chromium catalysts 20
5.1.1 Vanadia catalysts 20
5.1.2 Iron-chromium catalysts 29
5.1.3 Preparation of optimum catalyst formulations 44
5.1.4 Summary of catalyst physical properties 46
5.2 Parametric investigation of vanadia and iron-chromium
catalysts in the presence of SOX • 46
5.2.1 Parametric studies 47
5.2.1.1 V2Os catalyst 48
5.2.1.2 Fe-Cr catalyst 71
5.2.2 Durability tests in the presence of SOX 90
5.2.2.1 V2O5 catalyst 90
5.2.2.2 Fe-Cr catalyst 99
5.2.3 Recommended operating conditions 106
5.3 Investigation of new and promising catalysts ..106
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REFERENCES 110
APPENDICES
A 113
Table A-l 114
Table A-2 182
vi
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FIGURES
Number Page
1 Reduction of NO with NH« on 10$ V2°5'"A12O3 (Harshaw
V-0610T1/8), 14flCO0, 3% H0O, 3JO,, present in N0 carrier 9
& & & u
2. Reduction of NO with NH on 10$ Fe-Cr (5/l)-Al2O3 at 400°C.
14$ CO2, &<; H2O, 3$ O2 in N2 carrier 10
3. Reduction of NO with NHg on 0.5$ Pt-Al2Og (Engelhard)
at 250°C. 14£ CO,, 5$ HgO. 3$ O2 present in N2 carrier 11
4. Catalyst test apparatus 15
5. Reduction of NO (1000 ppm) with NHg (700 ppm) on V2O5-Al2Og
catalysts in simulated flue gas 22
6. Reduction of NO (1000 ppm) with NHg (1100 ppm) on V^g-ALO
catalysts in simulated flue gas 23
7. Influence of V2O concentration on catalyst activity in simulated
flue gas 24
8. Effect of ALOg support on NO conversion in simulated flue gas,
with 15$ V0O_ catalysts. 1000 ppm NO, 1100 ppm NH0 25
ft O O
9. Reduction of NO (1100 ppm) with NH_ (approx. 1100 ppm) on
prepared and commercial V0O_ catalysts in simulated flue gas 27
& 5
10. Removal of 1000 ppm NO with NH in simulated flue gas on 15$
V9O catalysts , 30
u 5
11. Comparison of 15$ V_O -ALO and commercial V2O -K.O-:SfO2
catalysts. 1000 ppm NO and 1100 ppm NH3 in simulated tlue gas 31
12. Effect of Fe-Cr ratio and percent active material on NO con-
version at 300°C and 400°C. 1000 ppm NO, 1100 ppm NH_ 36
3
vii
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Figures (Cont, )
Number Page
13 Effect of Fe-Cr ratio and percent active material on NO
conversion at 300° C and 400°C. 1000 ppm NO, 700-850
ppm NH., [[[ 37
O
14. Conversion of NO with Fe and Fe-Cr catalysts in simulated flue
gas ................ .... ..... ............ ....................... 39
15. Conversion of NO as a function of Fe0O_ and Cr0O0 eoncentra-
„ £ O & 3 *n
tions at 400°C .................................................. 42
16. Conversion of NO and NH3 on 10$ Fe-Cr catalysts in simulated
flue gas. 1000 ppm NO, 1100 ppm NH., ....................... • ---- 43
*J
17. Removal of NO with NH3 on V O5 at low NO concentrations in
simulated flue gas. 280 ppm NO .................................. 56
18. Removal of NO with NHg on VgOg at high NO concentrations in
simulated flue gas ............................................... 57
19. Effect of O_ concentration on NO reduction on VgO5 in simulated
flue gas at high NO concentrations ................................. 58
20. Effect of O- concentration on NO reduction on Y2O5 in simulated
flue gas at intermediate NO concent rations ...... . ....... ..., ....... 59
21. Effect of Q£ concentration on NO reduction in simulated flue gas
on V^Og catalyst at low NO concentrations ».. 60
22. Effect of water vapor on NO reduction in simulated flue gas
on V<>Oe .-.» 63
* o
23. Effect of CO2 on NO conversion in simulated flue gas on VgO-
at400°C 65
24. Effect of space velocity on conversion of NO in simulated flue gas
on V205 ;... 66
25. Conversion of NO in simulated flue gas on Fe-Cr catalyst 78
26. Conversion of NO on Fe-Cr catalyst M simulated flue gas
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Figures (Cont.)
Number^ page
27. Effect of water vapor concentration on conversion of NO In
simulated flue gas on Fe-Cr catalyst 82
28. Effect of CO, concentration on conversion of NO in simulated
flue gas on Fe-Cr catalyst (1000 ppm. NO, NH,, as specified) 82
o
29. Effect of O2 on conversion of NO with Fe-Cr catalyst in simulated
flue gas 87
30. Effect of space velocity on conversion of NO in simulated flue gas
on Fe-Cr, 1000 ppm NO * , 89
31. Conversion of NO on V^Og catalyst during SOX exposure test in
simulated flue gas (1000 ppm NO) at 400°C 100
32. Conversion of NO on Fe-Cr catalyst during SOX exposure test
period in simulated flue gas (1000 ppm NO)ai 4QO°C 104
33. Comparison of several active catalysts for NO reduction with NH3
in simulated flue gas 109
ix
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TABLES
Number Page
1. list of Catalysts Tested .......................................... 13
2. Crush Strength of Catalysts and Carriers .......................... 28
3 . Iron-Chromium Test Matrix ...................................... 32
4. Results of Activity Tests with Fe-Cr Catalysts ..................... 33
5. Conversion of NO at 400°C on Fe and Fe-Cr Catalysts ............... 40
6. Surface Area of Fe-Cr Catalysts .................................. 45
7. Effect of SO2 on Conversion of NO over Fe-Cr (9/1) Catalyst ......... 45
8. Catalyst Physical Properties ..................................... 46
9. Parametric Studies Test Data - V^O- Catalyst ..................... 49
10. Effect of Water Vapor Concentration on Reduction of NO on V«O_
in Simulated Flue Gas ........................................... 62
11. Effect of CO Concentration on Conversion of NO on V2O ............ 64
& ** o
12a. Experimental and Calculated Conversion of NO on V2°s"Al2°3
Based on Intrinsic Rate Expression (20, 000 hr~l, temp.£ 400OC ). ... 68
12b. Experimental and Calculated Conversion of NO on VgO
Based on Intrinsic Rate Expression (10, 000 hr'1, temp. £ 400<>c) .... 70
13. Experimental and Calculated Conversion of NO on
Based on Global Rate Expression (temp. > 400°C) ................... 72
14. Parametric Studies Test Data - Fe-Cr Catalyst in Simulated
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Tables (Cont.)
Number Page
15. Parametric Studies Test Data - Fe-Cr Catalyst in Simulated
Flue Gas - Effect of Water Vapor and Carbon Dioxide 81
16. Effect of Oxygen Concentration on NO Reduction with NHL in
Simulated Flue Gas - Fe-Cr Catalyst 83
17a. Experimental and Calculated Conversion of NO on Fe-Cr (9/1)
Based on Intrinsic Rate Expression (20,000 hi-1) 91
17b. Experimental and Calculated Conversion of NO on Fe-Cr (9/1)
Based on Intrinsic Rate Expression (10,000 hr-1) 94
18. Durability Test Results - VgCv Catalyst in the Presence of SOX
at 400°C 95
19.. Durability Test Results - ^2°5 Catalyst in the Presence of SOX
at Temperatures below 400°C 98
20. Durability Test Results - Fe-Cr Catalyst in the Presence of SO
at 400°C * 101
21. Conversion of Low Concentrations of NO in Presence of SO at 400°C
over Fe-Cr Catalyst 105
22. Durability Test Results - 10$ Fe-Cr-V (18/1/1) Catalyst in the
Presence of SO,, at 400°C 109
xi
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1. INTRODUCTION
There has been considerable work on the physiological effects of the oxides of
nitrogen, their role in the formation of smog and their production in fossil fuel-
burning power generation sources. For many years research has been directed
toward either preventing NO formation or after formation, its abatement.
Ji
Combustion modification methods have little effect on preventing the formation
of NOX from fuels containing nitrogenous compounds (1-1). The steadily increasing
use of fuels containing such compounds (particularly coal) emphasizes the need for
the development of post-combustion abatement methods.
A recent investigation performed by UCLA for TRW Systems Group under En-
vironmental Protection Agency Contract No. 68-02-0648 (1-2), indicated that cat-
alysis provides viable methods for controlling NOX emissions. The most promising
catalytic method is the selective reduction of NOX in the presence of oxygen using
ammonia as reductant. In brief, only ammonia has been identified as capable of
reducing NO selectively in the presence of O«; several catalysts have been develop-
ed that promote such selective reduction. During the TRW/UCLA project two catal-
ysts were shown to be particularly promising. These catalysts were vanadium
oxide (vanadia) - alumina and iron oxide - chromium oxide - alumina. In prelimin-
ary performance studies both catalysts were shown to be effective at flow rates and
temperatures consistent with stationary power plant adaptability. Both were shown
to be resistant to sulfur dioxide under short-term exposure.
In June 1975, UCLA initiated the present project 'EPA Grant R 803653-01-0) to
develop further these promising catalysts. The objectives of the project were to
optimize the compositions of the vanadia and iron-chromium catalysts for selective
reduction of NO with NHg, develop rate expressions for design use and perform long-
term durability studies of the optimum catalyst compositions in flue gas containing
sulfur oxides.
Subsequent sections of this report summarize the previous effort and the experi-
mental approaches and results of foe current project. Immediately following is a
description of the effort as delineated into separate study tasks.
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CONCLUSIONS
The important conclusions based on the results of the current study are as
follows:
1. Optimum loading of "V^Og-ALOg catalysts, prepared by impregnation of
A12O3 with aqueous ammonium vanadate-oxalic acid for reduction of NO
with NH3, is 13$ .
2. Optimum loading of Fe-Cr-AUOg catalysts, prepared by impregnation of
aqueous nitrate mixtures on the carrier, is 10$. Optimum Fe/Cr ratio is
9/1.
3. Conversion of NO on both catalysts is not affected by the presence of H2O,
CO2 or SOx-
4. The presence of Oo in the reactant gas mixture causes pronounced accelera-
tion of the rate of NO reduction reaction on both catalysts.
5. Typical conversion of NO in simulated flue gas containing 1000 ppm NO and
1000 ppm NH3 and SOX was about 90# and 80<£ for VgOg and Fe-Cr catalysts,
respectively, at 400°C and 20,000 hr~l space velocity. Lower space velo-
cities enable attainment of higher NO conversion levels.
6. The rate of reduction of NO with NH3 on 15#V2O5-A12O3 catalyst in simula-
ted flue gas up to 400°C can be described by the intrinsic rate expression,
f o nK m3 -9650/RT 0.30 0.22 0.05 , , .__, . . .
rate =2.05 x 10 e p p p (moles NO/gm cat.-hr)
NO Nflo On
7. The intrinsic rate expression for reduction of NO with NHg on 10# Fe-Cr
(9/l)-Al2Og in simulated flue gas is:
rate. 3.25 x 103 a'10*860 p^V'10 p^15 (moles NO/gm cat.-hr)
8. The V2O and Fe-Cr catalysts developed in this project suffered no degrada-
tion over extended periods of operation in simu&ted flue gas containing SOX.
In fact, some improvement in activity, particularly at low concentrations of
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NO, was observed after extended SOX exposure.
9. Both catalysts, which have been studied extensively in this project, require
excess NH3 for optimum operation. Residual NH3 exists in the NOX con-
verter effluent. This residual NH3 could present a secondary pollutant
problem. No other secondary pollutants were found in the converter exhaust
gases.
10. Although 15$ V2O5 loading was optimum for VgO -ALjCL catalysts, more
active catalysts can be prepared by substituting another active metal oxide
for part of the vanadia. For instance, a 15$ Fe-V (1/1) oxide on ALO was
more active than either 15$ VgO or 10$ Fe2O3. Also, a 10$ Fe-Cr-v
(18/1/1) oxide-AUO was more active than either 15$ V2O5 or 10<
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RECOMMENDATIONS
The following recommendations are based on the results and conclusions of the
current project:
1. The demonstrated activity and durability of 15#V2O5-Al2Og and 10#Fe-Cr
oxides (9/1) - Al-O at the bench scale c
at larger (either semi-pilot or pilot) sea
of combustion of sulfur-containing fuels.
oxides (9/1) - A1?O at the bench scale of operation should be corroborated
at larger (either semi-pilot or pilot) scale of operation using actual products
2. Recommended operating temperature for 15% V2O is 400°C and for 10$
Fe-Cr (9/1) is 425°C. A space velocity of 10,000 hr~l is recommended for
initial performance evaluation at the larger scale.
3. Ammonia level should be maintained at a molar NH3/NO ratio of 1 or higher
for best NO., removal.
2i
4. Further investigation should be made of the variation in activity of V2Og as a
function of concentration of other active metal oxides and the imparted, ap-
parent synergism. Parametric studies of these improved catalysts, parti-
cularly in the presence of varying 802/803 mixtures is recommended.
5. Further studies of catalyst deterioration in the presence of larger concentra-
tions of SOg than present in the current durability studies is of immediate
importance. The SOg-ALjOg interaction should be examined carefully and
the products or phase changes identified. Methods to improve the resistance
of A12O (additives, pretreatment, etc.) should be sought. Alternative car-
riers (e.g., zirconia) should be investigated to determine SO,, resistance.
6. Studies should be made of methods to abate, recover and recycle, or utilize
in other processes, the NHg remaining after NOX abatement. The most at-
tractive use of the NHg may be for SO abatement processes involving homo-
geneous reaction to form ammonium salts of sulfur oxides.
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2. STATEMENT OF WORK
The experimental program performed in fulfillment of the objectives of Grant
No. R 803653-01-0 "Parametric Studies of Catalysts for NOX Control from Station-
ary Power Plants" was organized into the following tasks.
Taskl. Optimization of composition and development of chemical specifications for
vanadia and iron-chromium catalysts^
Chemical composition and methods of preparation of vanadia and iron-chromium
catalysts were correlated with catalytic activity for the selective reduction of NO with
NH~ in the presence of SOX in simulated stack gas. Optimal concentrations of "V^Oc
on alumina and/or other carrier materials were determined. With the iron-chromi-
um catalysts, the optimum ratio of Fe to Cr as well as the most active catalyst-
carrier concentration ratio were determined. Commercial vanadia-based catalysts,
currently used for oxidation of SO2 to SO3 , in nitric acid production and in catalytic
stack gas desulfurization processes, were investigated for activity for NO reduction
with
Task 2. Parametric investigation of vanadia and iron-chromiun^catalysts in the
presence of SOg.
Process variables such as temperature and residence time were varied over
broad ranges with the optimized vanadia and iron-chromium catalyst formulations.
The effect of SO2 concentration on the temperature-activity characteristics was de-
termined. Tests of long duration were made to determine if slow, cumulative poi-
soning occurs. Working rate expressions were developed for scale-up use. Analy-
ses of the effluent gas stream determined not only the concentrations of the major
components of interest (e.g., NO, NO,, NH , SO-, SOg) but also those of other com
ponents which may represent deleterious secondary effects (e.g. , sulfates, H2S,
carbonyls).
Task 3. Investigation of new and promising catalysts.
i
Promising catalysts were tested when the literature or informal disclosures
showed evidence of high activity. Following preliminary assessment of these catal-
ysts based on available data, recommendations for further investigation were made
to the EPA and pursued, if merited, upon the directive of the project officer.
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3. BACKGROUND AND DESCRIPTION OF THE PROBLEM
Several approaches considered for abatement of NO in the exhaust of fossil fuel-
burning power plants involve catalysis. These approaches may be summarized as:
1. Catalytic Decomposition of NO
Nitric oxide is formed in combustion processes by direct combination of
nitrogen and oxygen at high temperature. The equilibrium concentration of NO
is determined by the flame temperature which depends on the air to fuel ratio.
Thermodynamically, nitric oxide should revert to nitrogen and oxygen as the
combustion gases cool. However, the kinetics of the homogeneous NO decompo-
sition reaction become infinitesimally slow as the gases are cooled and the NO
concentration in the flue gas is essentially that in the combustion zone. Cat-
alysts should exist that will accelerate the approach to equilibrium (lower com-
positions of NO) as the gases are cooled, at least until temperatures become so
low that kinetic restraints exist for the heterogeneous process. Some success
was achieved in Identification of such a catalyst for the direct decomposition of
NO in the previous program. The catalyst was platinum-alumina which, under
typical flue gas conditions, resulted in 60$ decomposition of NO. The moderate
conversion attained and the high cost of platinum indicate that continued develop-
ment of this process is only marginally attractive at the present time.
2. Nonselective Reduction of NO
It has been known for many years (e.g. tail-gas treatment operations in the
nitric acid industry) that the reduction of NO can be catalytically accomplished
by addition of sufficient reducing agent to reduce both NO and oxygen. Typical
reducing agents (R2» CH4» co» gasoline, etc.) will effectively reduce NO in the
absence of oxygen or, in the presence of oxygen if there is an excess of reducing
agent to reduce both the 03 and the NO. For conditions of substantial excess O2,
(typically, under optimum fuel-utilization conditions in a power plant), the heat
release in the preliminary O2-depletion reaction is such that interceding and
multistage reactors are necessary.
Nonselective reduction of NO presents two alternative requirements. Either
the combustion process must be conducted under uneconomical O-deficient
* Reference will be made in this report to the joint TRW/UCLA effort recently con-
cluded ( 1 -2Jf as the previous program.
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conditions (which also leads to lower formation of NO) or the reducing agent must
be provided from external sources. For this latter alternative, sufficient reduc-
tant must be added to consume also the CL as described above.
There are many catalysts which will simultaneously reduce both NO and O2, but
none has been identified that will promote the selective reduction of NO using
standard fuels, over practical operating ranges, in the presence of excess Og.
lii summary, non-selective reduction of NO is technically feasible for power plant
NO abatement but the economic shortcomings of the alternative of fuel-rich com-
bustion conditions or complicated reactor/intercooling systems with large excess
reductant requirements make such systems relatively unattractive.
3. Catalytic Oxidation of NO
Although thermodynamic analysis indicate that NO should readily decompose
to N« and Og at lower temperatures, the reaction is kinetically slow. The for-
mation of NO« from NO and O2 is also favored as the combustion gases cool.
However, the low residence times inherent in power plant exhaust systems limit
the degree of oxidation.
If the oxidation process can be accelerated by catalysis, removal of the more
active NO2 in secondary scrubbing processes is feasible. However, no hetero-
geneous catalyst has been identified as yet that will promote the oxidation process
to a significant extent under typical stack-gas conditions.
4. Selective Reduction of NO
Only one reducing agent, NH«, has been found that will react selectively with
NO in the presence of large amounts of O2 over wide range of reductant/NO mix-
ture ratios. During the previous project it was found that platinum, vanadia and
iron oxide-chromium oxide mixtures on alumina support material were effective
catalysts for the selective reduction of NO with NHq. The latter two catalysts
were disclosed in the patent literature by Nonnenmacher and Kartte (3-1)
and by Schmidt and Schulze (3-2),respectively.
Samples of each of the three catalysts, Pt-ALjOg (from Engelhard), V2O5-
A^Og (from Harshaw) or Fe-Cr oxide-AUO- (laboratory prepared) were subjec-
ted to a brief parametric investigation to study the effects of NH3/NO ratio,NO,O2
and SO2 concentrations, space velocity (s.v.) and temperature on the conversion
of NO. It was found that the non-noble metal catalysts promoted the selective
reduction of NO with a maximum in conversion of NO at 400°C for 20,000 hr"1
space velocity (STP). Although the platinum catalyst showed a conversion maxi-
mum at only 250°C, a major product of the reaction was N2O. On the other hand,
the non-noble metal catalysts did not promote extensive production of ^O. As
space velocity increased, conversion of NO on both VnO_ and Fe-Cr catalysts
-------
decreased substantially as depicted in Figures 1 and 2. Space velocity effects
were much smaller with the Pt catalyst, as shown in Figure 3, in accord with
results of Andersen et al (3-3).
Addition of up to 2000 ppm SO2 into a test gas with typical flue gas (composi-
tion: 14$ CO2, 5% HoO, 3% O2> 1000 ppm NO)^ resulted in negligible change in the
percent conversion of NO with 1100 ppm NH on the VgOg and Fe-Cr catalysts
operating at 400°C. When SO0 was added to the test gas with Pt catalyst at 250°C,
^J
however, a decrease in NO conversion occurred.
The results of the brief parametric tests in the TRW/UCLA project established
selective reduction of NO with NH« as a promising means of abatement of NO and a
preliminary economic analysis showed the process to be viable. Because of the
lower operating temperature, platinum catalyst was attractive for use with low-sulfur
fuels. The drawback of higher operating temperature with the non-noble metal catal-
ysts was offset by their sulfur resistance.
The V2O5 and Fe-Cr catalysts, in view of their sulfur resistance and their ten-
dency to promote reduction of NO to N2 rather than N£O as a final product, were
of sufficient promise to merit additional investigation. A detailed parametric study
to investigate more fully the effects of O2, H2O and CO concentrations and to estab-
lish rate expressions for design of larger-scale reaction equipment was warranted.
In addition, it was important to determine if the sulfur resistance shown over short-
term exposure was maintained during extended periods of operation. These results
of the TRW /UCLA project suggested further investigation of the non- noble metal
catalysts which in the present project was designed to assess more fully the utility of
VjjOs and Fe-Cr catalysts for use in the selective reduction of NO. As indicated in
the Introduction, the primary objectives of the present program were to: optimize
the compositions of the vanadia and iron-chromium catalysts for selective reduction
of NO with NH3> develop rate expressions for design use and perform long-term
durability studies of optimum catalyst compositions in flue gas containing sulfur
oxides.
A secondary objective of the project was to provide an update of current develop-
ments in NO catalysts in the published literature.
X *
-------
100
80
60
u.
o
S 40
LU
20
0.6
5,000 hr'»
000 hr
-I
20,000 hr'»
O
A
A
5000
5000
5000
10000
10000
10000
10000
20000
20000
ppmNO CAT wt. (gm)
1060
1000
350
1000
1000
500
250-300
IOOO
250
14
28
28
14
28
28
14
14
0.8 1.0
NH3/NO RATIO
1.2
1.4
Figure 1. Reduction of NO with NH on 10#V2O - AlgOg (Harshaw V-0610T1/8)
CO2, $ H2O, 3£02 present in NZ carrier, 400°C.
-------
100 r
80
60
g
V)
£40
8
20h
O 5000
A 10000
A 10000
• 20000
a 20000
y 20000
1000
1000
1000
1000
500
250
5,000 hr'1
I0,000hr-|
20,000hr'l
ppmNO Cat.wUgm.)
28
28
14
14
14
14
0.6
0.8
1.0
1.2
_J
1.4
NH3/NO RATIO
Figure 2. Reduction of NO with NH on 10$ Fe-Cr (S/IJ-ALO at 400°C.
5$ H2O, 3% O2 in Ng carrier. ^3
CO ,
2
10
-------
100
060
O
55
a:
UJ
o
o
20
10,000 hr"1
-BO B
20,000 hr'l
S.Vthr"1) ppmNO
A
a
o
a
a
10000
20000
20000
20000
1000
1000
800
500
20000 25O
0.4 0.8 1.2 1.6 2.0
NH3 /NO RATIO
2.4
Figure 3. Reduction of NO with NH, on 0.5#Pt-Al O (Engelhard) in simulated flue
gas. 14£ CO2, 5# H2O, 3$ Og present in Ng carrier; 250°C.
11
-------
4. EXPERIMENTAL
The equipment and procedures used in the catalyst optimization studies and the
parametric and durability tests are described in this section. A general description
of the computer programs used for data reduction and correlation is also presented.
4.1. CATALYST PREPARATION
Vanadia and iron-chromium oxide catalysts were prepared by impregnation tech-
niques using pre-formed alumina pellets as support material. Support materials
tested in this project were (a) Filtrol Grade 86 cylinders, nominally 1/8 in. dia. x
3/16 in. length; (b) Alcoa H -151 -8 spheres, 1/8 in. dia.; (c) Alcoa F-l -1/4-8 gran-
ules, irregularly shaped, up to about 1/4 in. ; and (d) American Cyanamid Aeroban
spheres (AO-SiCL mixture), 3/16 - in dia.
The vanadia catalysts were prepared by impregnating dry carrier pellets with an
aqueous solution of ammonium metavanadate and oxalic acid (2:1 molar ratio of
NH^VO- to ~3.2^2^± ' ^T^O). Because of solubility limitations a large amount of
water was necessary for preparing catalysts with 10$or more V2O (final, dried form)
preventing single-step solution absorption. The excess liquor was decanted from the
pellets which were then partially dried. The remaining solution was absorbed by the
semi-dried pellets. The pellets were fully dried at 160° C and then calcined in flowing
air at 500°C to decompose the vanadate to V2O and burn off the organic acid. No
other activation procedure was used before testing the catalysts.
Iron-chromium catalysts were prepared by impregnating alumina pellets with
aqueous solutions of Fe(NO ) * 9 HgO and CrO . Complete absorption of the liquor
was accomplished in a single step with the iron-chromium series of catalysts. The
moist pellets were dried and calcined under conditions similar to those used with V^Cv
catalyst. Complete details of the preparation of V9Cv and Fe-Cr catalyst showing
highest activity are given in Section 5 (Results).
Table 1 summarizes the catalysts prepared and tested in this project. Also in-
cluded in the table are several commercial catalysts tested for comparison purposes.
La the vanadium series the percent of active material (V2O_) and type of carrier were
of interest. With the Fe-Cr series the percent of active loading, as well as the Fe/Cr
weight ratio was studied.
12
-------
TABLE 1. LIST OF CATALYSTS TESTED
Preared Catalyst
Carrier *
Commercial Catalysts
104 V00C
2 5
15# VJX
^25
204 V205
254 V205
V* V2°5
154 V205
154 Y0C>
2 5
5* Fe-Cr (1/1)
54 Fe-Cr (3/1)
54 .Fe-Cr (9/1)
104 Fe-Cr (1/1)
105J Fe-Cr (3/1)
104 Fe-Cr (9/1)
104 Fe-Cr (9/1)
104 Fe-Cr (20/1)
104 Fe-Cr (50/1)
114 Fe-Cr (5/1)
20* Fe-Cr (1/1)
204 Fe-Cr (3/1)
204 Fe-Cr (9/1)
1'04 FefcjOjj
204 Fe2°3
Filtrol 86 Vanadia
Filtrol 86 104 V0C> Harshaw V-0601 T 1/8
2 5
Filtrol 86 (A10O0 carrier)
£t
-------
4.2. BENCH-SCALE TEST APPARATUS
Optimization, parametric and durability studies were performed in a tubular, up-
flow reactor operating under isothermal conditions. Figure 4 shows, in schematic
form, the reactor and associated equipment.
The reactor, as well as a tubular preheater, was maintained at preselected tem-
peratures in an air-flow, fluidized sand bath heater using powdered alundum as the
fluidized medium. A back pressure valve on the reactor outlet was adjusted to main-
tain a constant pressure in the system at all temperatures and to compensate for
changes in pressure drop across the reactor bed when switching from inlet to outlet
sampling modes.
Gaseous nitrogen, carbon dioxide and nitric oxide were mixed in a glass manifold
after passing through needle-valves and rotameters. Nitric oxide flow was measured
more accurately with a soap-bubble flowmeter.
Oxygen was added to the gas stream upstream of the vaporizer- mixer by appro-
priate injection of air. Ammonia and water were added at this point also. The am-
monia was fed from an anhydrous liquid NH« tank using a rotameter for coarse flow
adjustment. Water was injected in liquid form using a small rotary pump. The
vaporizer-mixer was a 5/8 - in. dia. stainless steel tube, 10 inches long filled with
1/8-in. glass beads. The tube was lagged with a heating tape and insulated to main-
tain a temperature of at least 350°C.
When SO2 was used, its injection point was immediately upstream of the vapori-
zer-heater. Earlier attempts to introduce SOg at the common entry for NH3, air.and
HgO invariably led to plugging of the system due to salt formation at low temperatures.
The reactor was a stainless steel tube with end fittings containing stainless steel
screen discs to retain the catalyst. Two reactor sizes were employed. The standard
size used in most of the tests was constructed of 5/8 in. dia. tubing to contain 14 ml.
of catalyst. The second reactor was constructed of 1.0 in. tubing and had an internal
volume of 28 ml.
4.3. ANALYTICAL EQUIPMENT AND PROCEDURE
Inlet and outlet analyses for NO were made with a Beckman Model 315A non-dis-
persive infrared analyzer. Routine analyses for NO2 were made with a Beckman
Model 77 visible-light analyzer.
Nitrous oxide (N2°) concentrations were determined with a Perkin-Elmer Model
990 chromatograph with a 6 ft, 1/8 in. -dia. column of Porapak Q operating at room
temperature. The temperature was varied periodically up to 150°C during analyses
of outlet gases in the presence of SO2 to check for the production of H2S and COS. In
view of the overall oxidizing nature of the test atmosphere, the presence of either
14
-------
MANIFOLD
•H20
VAPORIZER
HEATED LINES AND VALVES
MANOMETER^!
REHEATER
AIR
-TO ANALYZERS
AR
ELECTRICALLY HEATED
FLUIDIZED BATH
DRAIN
TO W.T. METER
DIAPHRAGM
PUMP
Figure 4. Catalyst test apparatus.
-------
species was considered unlikely; neither was found in any instance (surface dissocia-
tion of NH3 was considered to be a possible source of H2 which with H2O and CO2,
through the water gas shift, could be a source of CO).
Ammonia was analyzed by two methods. In the absence of SO-, a wet titration
method was employed. A volume of gas, measured with a wet-test meter, was drawn
through an absorber containing 4$ boric acid in water. The absorber contents were
titrated with 0.04 N HC1 using bromcresol green indicator. When SO- is present,
sulfite and sulfate interfere with the HCl titration. In these tests, NHo analyses were
performed on the contents of the absorber with an Orion specific ion electrode and a
Keithley electrometer.
Sulfur dioxide was determined indirectly by measuring separately sulfur trioxide
and total oxides of sulfur. In the former measurement, a known volume of gas was
absorbed in a train of bubblers containing 80£ isopropanol in water. An aliquot of the
solution was titrated with 0.01 N BaClO. using Thorin indicator. The precipitate
formed remains colloidal in the high concentration of non-aqueous solvent. Thorin,
which adsorbs on the precipitate, undergoes a color change from yellow to pink in
excess Ba . Sulfur dioxide, carbon dioxide and ammonia do notjnterfere with the
titration which is specific for SO (4-1). Oxidation of sulfite (SO~ from dissolved
SO ) is avoided by maintaining the absorbent at ice temperature until titration.
2
Total oxides of sulfur were determined by passing a known volume of gas through
bubblers containing basic 1.5$ H~O (equi-volume mixture of 0.2 N NaOH and 3$
HO). Any SO absorbed in the oubbler was oxidized by HLO_ to SO~. The contents
of the bubbler were acidified to prevent formation of Ba(OH)9 in the ensuing titration,
boiled to drive off CO2> passed through a cation exchange resin to remove interfering
sodium and then titrated as above.
The sulfur dioxide concentration was calculated as the difference between total
oxides of sulfur and SO . Although there was some difficulty in observing the end
point with laboratory-prepared solutions of H SO as a source of SO~ , it was found
that the technique was accurate to within 3% when gases with known concentrations of
SO2 were absorbed in basic H_O . The difficulty in applying the method to the solu-
tions of H_SO, may be related! to the dibasic acid equilibrium between SO^ and HSO~.
24 44
4.4. STANDARD FLUE GAS COMPOSITION AND FLOW RATE
In Task 1, optimization of catalyst composition was based on performance using
a single test gas mixture that had as the sole variable the NH concentration. This
mixture, called in this report the "standard flue gas" was also used in most of the
durability tests. The NH3 concentrations were either near-stoichiometric for reduc-
tion of NO to N or in excess.
A
The standard flue gas contained 12^ CO-, 5^ H^O, 3$ O- and 1000 ppm (parts
per million by volume) NO in N2» Ammonia was either 650-^750 ppm (670 ppm is
16
-------
stoichiometric) or 1000-1100 ppm. By using the 14 ml. reactor, the normal total
gas flow rate was 280 liters/hr (STP: 0°C, 1 atm) providing a space velocity of 20,000
hr"1. The 28 ml. reactor at the normal flow rate provided a space velocity of 10,000
hr-1.
4.5. TEST PROCEDURE
The typical start up procedure was to adjust N, flow rate temporarily to 266
liters/hr (corresponding to total dry gas in the flue gas mixture) and to introduce NO
at 1000 ppm in order to span the NO analyzer. The N2 flow rate was then decreased
to correspond to its concentration in the flue gas (allowing for the N_ introduced in the
air stream) and the other gas species (except for NH ) were added.
t>
The sand bath aid the vaporizer/mixer heaters and those on the lines to the ab-
sorbers were set to appropriate power levels. Using the analyzer calibration curves,
the desired NO concentration was obtained by adjusting the feed needle valve. The
desired ammonia concentration was estimated with a rotameter. The gas mixing
process was allowed to stabilize for about 30 minutes and the inlet stream was sam-
pled for NHo, using the titration method described above, and the NH., concentration
adjusted as required.
If SO2 was to be added, it was introduced using a rotameter as a guide. Analysis
of the inlel: stream followed the described procedure. After introduction of SO9, all
subsequent inlet and outlet NH analyses were performed with the Orion probe. Out-
let and inlet analyses were routinely performed using as a criterion for steady-state
the constant, analyzed concentrations of NO, N0O, NO9, and NHo for at least 30 min-
£t £t O
utes.
In the parametric studies (Task 2), NO, NEL, Og, CO2 and H2O concentrations,
as well as temperature and flow rate, were all varied to provide large perturbations
from the standard conditions.
In the durability studies with SO present, periods of steady-state operation under
SO -free conditions were frequently Tollowed to provide comparison data and to check
for catalyst degradation.
4.6. DATA REDUCTION
Development of empirical rate expressions proceeded according to the following
sequence. A rate expression of the following form was assumed:
, . n m q . -E/RT «n m q g-moles NO (1)
r, rate = k PNQ p p = Ae p^p p ^ >gm catalyst
& & O A
A computer program was employed that determines an experimental rate constant
(k ) for each data point and then determines by linear regression the best-fit A and
6XJ3
17
-------
E values for all data points. Specifically, the computer solves the combination of (1)
and the plug flow mass balance,
•
to give
3
where F = inlet feed rate of NO, gm mole NO/hr
W « weight of catalyst, gm.
Q = volumetric flow rate, 1/hr.
p = molar density of feed, gm mole/£
'PO = inlet partial pressures, atm.
p ,p ,p = instantaneous partial pressures, atm (Equation 1)
= conversion of NO
= fp° -p
^ PNONO
n, m, q = reaction orders ,
, .... . . gm moles
k - experimental rate constant, r* - •—: — r— : . . n+m
exp hr-gm catalyst- (atm)
S = stoichiometric factor = 3/2
rr = reactor pressure, atm.
The computer calculation determines the k for a large number of combinations
of n,m and q. For each combination, linear regression of kex_ as a function of (1/T)
is performed, giving the constants A and E (see Eq. 1). The program then determines
the sum of squares ( a ) of the difference between specific rate constants calculated
from the regression parameters and the experimental values, k »
exp
I
(k - k ) 2 (4)
x exp • v '
The minimum sum of squares, found by inspection of the output record, corres-
ponds to the combination of n, m and q which best describes the data.
The resulting rate expression describes global kinetics in the test system em-
ployed. This rate expression, by itself, cannot be used to predict performance in
other reactors unless it can be demonstrated that in the generation of experimental
data, there were no bulk diffusion and pore diffusion effects. That is, for design
purposes, an intrinsic (surface) rate expression must be available from which global
rates in other equipment can be predicted.
18
-------
To determine intrinsic rate expressions a second computer program was em-
ployed. This program determines, in a step-by-step manner from reactor inlet to
outlet, the surface concentrations of reactants and surface temperatures based on
mass and heat transfer correlations, and an effectiveness factor, r\ (defined below),
which parameterizes internal diffusion effects. By assuming an intrinsic (surface)
rate expression, the degree of conversion of NO is calculated throughout the catalyst
bed. The rate at any point (i) is determined by
ri * ^s PNO PNH P0,
o A
where k is the intrinsic rate constant and the partial pressures are those at the outer
o
surface, as determined in the bulk diffusion effect calculations. Calculated conversion
at the reactor outlet is compared with the experimental value and the process is re-
peated with modified forms of the assumed intrinsic rate expression until agreement
is obtained. Effectiveness factors were determined for each reactor segment in a
step-wise procedure using relationships involving the Thiele diffusion modulus (4-2,
4-3, 4-4). Near-unity values of TI indicate that pore diffusion effects are negligible.
For convenience, the calculation procedure begins by assuming that the intrinsic
rate parameters are those determined from the correlation of the global rates as
described earlier (i. e., initially assuming negligible mass transfer resistances).
The final form of the intrinsic rate expression can be utilized for the determina-
tion of global rates of reaction at any scale of operation (assuming catalyst surface
activity is unchanged) by calculating surface concentrations and temperatures and
effectiveness factors for the desired conditions. More details of the computer
program have appeared in other publications (4-4, 4-5).
4.7. LITERATURE ACQUISITION (Task 3)
The computerized literature survey at the UCLA library, augmented by compila-
tions from APTIC, provided appropriate references of articles and patents pertinent
to NO catalysis. A thorough analysis of each reference was not attempted in the
project;. This survey was used to identify particularly promising catalysts used for
the selective reduction of NO with NHo and to obtain, where possible, pertinent op-
erating data.
The primary source of literature was from patent files and, of these, by far,
the predominant sources were Japanese. A number of these patents were translated.
The majority of the literature sources could not be obtained during the course of the
project. Reliance on abstracts as published by the standard literature-retrieval ab-
stracting services was made to provide some information. A list of references was
made, including such pertinent data as was available, and is presented in Appendix A.
19
-------
5. RESULTS
The results of the experimental effort in each of the three tasks are summarized
in the following sections. Tasks 1 and 2 were performed chronologically, as de-
scribed, while Task 3 was performed as a continuing effort throughout the program.
5.1. Task 1. OPTIMIZATION OF COMPOSITION AND DEVELOPMENT OF CHEMICAL
SPECIFICATIONS OF VANADIA AND IRON-CHROMIUM CATALYSTS
Several catalysts were prepared with variations in the amount of active material
and, in the case of Fe-Cr catalysts, in the ratio of the metal constituents. In addition,
several commercial catalysts were obtained and tested. Tests in simulated flue gas
containing 1256 COn, 3/6 O, and 5$ HoO and either stoichiometric or excess NH3 were
performed to assess the effects of catalyst composition on catalyst activity. Tem-
perature was the only variable (other than the two NH concentrations) in the screening
studies. Although some of the catalysts, which have been shown to be inferior under
the present study, may be more active under other conditions, such operating modes
will probably be outside of practical operating regimes.
Prior to conducting the screening tests a check was made to determine if reac-
tion occurred in the empty reactor and feed systems and to determine the extent of
conversion of NO to NO- in colder parts of the system. Negligible conversion of NO
to N« or N2O was observed, although a small amount of NO2 was formed, depending
on O2 concentration. In general, NO2 production was less than 100 ppm with 1000
ppm NO in 3% O . It was deduced that the NO2 was formed in the NO2 analyzer itself
which has a 15 minute residence time at the sampling flow rate employed. Inlet and
outlet concentrations of NOX as tabulated in this report have been corrected to include
the small NO0 concentrations observed.
£ ' f
5.1.1. Vanadia Catalysts
Several vanadia-alumina catalysts were prepared with various concentrations of
V-O . Compositions are listed in Table 1. Filtrol Grade 86 AlgO, (1/8-in. dia. x
3/16 - in. long cylinders) was used as support material in the first series of prepara-
tions. Catalysts containing 10, 15, 20 and 25$ (by weight) V2O were prepared by
impregnating the AlgO pellets with aqueous solutions of ammonium metavanadate
(oxalic acid was usea to increase the solubility of the vanadate). The impregnated
pellets were dried and then calcined in air at 450°C to form the vanadium oxide and
drive off ammonia and organics.
20
-------
Catalyst activity was determined in a simulated flue gas stream containing 12$
CO2, 5$ H2O, 3$ O_ and 1000 ppm NO with approximately 700 ppm or 1100 ppm NHg
(balance N2>. The 700 ppm NH_ concentration represents a near-stoichiometric
amount for conversion of the NO to N2« The 1100 ppm NH represents a 65$ excess of
NKL. Temperature was varied from 100 to about 450°C with each catalyst. Flow
rates were maintained at 280 liters/hr (STP) to provide a space velocity of 20,000 hr"1
(STP).
Figures 5 and 6 show conversion of NO as a function of temperature for 700 and
1100 ppm NH_, respectively. Also included in the figures are data for the commercial
10% V O5-A12O3 catalyst (Harshaw V-0601T 1/8) obtained in the previous TRW/UCLA
project. Figure 5 shows that the prepared V2Og catalysts were of approximately equi-
valent activity at the stoichiometric NEL/NO ratio. Between 300-450°C the prepared
catalysts were more active than the commercial catalyst.
With excess NH3 (Figure 6) highest conversion levels for temperatures above
250°C were obtained with the 15$ catalyst. However, the differences in activity of the
prepared catalyst were not large. The commercial V«O catalyst was as active as
the 10 and 25$ catalysts at the higher temperatures.
Figure 7 shows that, at 300 and 400°C, the optimum composition occurs at about
15$ V2O . The decreased activity of the 25$ catalyst may be due to excessive loading
of V0O in the catalyst pores with a corresponding decrease in surface area.
u 5
The surface area of the Harshaw catalyst was reported as 115 sq. m/gm. Using
a chromatographic surface area measurement technique, the surface area was deter-
mined to be 103 sq. m/gm, indicating good agreement with the reported Harshaw BET
value. Surface areas of the 15 and 25$V2O catalysts were 198 and 154 sq. m/gm,
respectively, lending support to the hyposthesis that reduced activity above 15$ V2O
is related to decreased surface area.
Two additional catalysts were prepared using Alcoa activated aluminas as support
material for comparison with catalysts using the Filtrol-alumina support. The opti-
mum level of 15$ VnOg, as determined in the studies with the Filtrol support, was
impregnated on Alcoa F-l-1/4-8 and H-151 aluminas. The former was in the form of
irregular granules up to 1/4 in. Particles of about 1/8-in. were selected for use.
The H-151-8 alumina was in the form of 1/8-in spheres.
The F-l-1/4-8 and H-151 catalysts were tested in simulated flue gas with 1000
ppm NO and 1100 ppm NHq. Figure 8 shows that the F-l-1/4-8 support provided
significantly higher activity than H-151. Also shown in the figure are data for Filtrol
Grade 86 catalyst containing 15$ V.O for runs with 1100 ppm NH . Above 380°C the
Filtrol and the F-l-1/4-8 supported catalysts were equivalent in activity. Below that
temperature the latter support appeared distinctly superior. In particular, maximum
conversion (about 95$) occurred at only 340°C compared to a slightly lower conver-
sion maximum at 390°C with Filtrol alumina.
21
-------
80
o 60
u.
O
§««-
(£
UJ
O
o
20L
O 10% V205
D I8%V205
20%V205
V 25% V205
• 10% V205HARSHAW
V-601 T 1/8
100
200 300 40O
TEMPERATURE (°C)
500
Figure 5. Reduction of NO (1000 ppm) with NEL (700 ppm) on
in simulated flue gas. (s.v. = 20,000 hr-1)t
.-A10O0 catalysts
22
-------
lOOr
O 10% V205
a 15% »
A 20% "
• 25% -
A 10% " HARSHAW
200
30O 4OO
TEMPERATURE (°C)
50O
Figure 6. Reduction of NO (1000 ppm) with NH3 (1100 ppm) on
catalysts in simulated flue gas.(s.v.=20,000 hr"1).
23
-------
UJ
100 -
90-
80
70
u_
O 60
50
5 40
o
c?> 30
cr
UJ
o
20
10
0
10
OPEN SYMBOLS-700 ppm NH3
CLOSED SYMBOLS-I I 00 ppm NH3
15
20
25
V205 CONCENTRATION (Wt %)
Figure 7. Influence of VO concentration on catalyst activity in simulated
flue gas. (s.v.= 20,000
24
-------
100
UJ
80
z 60
u.
o
o
CO
g 40
O
20
100
SUPPORT
F-l-T-8,ALCOA
A H-I5I, ••
• FILTROL GRADE 86
200
300 400
TEMPERATURE (°C)
500
Figure 8. Effect of AlgO™ support on NO conversion in simulated flue
gas, with 15>V2O5 cJatalysts. 1000 ppm NO, 1100 ppm NH
25
(s.v.= 20,000 hr-
26
-------
With all the V2O5 catalysts tested, no N2O was detected in the exhaust gas
stream. NHg consumption was, in general, less than 65$ in excess of the theoretical
amount required to achieve total reduction of NO to Ng. Up to the temperature of max-
imum NO conversion with each catalyst, above the maximum, NH_ usage increased
sharply and, at about 420°C, reached values more than double that required for the
reduction of NO. It is probable that some of the NH, which reacted at higher tem-
peratures was oxidized directly to NO.
Additional tests of 15$ vo°5 catalyst on Alcoa F-l -1/4-8 activated alumina car-
rier were performed to verify tne initial, promising results which indicated somewhat
improved performance over the Filtrol Grade 86 carrier, particularly at the lower
temperatures. Repeat runs were made in simulated flue gas with 1100 ppm NH3 to
determine the repeatability of earlier data. Figure 9 shows that both sets of data are
within expected experimental error.
For reference, Figure 9 also includes data for the 15$ , laboratory-prepared cat-
alyst on Filtrol Grade 86 carrier and the two sets of data for the commercial Harshaw
V2O catalyst. The first set was obtained in the earlier UCLA/TRW program.
The second set of data was obtained during the present project. Again, satisfactory
repeatability is indicated. The data indicate that the Alcoa support provides superior
activity to either the commercial Harshaw or Filtrol A^Og -supported, prepared cat-
alyst at lower temperatures. On face value the results would seem to indicate better
carrier performance for the Alcoa compared to the Filtrol type. However, other
characteristics were considered in the selection of the most suitable carrier.
It was noticed during testing of the Alcoa catalyst that considerable fines were
produced, leading in one test to excessive back pressure in the system. This parti-
cular activated alumina is not normally marketed as a catalyst carrier, but is usually
used as a dessicant. Even though Alcoa reports that F-series activated aluminas have
high abrasion and water-breakage resistances, the present results suggested a com-
parison of the crush strengths of the various catalysts of interest.
Table 2 summarizes results of compression testing of the Harshaw commercial
catalyst, the laboratory prepared catalysts and the Filtrol and Alcoa carriers. The
H-151-8 is spherical and F-l -1/4-8 is granular; thus, only one mode of testing is
given for these materials. The Alcoa aluminas are noticibly weaker than either the
Filtrol or Harshaw catalysts. The low strength of the Alcoa aluminas eliminated
them from consideration for NOX control. Also, the degree of powdering observed
for this small, bench scale of operation is expected to be magnified under full-scale
operation.
It should be mentioned that another commercial V?O (10$ ) catalyst prepared by
Filtrol was tested in the earlier project and was found To oe physically inferior to the
Harshaw catalyst. More importantly, it was found to be chemically unstable. It is
interesting that only the Filtrol Grade 86 carrier is reasonably strong. No informa-
tion is available to indicate if the Filtrol V2O5 catalyst contains the Grade 86
26
-------
lOOr-
80
60
u_
o
LU
40
20
100
SUPPORT
OR
CATALYST
DATA
SET
O F-l-f-8,15% 1st
• n 2nd
D HARSHAW.10% 1st
| » 2nd
A FILTROL 86,15%—
I
200 300
TEMPERATURE l°C )
400
500
Figure 9. Reduction of NO (1100 pptn) with NHg (approx. 1100 ppm) on prepared
and commercial V2O5 catalysts in simulated flue gas. (s.v.=20,000hr"1)
27
-------
TABLE 2. CRUSH STRENGTH OF CATALYSTS AND CARRIERS
Material Crush Strength* (Ib force)
Longitudinal Radial
Harshaw 10% V_O
2 5
commercial catalyst 17 19
Alcoa H-151-8 carrier
Alcoa H-151-8 carrier
with 15 % V0O_
if 5
Alcoa F-l-1/4-8 carrier
Alcoa F-l-1/4-8 carrier
with 15% V0O_
u o
Filtrol Grade 86 carrier 20 12
Filtrol Grade 86 carrier
with 15% V O 24 13.5
* All data are averages of 4 tests.
28
-------
A brief series of tests was performed with catalysts using Aeroban ZW-1470 car-
rier (ALjO - SiC>2) from American Cyanamid to compare activity with catalysts using
the Filtrol Al O . Figure 10 shows that for a feed gas containing 1000
ppm NO and excess NH , there is substantially no difference between the two catalysts.
With stoichlometric Nrfl the Filtrol-supported catalyst appears slightly superior.
A commercial vanadia catalyst specifically developed for SO2 oxidation in contact
sulfuric acid plants was tested to complete the survey of in-house and commercially
prepared V2O- catalysts. The commercial catalyst was Girdler-Sudchemie type
G-101. This catalyst was particularly attractive because of its very high physical
strength (37 Ib. ), as reported by the manufacturer. The actual V2O content of the
catalyst is unknown. Information provided by the manufacturer indicate a silica
carrier impregnated with vanadium and potassium salts, the latter in a ratio (as
with V2O of about 2. 7/1. Although previous work in this laboratory has shown that
even small concentrations of alkali metals in V2
-------
lOOf—
20
0
200
AEROBAN CARRIER
FILTROL
OPEN SYMBOLS-STOICHIOMETRIC NH3
CLOSED SYMBOLS-1200 ppm NH3
I
_L
300 400
TEMPERATURE (°C)
Figure 10. Removal of 1000 ppm NO with NH in simulated flue gas on 15* V O
catalysts. 12*CC>2, 3* O^ & H*Q, balance N2. (s.v.=20,000 hr-i
30
-------
lOOr
80
LU
O
o:
60
40
o
V)
-------
TABLE 3. IRON-CHROMIUM TEST MATRIX
Percent Active Iron / Chromium Ratio
Material (weight basis)
5
10
20
1/1
1/1
1/1
3/1
3/1
3/1
9/1
9/1
9/1
Tests of activity in simulated flue gas were conducted with either 700 or 1100
ppm NH3 and 1000 ppm NO. Temperature was varied from 200 to 460°C. Table 4
summarizes the results of the screening tests.
In general, the catalysts showed either maximum activity at about 400°C, or a
broad maximum from 300° to 400° C, except for the 20<£ Fe-Cr oxide catalysts.
Large amounts of NoO, which maximized between 385 and 450°C (i.e., at tempera-
tures in excess of the point of maximum conversion), were produced on these three
20$ catalysts. At the temperature of maximum conversion (300°C) the activity of the
20$catalysts increased with increasing iron content. This observation is shown clear-
ly (see open points for the 20$active material) in Figures 12 and 13. At 400°C (closed
points) and excess NHg, Figure 12 shows that maximum conversion occurs at 10$
loading. The catalytic activity of the 9/1 catalyst is superior to both the 1/1 and the
3/1 catalysts at the 10< loading with the latter two of approximately equivalent activity.
Figure 13 shows a trend of higher activity with increasing iron levels at 400°C
and a near-stoichiometric NHg concentration at both 5 and 20$ loading. All 10$cat-
alysts were of approximately equivalent activity.
Analysis of these initial results indicates that optimum catalyst composition for
excess NHg operation at 400°C appears to be 10$ active material (Fig. 12). At 300°C,
however, a 204 catalyst with high iron content is indicated for use with either excess
or stoichiometric NH3-
Previous results (1-2, see Fig. 2) have shown that with 11$ Fe-Cr (5/1) catalysts
operating at stoichiometric NH3, conversion of NO at 400°C can be increased from
about 60$ to about 80> by decreasing the space velocity from 20,000 hr"1 to 5000 hr"1.
With excess NHL, however, the improvement in conversion by operation at lower
space velocities is more substantial. For purposes of catalyst selection for para-
metric studies it was assumed that a minimum space velocity of 10,000 hr~l would
be acceptable for practical reactor sizes.
Excess usage of NH3 does reflect strongly, of course, on the operating cost. A
32
-------
TABLE 4. RESULTS OF ACTIVITY TESTS WITH Fe-Cr CATALYSTS
Catalyst
Active Fe-Cr
Material
5% 1/1
5% 1/1
10# 1/1
10$ 1/1
20$ 1/1
20$ 1/1
5$ 3/1
5% 3/1
Inlet Gas
Temp.
(°C)
205
300
400
465
2~00~
300
400
478
200
295
400
450
200
300
400
205
305
390
460
200
300
385
460
200
300
395
455
220
300
400
455
NO
(ppm)
940
940
940
940
980
980
980
984
960
960
1040
930
1090
1040
1090
940
940
940
940
1070
1020
1025
1025
990
990
990
990
1050
1050
1050
1050
NHg
(ppm)
1036
1036
1036
1036
775
775
730
775
1100
1100
1140
1100
820
758
850
1060
1060
1060
1060
780
780
780
780
1095
1095
1095
1095
780
.780
780
780
NO
(ppm)
880
610
315
450
905
683
510
515
805
430
325
530
915
465
550
800
560
645
880
770
580
690
960
850
730
365
305
920
760
465
425
Outlet Gas
NH3
(ppm)
942
600
94
0
730
345
0
0
1012
412
0
0
753
0
0
942
0
0
0
294
0
0
0
1059
848
340
0
706
118
0
0
NO
N2O Conversion
(ppm) ($ )
0
0
50
50
0
0
0
0
0
0
0
0
0
0
0
0
190
420
330
0
180
220
165
0
0
0
0
0
0
0
0
6
35
66
52
8
35
48
48
16
55
68
44
16
55
49
23
46
38
15
28
43
33
6
14
26
63
69
12
28
56
57
(continued)
33
-------
TABLE 4 (cont.>
Catalyst
Active Fe-Cr Temp.
Material (°C)
10% 3/1 200
300
390
450
10# 3/1 200
300
400
445
20# 3/1 210
300
390
450
465
20£ 3/1 200
300
400
465
5$ 9/1 200
300
395
475
5% 9/1 200
310
400
470
10# 9/1 215
300
400
460
10$ 9/1 210
300
400
460
Inlet
NO
(ppjn)
1055
1120
1120
1120
1100
1100
1100
1100
1095
910
910
910
1110
1000
1000
1000
1000
1110
1110
1110
1110
1130
1130
1130
1130
975
980
970
970
1000
1000
1000
1000
Gas
NH3
(ppm)
1106
1106
1106
1106
735
735
735
735
1140
1140
1140
1140
1140
780
7»0
780
780
1120
1120
1120
1120
763
763
763
763
1106
1106
1152
1152
750
750
750
750
Outlet Gas
NO
(ppm)
820
465
395
560
815
520
530
640
600
335
690
730
900
780
480
665
975
965
805
335
425
965
690
430
510
865
410
235
450
825
480
515
605
NH3
(ppm)
824
259
0
0
530
118
0
0
918
153
0
0
0
563
0
0
0
1059
753
0
0
659
553
0
0
965
448
0
0
636
165
0
0
N20
(ppm)
0
0
150
0
0
0
0
0
0
0
400
N.A.
140
0
140
200
190
0
0
100
100
0
0
0
0
0
0
150
0
0
0
0
0
No Con-
versfott
<*)
22
58
65
48
26
52
52
42
40
63
24
20
19
22
52
34
3
13
27
70
62
15
39
62
55
11
58
76
54
18
52
49
40
(continued)
34
-------
TABLE 4 (cont.)
Catalyst
Active Fe-Cr
Mate rial
20£ 9/1
20$ 9/1
Inlet Gas
Temp.
(°C)
200
295
390
300
455
210
300
400
455
300
NO
(ppm)
1010
1010
1010
1010
1010
940
940
940
940
940
NHg
(ppm)
1118
1118
1118
1118
1118
742
753
753
753
742
Outlet Gas
NO
(ppm)
725
225
475
215
765
680
395
570
745
335
NH3
(ppm)
636
330
118
NA
0
378
0
0
0
0
N20
(ppm)
0
0
200
0
200
0
0
90
130
0
NO Con-
version
<*!_
28
78
53
79
24
28
62
45
28
64
s.v. = 20,000 hr"1. Simulated flue gas contains also 12$ CO2> 3«£ O2,
in N
35
-------
80r
70
60
(T
UJ
o
o 40
30
20
Fe/Cr
O • I/I
D • 3/1
A A 9/1
OPEN POINTS-300°C
CLOSED POINTS^OO'C
5 10 15
PERCENT ACTIVE MATERIAL
20
Figure 12. Effect of Fe-Cr ratio and percent active material on NO conversion
at 300°C and 400°C. 1000 ppm NO, 1100 ppm NH . (s.v.=20,000hr~1)^
36
-------
o
tn
tr
UJ
O
o
70
60
50
40
30
20
OPEN POINTS-300 °C
CLOSED POINTS-400°C
5 10 15
PERCENT ACTIVE MATERIAL
2O
Figure 13. Effect of Fe-Cr ratio and percent active material on NO conversion
at 300°C and 400°C. 1000 ppm NO, 700-850 ppm NH .. (s. v.=20,000 hr"1).
37
-------
complete economic balance between NH usage and required NOX abatement (at a par-
ticular site) may indicate acceptable operation at near-stoichiometric NHg levels.
However, to select the optimum catalyst for the parametric tests, the primary cri-
terion employed in this phase was maximum conversion of NO. Thus, the data in
Figure 12 was used to select the catalyst for operation with excess NH3.
Figure 12 shows that with Fe/Cr ratio of 9, conversion of NO for the 20% active
material at 300°C and for the 10$ active material at 400°C is approximately equivalent.
Selection of the 20$ catalyst would depend on whether cost savings occur by incorpor-
ation of flue gas diversion ductwork at 300°C rather than at 400°C (i.e., less insula-
tion and lower operating temperature for the fly-ash removal cyclone), and if such
savings compensate for the higher catalyst cost.
It has been shown (1-2) that operation at 400°C is amenable to existing economizer
outlet conditions with little heat loss. Operation at 300°C will probably require signi-
ficant alteration in air preheater conditions (normal flue gas outlet temperatures of
18QOC are common), such as initial cooling by air to 300°C and then final heat re-
covery by further cooling after catalytic conversion to desired stack gas temperatures.
Thus, potential cost saving inherent in lower-temperature ductwork (less insulation,
etc.) may be more than offset by additional equipment modifications.
It should also be noted (Table 4) that the 20$ oxide catalysts promote the formation
of N_O; its effect on air quality has not yet been fully assessed. Similarly, the data
indicate that the 20$ catalysts do not appear to be as efficient in decomposing (or
oxidizing) excess NHQ at 300°C compared to the 10$ catalysts at 400°C.
tj
These several factors suggested the tentative catalyst selection of the 10$ active
material and operation at 400°C. However, Figure 12 suggests that even higher im-
provement in activity may be possible if the Fe/Cr ratio is increased to values higher
than the maximum (9/1) employed in the preliminary survey.
In a second series of tests, catalysts containing Fe/Cr ratios of 20 and 50, both
at a 10$ loading, were prepared and tested. Figure 14 summarizes the results.
Table 5 identifies the catalysts represented. In addition, catalysts containing Cr-
free iron oxide were studied - 10$ Fe2O on A12O. 20$ Fe O~ on AlgO-, and com-
mercial 10$ Fe2O3 on AlgOg (Harshaw Fe^-0301 -Tl/8). Finally, to complete the
test matrix, the Fe-Cr composition examined in the previous program (with TRW)
was retested. This catalyst was about 11<^ active material on Al_O and contained an
Fe/Cr ratio of 5.
Figure 14 shows that the commercial Fe2O catalyst has significantly lower ac-
tivity than the laboratory-prepared catalysts. The former catalyst and the two pre-
pared Fe2O3 catalysts (10$ and 20$ Fe2O ) appear to exhibit maximum conversion at
temperatures somewhat higher than 400°C, which was the typical maximum tempera-
ture of the Fe-Cr series. Included in the figure are data points for the 5/1 Fe-Cr
38
-------
en
-------
TABLE 5. CONVERSION OF NO AT 400°C ON Fe AND Fe-Cr CATALYSTS
Catalyst
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Active
Material
5
5
5
10
10
10
10
10
10
11
20
20
20
20
Fe/Cr
Ratio
(wt)
1
3
9
1
3
9
20
50
00
5
1
3
9
00
"Vs
2.5
3.7
4.5
4.9
7.5
9.0
9.5
9.8
10.8
10.6
9.9
14.9
18.0
20.0
*Cr2°3
2.5
1.3
0.5
5.1
2.5
1.0
0.5
0.2
0
0.4
10.1
5.1
2.0
0
Conversion of
NO at 400°C
66
63
70
68
66
76
70
70
59
70
36
24
53
76
s.v. = 20,000 hr"1. 1000 ppm NO, 1100 ppm NHg, 12£ CO2,3£ O2> S^HgO in
40
-------
catalyst (No. 10) obtained in the previous program and the 9/1 Fe-Cr catalyst (No. 6),
which show that at 400°C with a 10$ catalyst there is a definite increase in activity
when a small amount of chromium is added to Fe O . The 20/lFe/Cr, 50/1 Fe/Cr
and 5/lFe/Cr catalysts are of equivalent activity. The 20$ Fe O catalyst is distinc-
tly superior to 10$ Fe O and, at 400°C, is equivalent to the Fe-Cr catalysts with
10$ loading. It is apparent from Figure 14 that optimum operation of the pure Fe O
catalysts will require temperatures of 450° or higher.
It is considered that 400°C is the maximum desirable temperature for operation
of the NO catalysts. Table 5 and Figure 15 summarize NO conversion at that tem-
perature as a function of absolute Fe O and Cr O concentrations in order to assist
in the selection of the optimum composition. The marked improvement in activity
near 10$ loading by addition of small amounts of Cr O is shown in the plot in the
direction perpendicular to the X -Fe O plane from point 9 to point 6.
£t «J
An initial, cursory examination of the results may suggest that the single-com-
ponent, 20$ Fe O formulation is the most economical catalyst. However, a more
careful examination indicates that a catalyst of equivalent activity can be prepared by
starting with the 20$ Fe O formulation and substituting over half of the Fe_O content
with an amount of Cr2Oq equal to only 9^ of the Fe2O replaced (i.e. , the catalyst
weight of active material is decreased from 20$ Fe O to a 10$ catalyst with Fe/Cr =
9/1). By assuming that commercial quantities of catalyst are prepared following the
procedure currently employed in the laboratory and assigning an arbitrary cost of 100
to the 20<* FegO catalyst, the calculated relative cost of the 9/1 Fe-Cr catalyst with
a 10^ loading would be 45. The relative cost is based on current, moderate-volume
prices for Fe(NO0)0 • 9 H0O and CrOQ.
<3 O 4
-------
CONVERSION
OF NO (%)
80
20Fe203(%)
Figure 15. Conversion of NO as a function of Fe2O3 and CrgO^ concentrations
at 400°C. See Table 5 for catalysts denoted by numbered points.
(s.v.= 20,000hr~1).
42
-------
100
80
60
I 40
20
O • AEROBAN SUPPORT
O • FILTROL SUPPORT
OPEN SYMBOLS-NO
"CLOSED SYMBOLS- NH
A GIRDLER 6 3A
200
300 400
TEMPERATURE (°C)
500
Figure 16. Conversion of NO and NH on 10# Fe-Cr catalysts in simulated flue gas,
1000 ppm NO, 1100 ppm NH, (s.v.=20,000 hr-1).
43
-------
SiO + graphite) in .the previous UCLA/TRW project were not particularly promising,
based on a single point screening test. Nevertheless, it was of interest to determine
the activity of this Fe-Cr catalyst under present test conditions. In particular, it
was considered possible that the temperature employed in the previous test (400°C)
may not have been that at which the maximum conversion of NO was realized with
this catalyst. Previously, at 400°C with stoichiometric NH3 in simulated flue gas,
conversion of NO was only 2$ and very extensive decomposition (or oxidation) of NHg
was observed.
Tests of the Girdler catalyst with stoichiometric NHg were conducted in the cur-
rent project at temperatures varying from 200 to 400°C. Figure 16 includes these
results. At 400°C conversion of NO was zero even though total usage of NH3 was ob-
served. At 300°C, at which point the NO conversion maximum was observed, NO
conversion was only 26$. Considerable ^O was produced, in contrast to the Fe-Cr-
ALO catalysts prepared at UCLA, which appeared to be formed primarily from the
reaction between NH» and O . No further tests were made with the G3A catalyst com-
pleting the catalyst optimization studies.
Surface areas of several of the Fe-Cr catalysts were measured to determine if
activity was related to area. Table 6 summarizes the results of the measurements
and includes NO conversion data at 400°C. There appears to be a correlation between
area and activity for the Fe-Cr catalysts although the deviation in areas of the three
catalysts are not markedly different (values given are averages of several measure-
ments, generally within + 5 sq m/gm). Conversion of NO on the two chromium-free
catalysts appeared to be more dependent on the amount of Fe O than on surface area
as shown in the table.
Based on the activity tests, the 10$ catalyst with an Fe/Cr ratio of 9/1 on Fil-
trol Grade 86 support was selected for further parametric tests. At that time there
was no reason to expect that the SOX resistance would be significantly different from
the 11< , Fe-Cr (5/1) catalyst, which had been previously shown to be unaffected by
SOX at 400°C for short exposure time tests. Nevertheless, parametric tests of the
9/1 Fe-Cr catalyst were preceded by a short experimental study of the effect of SOX
on conversion of NO on the 9/1 Fe-Cr catalyst in simulated flue gas. For short-term
exposure to SOX (8 hours) there was no evident deterioration in catalyst activity; (see
Table 7) thus, a final selection of the 9/1 Fe-Cr catalyst for use in further parametric
studies was made.
5.1.3. Preparation of Optimum Catalyst Formulations
The laboratory procedures used in the preparation of the 15$ V9O and the 10$
Fe-Cr (9/1) catalyst are described in this section. The selected carrier was Filtrol
Grade 86 AlgOg pellets (-1/8 in. dia. x 3/16 in. long).
The VgOg catalyst was prepared by impregnating 85 gm of dry A12O3 pellets
44
-------
TABLE 6. SURFACE ABEA OF Fe-Cr CATALYSTS
Fe/Cr Ratio Oxide Content Area Conversion of NOat400°c
(wt. basis) (%) (sq m/gm) (%)
3 10 240 66
9 10 260 76
50 10 240 70
59
76
Raw Fiitrol Carrier
10
10
10
20
0
260
240
240
200
270
TABLE 7. EFFECT OF SO2 ON CONVERSION OF NO OVER Fe-Cr (9/1) CATALYST
In
NO
(ppm)
900
900
890
890
ilet Gas Cone.
**»
(ppm)
1317
1323
1317
1323
*>*
(ppm)
0
800
0
800
Outlet
NO
(ppm)
375
690
240
250
Gas Cone.
^3
(ppm)
790
565
400
56
Temp.
rc)
295
295
400
400
Conv. of
NO
(%)
25
24
73
72
s.v. = 20,000 hr"1. Simulated flue gas contains also 12$ CO , 3£O2> 5«g HO in N2-
45
-------
with 60 ml of a solution containing 19.3 gm NH4VO3 and 10.4gmH2C2O4 • 2H O (2:1
molar ratio). Complete absorption of the solution could not be achieved in one step.
The excess liquor was decanted from the pellets. The latter were then dried in am-
bient air and subsequently impregnated with the decanted liquor.
The Fe-Cr catalyst was prepared by impregnating 90 gm of the dry alumina
pellets with a 64 ml solution of 45.5 gm Fe (NO0)0 • 9 HnO and 1.3 CrOQ.
332 «
Both the VoOg - AlgO and Fe-Cr-AlgO catalysts were calcined in flowing air
at 500 C for 16 hours. Calcination burned on the organic acid and decomposed the
vanadate to V2O5, decomposed the ferric nitrate and oxidized Cr(HT) to Cr(VI).
5.1.4. Summary of Catalyst Physical Properties
Table 8 summarizes the physical characteristics of the catalysts selected for
further study in the parametric and SCL durability studies. The pertinent parameters
are surface area, pore volume, bulk and particle density and average pore radius.
Pore volumes were measured by acetone absorption and bulk densities by mercury
displacement. BET surface areas were determined by N2 adsorption at the normal
b.p. of liquid nitrogen. Average pore radii were calculated from measured
surface areas and pore volumes.
TABLE 8. CATALYST PHYSICAL PROPERTIES
Surface Pore Bulk Particle Av. Pore
Catalyst Area Volume Porosity Density Density Radius
(sq. m/gm) (cu cm/gm) (% ) (gm/cu cm) (gm/cu cm) (A)
Filtrol Grade
86 Support
15# V0O_
A O
10$ Fe-Cr
(9/1)
270
220
260
0.68
0.48
0.60
70
58
69
1.02
1.21
1.16
3.38
2.90
3.72
51
44
45
5.2. Task 2. PARAMETRIC INVESTIGATION OF VANADIA AND IRON-CHROMIUM
CATALYSTS IN THE PRESENCE OF
In addition to the determination of the effect of the presence of SO on the tem-
perature-activity characteristics of V O and Fe-Cr catalysts during short and long-
term exposure, as stated in the title of this study task, a concurrent objective was to
develop rate expressions for the catalysts suitable for design use. The rate expres-
sions should represent intrinsic surface rates, including the effects of O2, H2O and
CO as well as SO , s.o that reasonable predictions of performance over a wide range
of operating conditions can be made.
46
-------
The approach used in this task was to vary widely the operating parameters about
the standard flue gas conditions (125? CO2> 3#O , S^HgO, 1000 ppm NO, stoichio-
metric or excess NH~ in Ng at 400° C and 20,000 hr-1 (STP) space velocity. The
parameters were varied individually or in various combinations. After establishing
tentative performance characteristics in the absence of SOx, the test procedure was
repeated, in part, with SCL. added to the flue gas. The data were correlated in the
X
development of empirical rate expressions.
At the conclusion of the parametric test program each of the catalysts was sub-
jected to long-term exposure to SOX under operating conditions. The important para-
meters, such as temperature, NH.,/NO ratio, and space velocity were varied during
the durability test program.
5.2.1. Parametric Studies
The results of previous studies and those obtained in Task 1 indicated that con-
version of NO in flue gas was the result of several parallel and consecutive processes.
Both V O_ and Fe-Cr catalysts exhibited maxima in conversion as a function of tem-
perature and both were sharply influenced by the presence of O0.
£
For design use, it Is desirable that working rate expressions be as simple as
possible. To meet this objective, power law rate expressions were used to corre-
late the experimental kinetic data. The effects of CO , I^O, O could be incorpora-
ted as individual concentration-reaction order terms. A thorough kinetic evaluation
involving surface phenomena and reaction mechanisms to determine the role of each
species was deemed beyond the scope of this project.
The NO-NEL reaction is sufficiently complex that the determination of a single,
simple rate expression which will be valid over entire spectrum of possible flue gas
conditions is not likely. The rate of NO reduction on both catalysts was markedly in-
creased by increases in O content at low O« levels. Above about 0.5$ the conversion
of NO was not as markedly increased with increase in O?. Depending on temperature,
O2 may have either an enhancement or an inhibition effect on removal of NO. Although
the influence of H9O and CO2 on the rate of reaction was not known, the exhaust of
fossil fuel-burning plants will never be devoid of CO2 or H^O. Therefore, it is rea-
sonable to examine only the expected concentrations of these species for fuels ranging
from coal to natural gas. In the earlier program, the presence of SOX at concentra-
tions of 1000-1500 ppm did not appear to influence the reduction of NO in excess NH3.
However, a poisoning term may be required in the rate expressions at higher SOX
concentrations.
The most difficult task is the mathematical representation of the rate of reduc-
tion of NO near and above the temperature of maximum conversion. Two approaches
were considered. First, simple separate rate expressions for apparent conversion
of NO may be developed to define the ascending and descending portions of the con-
47
-------
version curve. Second, since the maximum in the conversion of NO is probably
caused by the onset of NH oxidation with subsequent depletion of the reducing agent
(and, frequently, the actual production of NO), it may be possible to combine a single
expression for the rate of reduction of NO with a parallel rate expression for the oxi-
dation of NH .
O
The experimental approach that was followed in the parametric tests was to
first use the standard simulated flue gas mixture typical for coal combustion (12$
COg, 5$ HgO, 3# O ) varying the NO concentration from 250 to 1500 ppm and the NHL
concentration between about 0.5 to 1.5 times the stoichiometric requirement for each
NO concentration. Then, at the maximum conversion point with each NO/NBL ratio,
the CO2 and HO concentrations were perturbed from the standard flue gas concen-
trations to the maximum and minimum values expected in actual use (e.g., from
about 8$to 15< CO and from about 3$ to IS^ELO). Also, additional tests were con-
ducted with gas containing neither CO2 nor HoCT(for use as a reference base).
The effect of changes in the O2 concentration were investigated at concentra-
tions of NO of 750 ppm and 1000 ppm with at least two concentration levels of NH«
(stoichiometric and 1.5 times stoichiometric) and oxygen concentrations varying Trom
0 to 5 % . In these tests, temperatures were varied from 280 to 500°C.
The last phase of the parametric tests included the addition of SOX at various
concentrations to the test gas. In this latter series of tests, the possible cross ef-
fects with H0O, O and NH0 were assessed by including SOX in a test matrix.
M 2 «3
5.2.1.1. VgO_ Catalyst
Table 9 presents typical preliminary parametric data obtained for the V O cat-
alyst at 20,000 hr~l space velocity for variations in temperature and concentrations
of NO , NH0 and O . The following tentative conclusions are indicated from the data:
X o 2
1. Nitrous oxide (NO) is not a significant product with the VnO- catalyst except
at high concentrations of NO and NH and then only at temperatures well
above that for maximum conversion (conversion maximized at 400°C).
2. Conversion of NBL continues to increase monotonically with temperature be-
yond the point of maximum NO conversion.
3. The NHq concentration influences NO conversion most strongly below about
1.5 times the stoichiometric level (i.e. NH../NO inlet concentration ratio of
1). Above this concentration ratio, excess NHg does not influence the reac-
tion substantially.
4. Varying the H2O concentration from 0 to 18$ does not have a significant in-
fluence on the conversion of NO.
48
-------
TABLE 9. PARAMETRIC STUDIES TEST DATA - V0O_ CATALYST
-------
TABLE 9 (cont.)
Inlet Gas Composition
NO
X
(ppm)
770
n
u
it
975
tt
it
tt
980
tt
tt
M
980
M
ft
If
985
n
it
M
1005
995
n
it
1460
tt
it
it
1475
1460
tt
tt
1410
it
™3
(ppm)
1189
it
tt
tt
524
tt
tt
tt
583
tf
tt
tt
957
967
tt
tt
1259
tt
u
u
1480
1468
it
tt
781
it
it
M
1002
967
it
it
1457
it
C°2
(%)
12
M
it
it
12
tt
tt
it
12
n
tt
tt
12
tt
ti
n
12
M
tt
M
12
M
M
It
12
tf
n
tt
12
ti
tt
tt
12
it
H2°
(%)
5
tt
tt
ti
5
tt
tt
it
5
it
tt
it
5
tt
ti
M
5
n
n
ti
5
tt
M
It
5
tt
it
tt
5
tt
it
tt
5
tt
°2
(%)
3
it
it
tt
3
ti
IT
tt
3
tt
it
n
3
tt
n
n
3
it
M
n
3
M
ii
M
3
it
tt
n
3
n
it
tf
3
it
Outlet Gas Comp. Temp.
Conversion of
NO
X
(ppm)
560
215
100
205
715
405
370
535
705
425
405
537
710
340
205
385
720
275
160
305
735
275
105
275
1100
740
675
815
1090
645
545
785
1040
460
NO
2
(ppm)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
NH
3
(ppm
851
676
466
140
396
140
0
0
350
128
70
0
641
326
198
70
758
513
303
140
1270
816
629
221
455
150
0
0
466
210
93
0
1084
548
NO
200
300
395
495
200
300
400
490
200
300
400
495
200
300
400
495
200
300
400
495
200
300
395
495
200
300
400
500
200
300
395
495
200
300
27
72
87
73
27
58
62
45
28
57
59
45
28
65
79
61
27
72
84
69
27
72
89
72
24
49
54
44
26
56
63
46
26
NH
28
43
61
88
24
73
100
100
40
78
88
100
33
66
80
93
40
59
76
89
14
44
57
85
42
81
100
100
53
78
90
100
67
(continued)
26
62
50
-------
TABLE 9 (Cont.)
Inlet Gas Composition
Outlet Gas Comp.
Conversion of
NO
X
(ppm)
1485
1475
tt
tt
1485
tt
it
M
1025
M
it
1070
985
1030
M
990
1000
960
850
11
M
965
970
950
it
n
1000
985
955
990
n
tt
ft
M
NH3
(ppm)
1980
1980
M
tf
2400
n
tt
M
676
it
it
"
"
1480
"
1503
tt
tt
1165
it
tt
1165
"
734
ti
tt
"
n
n
1442
n
it
it
ii
C°2
(%)
12
it
ii
it
12
it
tt
M
12
8
14
12
tt
12
8
14
12
if
12
8
14
12
n
12
8
14
12
tt
it
12
ti
ti
11
M
H2°
(%)
5
n
it
tt
5
n
ii
it
5
tt
it
10
0
5
"
"
10
0
5
ti
n
10
0
5
tt
n
10
0
0
5
11
M
n
"
°2
(%)
3
tt
"
n
3
tt
ti
"
3
tt
M
n
n
3
tt
it
it
n
3
"
n
tt
n
3
n
it
11
ft
n
5
3
1
0.5
0
NO
X
(ppm)
1090
435
225
485
1070
415
175
370
395
370
390
405
335
95
105
140
135
85
155
140
165
n
105
245
225
235
n
165
175
105
135
167.
195
845
N2°
(ppm)
0
0
0
100
0
0
0
100
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
NH3
(ppm)
1755
1165
635
233
1865
1492
1165
350
0
0
0
0
0
338
326
536
338
299
443
456
443
n
tt
93
186
105
163
93
116
559
513
606
653
1235
(°C)
200
300
395
495
200
300
400
500
400
tt
n
tt
"
400
ti
"
M
1!
400
tt
"
n
it
400
it
"
it
n
it
400
ti
tf
It
NO
(%)
27
71
85
67
28
72
88
75
62
65
62.
62
66
91
90
86
87
91
82
84
81
83
89
74
76
75
77
83
82..
89
86.
83
80.
15
(continued)
NH3
(%)
11
41
68
88
22
38
52
85
100
n
n
tt
tt
77
78
64
77
80
62
61
62
tt
ti
87
75
86
78
87
84
61
64
58
55
14
51
-------
TABLE 9 (cent).
Inlet Gas Composition
NO
X
(ppm)
985
tt
1050
tt
it
990
990
970
1030
1070
1070
990
980
1020
1025
1080
985
970
1020
1060
1075
955
970
990
1035
995
490
500
570
599
590
510
510
560
565
560
NH
3
(ppm)
1491
M
1445
"
tt
1492
1459
1459
1459
1459
1459
652
652
641
641
641
688
688
688-
676
676
699
699
699
676
676
384
M
tt
tt
tt
734
"
it
it
"
CO
2
(%)
12
tt
tt
"
n
"
ti
it
M
ti
it
n
it
it
tt
it
M
it
M
n
M
n
M
tf
M
It
12
it
it
it
it
12
"
"
tt
"
H O
2
(%)
5
it
it
it
tt
tt
"
it
it
M
"
It
"
II
It
It
II
It
II
II
"
tf
It
"
It
"
5
"
tt
"
M
5
tt
M
tt
it
Q
2
(%)
5
3
1
0.5
0
3
3
5
1
0.5
0
3
5
1
0.5
0
3
5
1
0.5
0
3
5
1
0.5
0
5
3
1
0.5
0
5
3
1
0.5
0
NO
X
(PPmj
235
257
305
375
885
300
320
290
340
435
845
450
405
475
525
905
305
280
350
395
855
475
500
535
565
755
180
185
240
270
430
140
150
180
200
440
Outlet Gas Comp. Temp. Conversion of
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
NH
3
(ppm)
858
904
816
ii
1457
210
210
186
0
185
1014
221
210
220
198
454
0
0
175
116
478
0
0
47
186
396
175
198
210
245
303
373
396
420
443
664
(°C)
300
tt
tt
n
tt
490
500
"
tt
tt
tr
300
ft
ti
it
"
400
ii
n
n
M
500
"
it
it
"
300
M
"
it
it
300
tt
M
tt
"
NO
(%)
76
74
71
62.
10
70
68
70
67
59
21
55
59
53
51
16
89
71
66
63
20
50
49
46
45
24
63
63
58
55
27
73
71
68
65
21
NH.
(%)
43
39
43
36
2
86
86
87
100
87
30
66
68
66
69
29
100
100
75
83
29
100
100
93
72
41
54
48
45
36
21
49
46
43
•40
10
(continued)
52
-------
TABLE 9 (cont).
Inlet Gas Composition
Outlet Gas Comp.
Conversion of
NO
X
(ppm)
490
500
520
515
540
495
485
525
535
520
490
505
530
520
530
480
435
520
n
540
810
800
850
865
855
795
790
880
870
885
750
780
835
840
850
™3
(ppm)
373
"
tt
it
M
781
»»
tt
it
it
781
M
n
769
M
352
ti
"
"
M
1130
H
it
it
-"
580
ti
n
tt
tt
571
it
tt
n
tt
2
(%)
12
"
tt
tt
n
12
tt
tt
"
if
12
"
"
tt
tt
12
M
tf
II
It
12
"
H
"
tt
12
"
"
"
ti
12
it
n
tt
ti
2
(%)
5
"
M
II
tt
5
"
n
tt
"
5
"
"
tt
ti
5
"
"
n
n
5
"
"
H
tt
5
tt
it
it
H
5
"
tt
tt
n
°2
(%)
5
3
1
0.5
0
5
3
I
0.5
0
5
3
1
0.5
0
5
3
1
0.5
0
5
3
1
0.5
0
5
3
1
0.5
0
5
3
1
0.5
0
NO
X
(ppm)
155
170
190
200
320
125
130
135
150
275
270
265
325
320
330
335
370
370
380
365
172
190
250
300
690
275
300
395
475
770
260
270
335
350
625
NH3
(ppm)
0
0
105
tt
280
326
338
361
385
536
93
105
140
158
629
0
0
0
47
193
571
594
710
664
990
117
140
152
175
385
58
82
105
163
290
N20
(ppm)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
CO
400
tt
ft
ft
ft
400
II
It
tt
tf
500
tf
tf
ft
tf
500
11
tf
"
"
300
"
tt
n
M
300
tt
n
it
tt
400
tt
tt
tt
"
NO
(%)
68
66
63
61
41
75
73
74
72
47
45
48
39
39
38
30
24
29
27
32
79
76
71
65
16
35
62
55
45
13
65
65
60
58
26
NH3
(%)
100
it
72
"
25
58
57
54
51
31
88
87
82
79
18
100
"•
«»
87
45
50
47
37
41
12
80
75
74
70
34
90
86
82
72
49
(continued)
53
-------
TABLE 9 (cont.)
Inlet Gas Composition
Outlet Gas Comp. Temp.
NO
X
ppm)
760
770
800
870
890
tt
785
775
860
855
885
750
800
815
tt
NH
3
(ppm)
1095
ti
1107
it
"
tt
1105
tt
tt
"
ti
548
n
"
tt
con
2
(%)
12
"
tt
n
it
it
12
it
tt
tt
"
12
it
tt
tt
H O
2
(%)
5
it
M
it
tt
it
5
ti
tt
tt
tt
5
tt
it
tt
O
2
(%)
5
3
ti
1
0.5
0
5
3
1
0.5
0
3
1
0.5
0
NO
X
(ppm)
155
160
155
185
205
730
340
367
380
397
635
495
515
545
530
NH
3
(ppm)
408
443
385
396
419
839
117
128
152
163
862
0
35
58
198
N
(PI
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
400
it
ti
it
n
495
tt
ti
M
n
495
ti
n
ti
Conversion of
NO
80
79
80
79
77
18
57
53
56
54
28
34
36
33
35
63
60
65
64
62
24
89
88
86
85
22
100
94
89
64
20, 000 hr space velocity
54
-------
5. The influence of CC>2 on NO conversion appears to be quite small between 8
and 14^8 CO_. The largest effect observed is at stoichiometric NEL levels
or lower ana may be of only academic interest (all indications are that ex-
cess NH_ will be required for optimum NO conversion).
o
6. Oxygen strongly influences the rate of NO reduction below 0,5^ O« with either
stoichiometric or excess NEL. The effect is one of definite enhancement with
excess NH~. Interestingly, me enhancement effect is also-apparent at temper-
atures greater than that at maximum NO conversion. Previous work in this
laboratory, .with platinum catalyst; indicated that O« inhibits the NO reaction
at temperatures greater than that at maximum conversion (about 200°C with Pt).
The influence of the NH3/NO ratio on the conversion of NO is shown clearly in
Figures 17 and 18 for NO concentrations of 280 ppm and from 770 to 1485 ppm respec-
tively. It can be seen that with an NO concentration of 770 ppm or higher (Fig. 18),
the absolute NO concentration, at a given temperature, does not influence the rate of
NO conversion; instead, it appears that the reactant ratio and temperature controls
the conversion of NO. This observation was also made in the earlier program with
Pt, V0O and Fe-Cr catalysts.
2 5
Figure 17 shows a conversion maximum at NEL/NO ratios of about 1.1:1 at all
temperatures, whereas no such behavior is evident in Figure 18. It is not known if
this apparent difference in the relationship between conversion and reactant ratio for
low NO concentrations indicates a change in mechanism. It is possible that uncer-
tanties in establishing and maintaining the low flow rates may have magnified the ex-
perimental error. In fact, some difficulty was experienced in the operation of the
water vaporizer, which could have led to fluctuations in the total flow (and, hence,
concentrations) and back pressure.
Oxygen strongly affects NO conversion below 0.5% O_. The O, effect below 0.5$
O2 is shown clearly in Figures 19,20and 21 for 1000 ppm,790-890 ppm and490-6QO ppm
NO, respectively. Although the nitrogen carrier gas may contain as much as 1000 ppm
On, the data for "zero"O2 are shown on the ordinate. It is quite likely that conversion
for completely On-free conditions may be even lower than the values shown.
Even under "low excess air firing," ^ concentrations are rarely below 0.5$.
Furthermore, such near-stoichiometric combustion has not been fully perfected for
solid fuel (coal). Therefore, the projected mathematical modelling was designed to
cover O0 concentrations above 0.5$ .
a
Reduction of NO is enhanced by Q^ up to the temperatures of maximum conver-
sion (400°C) for all NO levels. For 1000 ppm NO, enhancement was observed at
500°C with both NEL levels (Figure 19). With 790-890 ppm NO, enhancement occurs
with excess NHg but not with stoichiometric NEL (Figure 20). However, with 490-
600 ppm NO, no significant enhancement occurs with either NHL level at 500°C (Fig-
ure 21).
55
-------
lOOr
0.7 Q9 I.I
REACTANT RATIO (ppmNH3/ppmNO)
Figure 17. Removal of NO with NH3 on VgO at low NO concentrations in simulated
flue gas. 280 ppm NO. (s.v.= 28,000 hr"1).
-------
lOO
80
eo
o
CO
IT
LU Ar.
> 40
o
o
20
400^
200°C
NOCONC
(ppm.)
770-805
975-1005
1410-1485
TEMPERATURE (°C)
200 300 40O
O
•
3
D
•
a
A
A
A
500
O
+
O
t5
0.7 0.9 I.I 1.3
REACTANT RATIO (ppm NH3/ppm NO)
1.5
1.7
Figure 18. Removal of NO with NH on V O at high NO concentrations in simulated
flue gas. (s.v.= a-
5t
-------
lOOr
0
A
NH,CONC. TEMPERATURE (°C)
(ppm) 300 400
1440-1490 O
641 -699 •
NO'985-l080ppm;CO£l2%
A
A
;H20= 5%
50O
n
•
234
OXYGEN CONCENTRATION (%)
J
5
Figure 19. Effect of Q£ concentration on NO reduction on VnOr in simulated
flue gas at high NO concentrations. (s.v.= 20,000 hr-1).
58
-------
A
D
O 300 °C
500 °C
400 °C
OPEN SYMBOLS-EXCESS NH3
CLOSED SYMBOLS-STOICHIOMETRIC NH3
_L
I
02 CONCENTRATION (%)
Figure 20. Effect of O2 concentration on NO reduction in simulated flue gas
on V2O5 catalyst at intermediate NO concentrations. 790-890
ppm NO, 12$ CO2, 5#H2O (s.v.= 20,000 hr"1).
-------
80r
o>
o
20
ts •
0
P.:-'
; 1
1
)
S0;~
A
a
o
i
i
500 °C
400 °C
300°C
i
OPEN POINTS-EXCESS NH3
CLOSED POINTS- STOICHIOMETRIC
i i i i .
234
02 CONCENTRATION (%)
N
I
5
Figure 21. Effect of O concentration on NO reduction on VgO in simulated
flue gas at low NO concentrations. 490-600 ppm Nu (s.v. = 20,000 hr"1).
-------
The absence of Oo enhancement of the reduction of NO at 500°C with stoichio-
metric NH3 for intermediate NO levels and with both stoichiometric and excess NH
for very low NO levels is not immediately obvious. Since the NHg-O reaction should
predominate at 500°C, the observed effect may be related to a balance between the re-
duction of inlet NO and the formation of NO from NKL oxidation.
O
The effect of water vapor on NO reduction in simulated flue gas was studied
by varying the water vapor concentration to 18$ (simulation of methane combustion).
The preliminary test results given in Table 9 indicated that NO conversion was not
appreciably changed between water vapor concentrations of 0 to 10$. Additional data
presented in Table 10 and Figure 22 show that conversion of 855 to 1030 ppm NO was
not affected by variable I^O concentrations with either stoichiometric or excess NH,,.
The preliminary observation that CO had only a slight effect on NO conversion
(Table 9) was confirmed by the results of additional tests shown in Table 11 and Fig-
ure 23. The effect on NO conversion over practical CO2 concentrations between 8 to
can be considered to be negligible.
A study of the effect of residence time (or space velocity) was made. Typical
data are shown in Figure 24 along with representations of data taken at 20, 000 hr~l in
earlier studies. It can be seen that conversion of NO is not significantly affected by
reactor volume at a constant space velocity (10, 000 hr~*) indicating negligible bulk
diffusion effects at that space velocity. An increase in space velocity (decrease in
residence time) causes a definite decrease in conversion as expected.
The fact that CO£ and ELO had negligible effects on the rate of reduction of NO
eliminated the necessity for incorporating concentration terms for these species in
the rate expression. The slight increase in conversion of NO with increasing Oo con-
centration above 0.5- indicated that a power-law reaction order for Q^ would be
finite but quite small.
The parametric data were correlated for individual concentrations of ©2 by the
method of minimization of the sum of squares of the difference between experimental
and calculated reaction rate constants, as described in Section 4. Initial data reduc-
tion was based on the global rate for the test system employed. In this initial analy-
sis, bulk and internal diffusion effects are not considered. A least square fit of the
logarithm of the rate at various G£ partial pressures versus the logarithm of Oo par-
tial pressure was then performed for the individual ©2 concentrations. The rates
used in this regression were calculated from best-fit reaction- rate parameters (E,
activation energy, A, pre-exponential factor, n, reaction order for NO and m, reac-
tion order for NH«) determined for sets of data at constant ©2 concentrations.
The apparent reaction order for O« determined by the above technique was 0. 05.
A rate expression of the form,
61
-------
TABLE 10. EFFECT OF WATER VAPOR CONCENTRATION ON REDUCTION
OF NO ON V2O5 IN SIMULATED FLUE GAS
Inlet Gas Composition
NO
X
(ppm)
855
ii
915
950
990
1050
915
tt
970
990
1030
1050
NH3
(ppm)
664
M
"
653
M
tt
1433
it
tt
M
"
it
°°2
12
M
it
it
tt
n
12
M
II
fl
II
tt
H2°
0
1
3
5
10
18
0
1
3
5
10
18
°2
3
M
II
M
M
tl
3
tt
ii
M
11
It
Outlet Gas Comp.
NO
X
(ppm)
290
300
285
305
350
370
150
160
164
11
170
tt
(ppm)
0
0
0
0
0
0
256
ti
490
559
629
676
(ppm)
.0
0
0
0
0
0
0
0
0
0
0
0
Temp.
CO
400
"
tt
it
M
it
400
it
ii
"
it
ti
Conversion of
NO
66
65
69
68
65
ti
83
82
83
"
M
84
NH3
100
II
II
It
ft
II
82
M
66
61
56
53
s.v. = 20,000 hr"1
-------
-0
P
CONVERSION OF NO (
OJ at ->l
~0 0 ^0
L A A A
A A
O
A
i i
) 5 10
A
EXCESS NH3
STOICHIOMETRIC NH3
i i
15 20
WATER VAPOR CONCENTRATION 1%)
Figure 22. Effect of water vapor on NO reduction in simulated flue gas at 400°C
onV.O. 855-1030 ppm NO, 12% CO., 3 O0. (s.v.= 20,000 hr'1).
4 O £ a
-------
TABLE 11. EFFECT OF CO2 CONCENTRATION ON CONVERSION OF NO ON V2O
Inlet Gas Composition Outlet Gas Comp. Temp. Conversion of
NO NH
x 3
(ppm) (ppm)
915 1468
995 "
it it
M it
990
995 "
M ii
965 746
M M
1000 "
990 "
M M
II M
995 "
C°2
(%)
0
1
3
5
12
14
20
0
1
3
5
12
14
20
2
(%)
5
it
it
M
ii
IT
It
5
ii
it
M
M
II
M
00 NO
2 x
(%) (PPm)
3 100
" 125
" 130
" 140
" 160
11 170
" 170
3 305
M it
340
It M
" 355
" 365
" 360
NH3
(ppm)
513
it
524
559
489
559
524
105
58
70
it
82
70
"
N20
NO
(ppm) (° C) (%)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
400
it
it
IT
IT
M
IT
400
"
"
"
M
M
II
89
87
86
it
84
83
it-
68
"
66
IT
64
63
64
s.v. = 20,000 hr'1
65
M
64
62
67
62
64
86
92
91
ti
89
91
64
-------
80
i
0 (
fe 60
0
CO
o:
UJ
2 40
o
o
s>n
A * A
^_ o
o
A 1470 ppm NH3
O 746 ppm NH3
•
1.1.1,1.1.1.1.1.1.1
6 8 10 12 14 16
C02 CONCENTRATION (%)
18 20
Figure 23. Effect of CC^ on NO conversion in simulated flue gas at 400°C on
V2O5. 915-995 ppm NO, 3 £ O2> 5$ HgO. (s.v.= 20,000 hr"1).
-------
lOOr
80-
60-
co
£
40
8
20
NH3
CATALYST CCNC.
CHARGE (pom)
14ml 1200 A
720 O
28 1240 a
700 O
14
10,000 hr'1
.-I
I
_L
300 40O
TEMPERATURE (°C)
50O
Figure 24. Effect of space velocity on conversion of NO in simulated flue gas
on V2O5. 980 ppm NO, 12$ CO , 3# O2, 5% HgO.
66
-------
. -E/RT n m 0.05
rate = Ae PNQ p p
o ft
was then used.
A second iteration of the procedure for the determination of A, E, n and m was
performed to refine the preliminary values. The new parameters thus obtained were
used in a second computer program which determines the conversion of NO from the
assumed rate expression for the experimental inlet concentrations and temperatures
(see Section 4). As before, interparticle and intraparticle diffusion resistances were
not considered in the determination of the global rate expression. The calculated and
experimental values for conversion were then compared and several additional adjust-
ments in the reaction rate parameters were made until a minimum in the differences
between calculated and experimental conversion was obtained.
The final global rate expression which provides the best agreement between ex-
perimental and calculated conversion values for T £400°C is
,, 0 -3650/RT 0.5 0.4 0.05, , XT^, , . , . %
rate = 14.8 e p Q p p (moles NO/gm catalyst - hr) (A)
3 2
It should be emphasized that the above power law rate expression is only an empirical
representation of the experimental data and does not imply any actual reaction mech-
anism.
The global rate expression (A) was then used as a first approximation of the in-
trinsic rate expression (which describes the rate of the surface reaction) in the itera-
tive calculation of the conversion of NO in which the effect of external and internal
mass and heat transfer was considered. The step-by-step procedure involved the
determination of the effectiveness factor for reactor length increments. The indivi-
dual kinetic parameters (A, E, m, n) were adjusted until the best agreement between
experimental and calculated percent conversion of NO for all runs was achieved.
The intrinsic rate expression that best describes the data up to 400°C is,
» ne ,n3 -9650/RT 0.30 0.22 0.05, , XT^, . . .
rate = 2.05 x 10° e p p p (moles NO/g cat-hr) (B)
3 2
Equation (B) predicts conversion of NO well, as shown in Tables 12a and 12b , for
space velocities of 20,000 hr~^ and 10,()00 hr~l, respectively. The differences in
the activation energy and the reaction orders between Equations (A) and (B), and the
low effectiveness factor values indicate substantial pore diffusion effects.
For temperatures above 400°C, two approaches were used to establish a work-
able global rate expression. The simplest technique was to fit directly the experi-
mental data for NO conversion to a power law rate expression. The resulting expres-
sion which provided the best fit of all data for T >_ 400°C is:
67
-------
TABLE 12a. EXPERIMENTAL AND CALCULATED CONVERSION OF NO ON VgO -
g BASED ON INTRINSIC RATE EXPRESSION (20,000 hr-1, Temperature < 4050°C)
Inlet Partial Pressures
Temp.
(°C)
205
200
200
200
200
200
200
200
200
200
200
200
200
305
300
305
300
300
300
300
300
300
300
300
300
300
395
400
400
400
400
400
400
400
400
395
400
400
P°
NO
(atm x 106)
285
275
280
770
770
985
980
1005
1475
1410
1485
1485
1460
285
280
785
805
770
770
980
995
1460
1410
1485
1475
510
770
785
770
770
985
980
850
990
990
1420
1410
1485
P°
NH3
(atm x 106)
315
359
365
921
1189
1259
957
1485
1002
1457
2400
1981
785
315
245
769
501
1189
921
967
1468
967
1457
2400
1981
734
1189
769
921
435
1259
967
1165
1433
1468
967
1457
2400
po
(atm x 102)
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
Conversion
Exptl.
<*)
39
31
32
27
27
27
28
27
26
26
28
27
25
77
63
70
61
72
70
65
65
56
67
62
61
71
87
80
84
74
84
79
82
83
84
73
83
78
Calculated
(*)
40
40
40
33
34
32
31
33
28
29
31
30
24
71
68
62
56
63
62
59
59
52
57
58
58
66
84
83
84
69
83
81
84
83
83
73
79
80
(continued)
TI, Effec-
tiveness
Factor
0.14
0.14
0.14
0.18
0.17
0.18
0.19
0.18
0.22
0.21
0.19
0.20
0.18
0.05
0.05
0.06
0.07
0.06
0.06
0.07
0.07
0.08
0.07
0.07
0.07
0.05
0.02
0.03
0;02
0.03
0.03
0.03
0.02
0.02
0.02
0.04
0.03
0.03
68
-------
TABLE 12 a (cont.)
Inlet Partial Pressures
Temp.
(°C)
400
300
300
300
300
300
300
300
300
300
300
300
300
300
300
300
300
300
300
300
300
395
400
400
400
400
395
400
400
400
400
400
400
200
200
200
200
200
200
po
N° ft
(atm x 10 )
1475
770
510
510
565
500
490
265
570
595
865
790
850
870
795
990
1000
980
1020
1075
1050
285
760
800
870
890
995
1030
990
990
990
990
1060
285
805
785
770
980
980
P°
NH3
(atm x 10b)
1981
1095
734
734
734
385
385
408
385
385
1130
580
580
580
580
1491
652
652
641
641
1445
315
1095
1107
1107
1107
1468
1480
1442
1442
1442
1442
676
256
536
769
455
664
583
P°,
°2
(atm x 102)
3
3
5
1
0..5
3
5
3
1
0..5
0.5
3
1
0.5
5
0.5
3
5
1
0.5
1
3
5
3
1
0.5
3
3
3
5
1
0.5
0.5
3
3
3
3
3
3
Conversion
Exptl.
<*)
85
79
73
68
65
63
63
66
58
55
65
62
55
52
60
62
55
59
53
51
63
86
80
80
79
77
89
91
86
89
83
80
71
32
22
26
24
29
28
Calculated
& )
80
84
67
65
63
62
63
72
58
57
60
58
55
54
59
59
55
56
53
51
59
89
85
84
83
81
83
83
83
84
82
81
73
38
30
32
29
29
28
^.Effec-
tiveness
Factor
0.03
0.02
0.05
0.05
0.06
0.06
0.06
0.04
0.07
0.07
0.06
0.07
0.08
0.08
0.07
0.06
0.08
0.07
0.08
0.08
0.06
0.02
0.02
0.02
0.03
0.03
0.03
0.02
0.02
0.02
0.03
0.03
0.04
0.15
0.20
0.18
0.19
0.21
0.20
69
-------
TABLE 12b. EXPERIMENTAL AND CALCULATED CONVERSION OF NO ON V O -
g BASED ON INTRINSIC RATE EXPRESSION. (10,000 hr-1, Temperature 148o°C)
Inlet Partial Pressures
Temp.
<°C)
300
400
300
300
300
400
400
400
pO
NO
(atm x 106)
960
970
970
980
970
970
1020
1000
P°
NH3
(atm x 106)
722
1189
1189
699
1239
1239
1445
932
O°
NH
(atm x 102 )
3
3
3
3
3
3
3
3
Conversion
Exptl.
<*)
71
91
87
71
82
87
90
86
Calculated
(*>
71
94
75
71
75
84
94
93
TI , Effec-
tiveness
Factor1
0.09
0.02
0.08
0.10
0.08
0.03
0.02
0.03
70
-------
8050/RT 09 05 02
rate =0. 30 e p " p ' p ' (moles NO/gm catalyst-hr) (C)
NO
The negative activation energy predicts decreasing rates of NO conversion with
increasing temperature, as observed experimentally. Table 13 shows reasonable
agreement between experimental and calculated conversion of NO. The largest dis-
crepencies occurred at 500 C with excess NH0.
«i
For the conditions to which Equation (C) applies, the apparent, net conversion
of NO decreases with increasing temperature because (a) NH is being depleted due
to reaction with Q and (b) under some conditions, NO is the product of NH oxidation
with O . It can be shown that in the absence of such competing reactions, line actual
rate or reduction of NO does not pass through a maximum over the temperature range
of this study.
A second method examined for correlating the kinetic data above 400°C used
Equation (A) in conjunction with an expression for NH,, reaction due to decomposition
and oxidation by O2 as measured under NO-free conditions. As an approximation, it
was assumed that the reactions were consecutive and the appropriate NH~ partial
pressure for Equation (1) was that remaining after the latter reactions. This study
was not successful. It is quite apparent that the individual reactions are not consecu-
tive as assumed. In fact, it has been shown (5-1) that even in the ascending- tempera-
ture region, for which an adequate empirical rate expression was obtained, the reac-
tions of NO, NH» and O are interrelated in a complex manner.
O £i
An analysis of the experimental kinetic data above 400°C considering external
and internal diffusion was not attempted.
5.2.1.2. Fe-Cr Catalyst
The selected 1056 iron-chromium oxide catalyst with an Fe/Cr ratio of 9/1 was
submitted to a parametric test program following the general procedure used for V2O
Preliminary tests were concerned primarily with establishing the effects of NO
and NH« concentration on conversion of NO. Table 14 summarizes typical data for
temperatures from 200 to 490°C with NO varying from about 320 to 1400 ppm and NH
varying in amount slightly below stoichiometric to a 3/1 ratio with respect to NO.
The standard flue gas composition (124CO2> 3#O2, 5$ H2O in N2) was used at 20,000
hr~* space velocity. Nitrous oxide was produced only with large concentrations of
NO at 490°C. The data indicate that conversion of NO is a function of the NHo/NO
ratio as observed with the VJD catalyst. Figure 25 shows this dependency for tem-
peratures up to 395°C -
As with the VgO catalyst, conversion of NO did not vary above NH3/NO ratios
of about 1.1 (0.67 NH^/NO is stoichiometric for conversion of NO to-Ng). For NHo/
NO < 1, a change in tne reactant ratie has a significant effect on the conversion of NO;
71
-------
TABLE 13. EXPERIMENTAL AND CALCULATED CONVERSION OF NO ON
V0O -ALO0 BASED ON GLOBAL BATE EXPRESSION (Temp.>400oC)
& 5 2 &
Conversion
Temp.
<°C)
400
400
395
400
400
400
400
400
400
400
400
400
400
400
395
395
400
395
400
400
400
400
400
400
400
400
400
400
490
49&
500
495
500
500
490
495
480
485
PNO
(atm x 10 )
1485
1410
995
980
805
770
990
1060
890
970
990
1020
990
870
1475
1460
1030
995
990
985
980
985
950
985
975
950
785
770
275
280
285
805
785
770
975
995
980
985
PNHg
(atm x 10 )
2400
1457
1468
583
501
921
1442
676
1110
688
1442
688
1442
1110
1980
967
1480
1468
1440
1259
967
690
655
688
524
1165
769
921
350
245
186
501
769
1189
524
1468
967
1259
p° Exptl. Calculated
°2 2
(atm x 10) (%) (%)
3
3
3
3
3
3
0.5
0.5
0.5
5
5
1
1
1
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
88
83
89
59
61
84
80
63
77
71
89
66
83
79
85
63
91
89
86
84
79
69
68
69
62
82
80
84
47
50
35
45
64
73
45
72
61
69
90
82
86
64
63
78
75
57
70
71
87
61
79
75
88
72
85
86
85
83
77
68
67
68
61
81
74
78
44
38
32
42
50
59
42
63
54
60
(continued)
72
-------
TABLE 13. (cent.)
Conversion
Calculated
J. Ci^JL^F*
495
495
495
495
440
500
500
500
495
495
495
N0 6
(atm x 10 )
980
750
505
275
265
520
520
520
860
800
815
(atm x 10 )
583
548
781
291
180
380
352
769
1105
548
548
°2 2
(atm x 10 )
3
3
3
3
3
0.5
1.0
0.5
1.0
1.0
0.5
(*)
45
50
48
35
57
27
29
39
56
36
33
<%)
44
45
55
40
52
31
33
42
51
38
35
s.v. = 20,000 hr'1. Simulated flue gas contains also 12
-------
TABLE 14. PARAMETRIC STUDIES TEST DATA - Fe-Cr CATALYST IN
SIMULATED FLUE GAS.
Inlet Gas Comp.
Outlet Gas Comp.
Conv. of
NO
X
(ppm)
950
940
955
950
805
815
805
740
420
465
450
465
345
335
340
315
325
325
505
480
465
470
460
915
915
745
800
745
760
1325
1375
1375
1325
*»»
(ppm)
746
957
1305
1859
559
670
897
1340
513
559
722
1165
489
676
1026
475
618
862
536
862
886
618
1084
723
1026
490
653
1002
1328
724
897
1375
2293
NO
X
(ppm)
920
890
940
815
765
770
755
590
400
430
420
385
325
315
310
205
195
190
280
300
255
280 •
255
640
630
430
450
410
440
920
915
900
860
NH3
(ppm)
676
862
1200
1773
524
629
823
1142
466
478
664
1085
466
629
956
315
443
676
291
618
629
396
850
147
850
233
385
653
962
375
501
897
1643
N2°
(ppm)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Temp.
(UC)
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
300
300
300
300
300
300
300
300
295
295
300
300
300
300
300
300
300
300
(continued)
NO
(%:
3
5
12
14
5
6
6
20
5
7
7
17
6
6
9
35
40
42
45
38
45
40
45
30
31
42
44
45
42
31
33
34
35
74
-------
TABLE 14. (cont.)
Inlet Gas Comp.
Outlet Gas Comp.
Conv. of
NO
X
(ppm)
490
535
545
1000
1000
1010
490
490
480
480
490
480
480
490
490
515
515
515
755
770
765
765
1010
985
955
965
990
1040
900
990
NH3
(ppm)
678
1077
1573
1574
2905
2905
520
884
1150
1450
884
1105
1450
520
460
775
1132
1524
569
775
1524
2290
557
920
1162
1474
800
920
1215
1501
NO
X
(ppm)
245
215
210
305
295
270
165
155
155
140
155
140
155
165
215
185
185
175
370
300
215
215
505
285
255
240
390
340
235
230
NH3
(ppm)
290
642
1040
546
1420
1307
121
278
448
932
278
448
932
121
60
106
206
355
48
97
290
533
0
133
254
399
89
121
166
266
N2°
(ppm)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Temp.
(°C)
390
390
390
440
440
480
440
440
440
440
440
440
440
440
480
480
495
490
490
490
490
490
445
445
445
445
490
490
490
490
NO
<*)'
50
60
61
70
71
73
66
68
68
71
68
71
68
66
56
64
64
66
51
61
72
72
50
71
73
75
61
67
74
77
(continued)
73
-------
TABLE 14 (cont.)
Inlet Gas Comp.
Outlet Gas Comp.
Conv. of
NO
X
(ppm)
1425
1435
1415
1435
870
770
795
785
785
890
520
515
520
560
475
1300
1400
1345
1290
1335
1335
780
805
770
390
405
395
405
555
565
540
555
™3
(ppm)
690
1132
1573
2397
1305
569
762
1015
1307
1015
460
544
859
1260
859
508
508
820
1130
1586
1586
763
1114
1935
524
792
1189
1573
629
758
1141
1573
NO
X
(ppm)
830
685
490
435
260
285
275
270
225
295
220
215
205
190
185
1020
1070
740
605
450
390
235
240
205
165
160
155
165
225
225
210
205
NH3
(ppm)
0
73
254
440
400
48
169
363
678
339
121
230
470
654
470
44
44
157
277
375
12
204
350
859
237
490
932
1107
28
40
718
1038
N20
(ppm)
0
65
80
75
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Temp.
<°C)
485
490
490
490
400
400
400
400
400
400
400
400
400
400
400
400
400
400
400
440
485
440
440
440
360
360
360
360
460
360
360
360
(continued)
NO,
<*)'
42
52
65
70
70
63
65
66
71
67
58
58
61
66
61
22
24
45
53
66
71
70
70
73
58
60
61
59
59
60
61
63
76
-------
TABLE 14. (cont.)
Inlet Gas
NO
X
(ppm)
1035
1030
1060
1080
1295
1340
965
965
965
965
Comp.
NH
3
(ppm)
522
788
1119
1608
1130
1608
533
932
1065
1465
NO
X
(ppm)
515
390
380
370
500
480
490
300
290
270
Outlet Gas
NH,
3
(ppm)
77
163
454
839
443
769
73
194
327
617
Comp.
N.O
2
(ppm)
0
0
0
0
0
0
0
0
0
0
Conv. of
Temp. NO
360 50
360 62
360 64
360 66
360 61
360 64
395 49
395 69
395 70
395 72
20, 000 hr~ (STP) space velocity
CO , 5$ HO, 3% O in N carrier gas present.
2 2 £t £t
77
-------
100
60
ppm NO
-------
and there is a trend toward increasing dependency on the reactant ratio with increasing
temperature. This result was also observed with the V2O catalyst. For tempera-
tures of 390°C and higher, Figure 26 shows that the conversion of NO is not dependent
on the individual concentrations of NO and NH3 but dependent on the NEU/NO ratio.
The lower and upper curves are for 400 and 440°C, respectively. The data indicate
that a broad maximum in conversion on the Fe-Cr catalyst occurred at 440°C and a
sharp decrease at temperatures above 400°C was not observed as was observed for the
V2°5 catalyst* Figure 26 also shows that conversion at 490°C (half-filled points) is
equivalent to that at 400<>C for low NH3/NO ratios and to that at 440OC for higher NH3/
NO ratios.
The broad maximum in conversion for the Fe-Cr catalyst offers the operational
advantage that temperature regulation of the reactor will not be as strict as for the
V_O5 catalyst. A single rate expression for design use up to 450°C should be appli-
cable. For instance, nominal operation at 425°C could tolerate a ^ 25° temperature
variation with only a 2% change in conversion.
The effects of H2O and CO2 on NO conversion were determined by varying the
ELO and CO2 concentrations about the nominal, simulated flue gas values. Carbon
dioxide concentration was varied from 0 to 20$ (nominal = 12$ ) and water vapor was
varied from 0 to 1858 (nominal = 5$ ). These effects were studied at 400 and 450°C
with both stoichiometric and excess NH3 for the CO2 tests and with excess NH3 for
the H0O tests.
U
Table 15 presents typical data for the parametric study. Figures 27 and 28
show that neither CO2 nor H2O have any appreciable effect on the conversion of NOX.
As with the V2O_ catalyst, such insensitivity to either constituent significantly sim-
plifies the development of the rate expression.
Oxygen concentration was varied from 0 to 5$ to determine the extent of the en-
hancement effect. Data were obtained for NO concentrations of about 750 and 950 ppm
with stoichiometric and excess NEL at temperatures from 300 to 450°C. Table 16
shows some typical data.
Figure 29 shows that with stoichiometric or excess NHg and at all temperatures
studied, the presence of a small amount of O2 produces substantial enhancement of the
conversion of NO. Above 0.5$ an increase in Og affects conversion only slightly. By
assuming that only O~ levels above 0.5# will be considered for design use (low excess
air firing cannot realistically be pushed to this low limit), the data indicate a positive,
near-zero reaction order for O . With VgOg, a low reaction order (0.05) was also
found. The nearly parallel NO conversion - O2 concentration curves above 0.5#O2 in-
dicate that the reaction order for O« will be essentially independent of temperature
and NO/NHQ ratio.
O
The effect of space velocity on conversion of NO was assessed in a series of
79
-------
lOOr
60
2- 60
O
u.
o
o
to
tr
UJ
o
o
40
20
CONG of NO
( ppm)
460-515
770-785
890-1040
1300-1435
I
390-400
O
D
O
TEMP(°C)
440-445
480-490
0.5
1.0
1.5
2.0
2.5
3.0
REACTANT RATIO
Figure 26.
Conversion of NO over Fe-Cr catalyst at temperatures above 390°C
in simulated flue gas.. (s.v.= 20,000 hr'1).
80
-------
TABLE 15. PARAMETRIC STUDIES TEST DATA - Fe-Cr CATALYST IN SIMU-
LATED FLUE GAS -EFFECT OF WATER VAPOR AND CARBON DIOXIDE
Inlet Gas Composition
NO
X
(ppm)
1005
1090
1005
1070
1070
1060
1000
1075
1000
1045
1040
1040
1055
1050
1090
1090
1095
1020
1030
1060
1095
1060
1035
1070
1050
1080
1105
1147
1127
1040
1100
1094
NHg
(ppm)
690
690
690
707
707
707
671
717
738
717
763
749
1185
1186
1186
1186
1186
1198
1198
1198
1185
1185
1198
1198
1186
1162
1162
1235
1154
1198
1186
1162
C°2
(%)
12
20
14
5
3
0
12
20
14
5
3
0
12
14
10
5
0
12
14
10
5
0
12
12
12
12
12
12
12
12
12
12
H2°
(%)
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
18
10
5
3
0
18
10
5
3
0
°2
(%)
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
Outlet Gas Com p.
NO
X
(ppm)
470
510
480
480
480
480
450
460
450
480
480
475
390
395
390
385
390
290
305
300
315
315
388
398
365
382
373
353
331
. 300
285
326
NH3
(ppm)
178
142
169
169
157
145
85
73
85
83
73
73
472
460
460
484
506
280
293
266
266
320
520
508
484
460
351
387
363
303
278
182
N2°
(ppm)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Temp
("C)
400
400
400
400
400
400
445
445
445
445
445
445
390
390
390
390
390
445
445
445
445
445
400
400
400
400
400
450
450
450
450
450
Conv. of
NO
(%)
53
53
52 .
55
55
55
55
57
55
54
54
54
63
62
64
65
64
72
70
72
71
70
63
63
65
65
66
69
71
71
74
70
81
-------
80f
450° C
-O—O-
400°C O"
1
0
1
5 10 15
INLET WATER CONCENT RATION (%)
2O
Figure 27. Effect of water vapor concentration on conversion of NO in simulated
flue gas over Fe-Cr catalyst (12$ CO , 3$ O , 1000 ppm NO,
1200 ppm NEL in N). (s.v.= 20,000 hr3-!). 2
~80
£
L
o /
L.60
0 /
CONVERSION
oS .
A 45O°C
i" • **
5 A 390 °C
) 0 Q 400-445
^ A .• i
7k 1
> 1200 ppm NH,
A Ai. -a 7
A A*
°C <^ n
_ W W 700ppm NH3 ° O
1 1 1
5
INLET C00
10 15
CONCENTRATION (%)
3
0
|
20
Figure 28. Effect of COo concentration on conversion of NO in simulated flue gas
over Fe-Cr eatalyst (5$ HO, 3$ O2> 1000 ppm NO in N2>
as specified), (s.v. = 20,000 hr-1).
82
-------
TABLE 16. EFFECT OF OXYGEN CONCENTRATION ON NO REDUCTION WITH
NH3 IN SIMULATED FLUE GAS -Fe-Cr CATALYST
Inlet Gas Comp. Outlet Gas Cpmp. Conv. of
NO
X
(ppm)
720
735
745
760
750
720
735
740
740
950
940
960
975
1010
940
1010
1015
1030
1065
725
720
760
760
800
920
950
960
990
1005
NH3
(ppm)
546
546
506
506
506
866
852
923
852
796
799
799
764
787
1227
1259
1283
1283
1283
908
908
905
905
905
750
750
750
706
653
°2
(%)
0
0.5
1
3
5
0
0.5
1.0
3.0
0
0.5
1.0
3.0
5.0
0
0.5
1.0
3.0
5.0
0
0.5
1.0
3.0
5.0
0
0.5
1.0
3.0
5.0
NO
X
(ppm)
670
500
480
460
435
650
475
465
490
875
680
640
590
600
905
715
880
645
630
615
305
295
265
265
820
475
455
445
440
NH3
(ppm)
484
346
333
320
266
759
626
618
545
666
472
436
417
426
1162
959
908
932
847
820
411
436
389
387
493
181
160
133
121
N20
(ppm)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Temp.
ro
300
300
300
300
300
305
305
305
305
305
305
305
305
305
305
305
305
305
305
400
400
400
400
400
395
395
395
395
395
NO
(%)
7
32
36
39
42
10
35
37
34
8
28
33
39
41
4
29
33
37
41
15
58
61
65
67
13
50
53
55
56
(continued)
83
-------
TABLE 16 (cont.)
Inlet Gas Composition
NO
Outlet Gas Composition
NO
A^ V^
X
(ppm)
955
980
990
990
1030
995
760
795
735
750
760
765
740
730
775
760
1050
970
965
990
1285
1390
1265
1015
1345
1460
925
960
780
710
735
770
1015
1055
3
(ppm)
750
750
750
557
557
557
587
587
557
557
557
557
610
777
777
111
777
845
845
845
1065
1065
1065
1065
760
760
830
830
448
448
1100
1053
1100
1100
2
(*)
1
3
5
1
3
5
1
3
1
5
1
3
5
1
3
5
3
1
3
5
3
1
5
3
1
5
1
5
1
5
1
5
1
5
Al^.^
X
(ppm)
870
840
860
925
920
900
690
660
680
645
610
580
560
590
570
555
825
800
750
740
1050
1145
990
820
1135
1140
755
730
615
525
505
485
695
640
3
(ppm)
690
633
640
480
440
425
533
520
488
460
425
405
725
700
654
700
702
665
615
847
896
812
599
533
738
605
424
344
980
738
799
741
2
(ppm)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
o-
0
0
0
0
0
.J. XS&JkA^
(°C)
205
205
205
205
205
205
205
205
205
205
260
260
260
260
260
260
260
260
280
260
260
260
260
260
255
255
255
255
240
250
300
300
300
300
A i -*~f
3
<*)
9
14
13
7
11
10
9
17
8
14
20
24
24
19
26
27
21
18
22
25
18
17
22
19
16
22
18
24
21
26
31
37
31
39
(continued)
84
-------
TABLE 16 (cont.)
Inlet Gas Composition
NO
x
(ppm)
(Ppm)
740 714
760 714
955 810
960 810
945 1485
960 1485
1300 1529
1375 1529
1335 865
1405 865
740
805
755
790
1030
1060
1005
1095
1030
1105
990
1050
1020
1040
685
780
760
800
1320
1318
639
639
639
639
905
905
703
726
1330
1330
1330
1330
1235
1235
706
720
°2
<*)
1
5
1
5
1
5
1
5
1
5
1
5
1
5
1
5
1
5
1
5
1
5
1
5
1
5
1
5
Outlet Gas Composition
NO
X
(ppm)
360
315
515
435
500
410
735
630
810
750
260
225
280
240
505
460
405
340
460
410
340
270
325
275
205
200
290
250
NH
3
(ppm)
363
278
424
322
973
884
826
666
426
280
612
400
213
120
133
100
194
206
169
107
460
373
360
293
426
332
194
121
NO
2
(ppm)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Temp
355
355
355
355
355
355
355
355
355
355
445
445
450
450
450
450
450
450
450
450
450
450
495
495
485
485
488
488
Conv. of
NO
x
<*>
51
58
46
54
47
57
43
54
39
47
65
72
63
70
51
57
60
69
55
63
66
74
68
74
70
74
62
69
(continued)
85
-------
TABLE 16. (cont.)
Inlet Gas Comp.
Outlet Gas Comp.
NO
X
(ppm)
920
920
915
960
970
NH0
3
(ppm)
1236
1234
1122
1234
1162
O0
2
(%)
0
0.5
1.0
3.0
5.0
NO
X
(ppm)
800
355
345
300
315
NHL
3
(ppm)
1017
508
488
436
392
N_0
2
(ppm)
0
0
0
0
0
730
750
765
765
795
932
918
905
905
905
0
0.5
1.0
3.0
5.0
525
275
260
235
230
639
266
242
182
226
0
0
0
0
0
Temp.
395
395
395
395
395
450
450
450
450
450
Conv. of
NO
13
61
62
69
68
28
63
66
69
71
-1
20, 000 hr space velocity
5% HoO, 12$ CO0 in N0, other constituents as given above.
£t c* &
86
-------
TEMP(°C) NO (ppm)
450°C EXCESS NH
400°C EXCESS NH
400°C,STOICH. NH,
1234
OXYGEN CONCENTRATION (Vol. %)
Figure 29. Effect of O2 on conversion of NO with Fe-Cr catalyst in simulated
flue gas (s. v.= 20,000 hr~l).
87
-------
tests using the 28-ml. reactor. Ammonia concentrations of 720 and 1200 ppm were
employed in standard flue gas containing 1000 ppm NO. Figure 30 shows typical data
along with representations of composite data taken at 20,000 hr-1 space velocity and
additional data for 10,000 hr"1^/^ flow rate) in the 14 ml. reactor. The conversion
maxima are seen to be broadened somewhat at the low space velocity. Above 400°C,
space velocity has little effect on NO conversion with either stoichiometric or excess
NHg. Above 350°C with excess NH3, reactor size has little effect for a given space
velocity (10, 000 hr~l) indicating that resistance to mass transfer from the bulk gas
stream to the catalyst surface is small for flow rates of that magnitude and larger.
The data were assembled in computer input format for determination of the
specific reaction rate constants (k) for various reaction orders of NO, NHg and On in
the rate expression,
, , m n q
rate = k PNO X P09
o &
The sum of the squares of the difference between individually calculated rate constants
and those determined from a least square regression of log k versus 1/T was deter-
mined for each set of m,n and q.
The reaction order values which resulted in the minimum sum of squares are
given in the global rate expression (the apparent activation energy and pre-exponen-
tial factor were the slope and intercept of the linear regression, respectively).
oo , -5400/RT 0.65 0.15 0.15 , ™ A. * i .
rate = 32.4 e p PVTTT Po (S131 moles NO/hr-gm catalyst (D)
O a
The small influence of oxygen on the rate of conversion of NO is reflected in
the low reaction order (0.15) which was, however, larger than that found for V2O5
(0. 05). The reaction order of NO was higher for the Fe-Cr catalyst (0.65 compared
to 0.5) and that of NH was lower (0.15 compared to 0.4) than for the V^O catalyst.
For both catalysts the sum of the reaction orders was 0.95 in the global ra\e expres-
sions.
The very broad maximum in conversion of NO on the 9/1 Fe-Cr catalyst pre-
cludes separate rate expressions for the ascending and descending portions of the NO
conversion-temperature curve. The single rate expression would be applicable to
450°C. Recommended operation is at 425°C, providing for a considerable tempera-
ture excursion (+ 25 C).
The intrinsic rate expression best describing the kinetic data, developed in the
iterative process described for the 9/1 Fe-Cr catalyst is:
o -10,860/RT 0.45 0.10 0.15, , „ . , , , _.
rate = 3.25 x 103 e PNQ PNH PQ (molesNO/gmcatalyst/hr) (E)
88
-------
80
£
o
Q
to
tr
ui
o
60
40
20
SPACE
VELOCITY
hr
-I
10,000
10,000
10,000
20,000
20,000
NH.
o
ppm
720
1200
1100
720
1200
VOL
CATALYST
ml
28
28
14
14
14
00
300 400
TEMPER ATURE(°C)
500
Figure 30. Effect of space velocity on conversion of NO IB simulated flue gas
on Fe-Cr.1000 ppm NO,
CO
H
2-
89
-------
Tables 17a andlTb list experimental and calculated conversion of NO based on Equa-
tion (E). Agreement is good for the 20,000 hr"1 data (Table 17a), but consistently
higher conversion of NO is predicted for 10,000 hr-1 space velocity (Table 17b). It is
probable that plug flow conditions were not attained at the lower space velocity.
As with the VgO catalyst, differences in activation energy and the reaction or-
ders between Equation (D) and (E) as well as the small effectiveness factors for the Fe-
catalyst indicate the existence of strong pore diffusion effects.
5.2.2. Durability Tests in the Presence of SO,,.
A primary objective of this project was to determine the effect of prolonged ex-
posure of the selected catalysts to SO^. In the previous study it was found that neither
catalyst suffered degradation for periods of exposure of about 50 hours. Target per-
iods greater than 100 hours were desired.
The procedure, initially, was to obtain durability data at the standard opera-
tional conditions: 20,000 hr-1 (STP) space velocity, 400°C reactor temperature, and
flue gas containing 1000 ppm NO, 700 to 1100 ppm NH3> 12$ CO , 3$ Og, 5£ H2O in
N_ with up to 2500 ppm of SOX.
5.2.2.1. V2O5 Catalyst
The "v^Og catalyst was first subjected to a series of intermittent exposure per-
iods of up to 9 hours or less. The intermittent periods were necessitated by. the lack
of capability, at that time, to handle the large volumes of gases involved. Subsequen-
tly, longer exposure periods were employed. Because of the large number of start-
up and shut-down periods, each test period with V2O consisted of initial steady-state
operation under SOx-free conditions. This data provided a reference base for com-
parison with operation in the presence of SOx« Steady-state runs with constant 6OX
concentrations were then conducted. After each such run, the SQx flow was termina-
ted and a second steady-state run was conducted in the absence orsOx. Periodic in-
let and outlet concentration measurements were performed during each test period.
Table IB summarizes the results of the SOX exposure tests with the VgOj. cat-
alyst. The SOo present was formed by homogeneous oxidation of the SO2 in the feed
system. The amount of SO3 formed in the catalytic reactor itself was quite small. 'Some
SO oxidation on the VO catalyst, although not alkalirdoped as is typical of QQ ox-
2 g ,
idation catalysts, was expected. However, the above results indicate that, under the
present conditions, a single, undoped V-O catalyst bed does not simultaneously re-
duce NO with NH3 and oxidize SO£ with D at 400°C.
The dashes in the beginning of the table represent analyses not performed for
the indicated species. In particular, the missing data in several tests include NH3
analyses of the reactor outlet gas in the presence of SOg- Even though the SOg/SO-
analytical method performed well, some difficulty in obtaining reliable NHg data with
90
-------
TABLE 17a. EXPERIMENTAL AND CALCULATED CONVERSION OF NO ON
Fe-cr-(9/1 ABASED ON INTRINSIC RATE EXPRESSION (20,ooohr-i).
Inlet Gas Concentrations
Temp.
(°C)
200
200
200
200
295
295
300
300
300
300
300
300
300
300
300
300
300
300
300
300
360
360
360
365
390
390
395
395
400
400
400
400
400
400
400
400
400
440
po
^ro
(atm x 106)
955
950
740
465
915
915
940
325
480
505
465
460
460
745
800
760
1375
1375
1325
1325
555
565
1030
1080
545
1055
965
950
1050
1005
860
785
890
785
785
770
1290
1335
po
NH
(atm x 106)
1305
1859
1340
1165
723
1026
957
618
862
536
886
1084
618
1002
653
1328
1375
897
724
2293
629
758
788
1608
1573
1186
932
1065
1186
690
1307
1307
1017
1017
762
569
1130
1586
PO
(atm x 106)
3
3
3
3
3
3
3
3
3
3
4
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
Conversion
Exptl.
<*)
12
14
20
17
30
31
38
40
38
45
45
45
40
45
44
42
34
33
31
35
59
60
62
56
61
63
69
70
65
53
70
71
67
66
65
63
53
66
Calculated
(*)
16
17
18
20
37
38
38
47
44
43
45
43
44
41
40
41
36
35
30
37
58
59
52
54
59
60
62
62
62
61
65
65
64
65
64
64
60
69
T), Effec-
tiveness
Factor
0.45
0.44
0.43
0.37
0.16
0.16
0.15
0.11
0.12
0.13
0.12
0.09
0.12
0.14
0.15
0.14
0.17
0.17
0.13
0.16
0.07
0.07
0.09
0.08
0.04
0.07
0.07
0.06
0.06
0.07
0.06
0.04
0.06
0.06
0.06
0.06
0.07
0.05
(continued)
91
-------
TABLE L7a fcont).
Inlet Gas Concentrations
Temp.
<°C)
440
440
440
440
445
450
445
450
485
490
300
300
300
300
305
305
305
305
305
305
305
305
305
305
305
300
300
300
395
395
395
395
395
395
395
400
400
400
400
450
pO
NO
(atm x 106)
805
490
480
480
985
945
1020
1140
1335
900
735
745
760
750
940
960
975
1005
735
740
840
1011
1015
1030
1060
1015
1055
770
710
760
920
915
970
950
960
720
760
760
800
795
po
NH3
(atm x 106)
1114
884
1150
1450
920
1162
1198
1198
1586
1215
545
506
506
506
799
799
764
787
852
925
787
1259
1283
1283
1283
1100
1100
1053
726
726
1234
1122
1162
750
750
908
905
905
905
905
*£
°2
(atir x 106)
3
3
3
3
3
3
3
3
3
3
0.5
1
3
5
0.5
1
3
5
0.5
1
5
0.5
1
3
5
1
5
5
1
5
0.5
1
5
0.5
1
0.5
1
3
5
5
Conversion
Exptl.
cO
70
68
71
68
71
73
72
74
71
74
32
36
39
42
28
33
39
41
35
37
43
29
33
37
40
31
39
39
59
70
61
62
68
50
53
58
61
65
67
71
Calculated
(*)
73
74
72
69
72
74
72
72
77
80
35
37
39
41
35
37
39
40
38
39
42
35
37
40
40
36
39
42
61
65
58
59
64
56
57
61
62
65
66
76
r\t Effec-
tiveness
Factor -
0.03
0.03
0.03
0.03
0.04
0.04
0.04
0.05
0.04
0.02
0.17
0.16
0.15
0.14
0.17
0.16
0.15
0.14
0.16
0.15
0.14
0.17
0.16
0.15
0.14
0.17
0.15
0.13
0.07
0.06
0.07
0.07
0.06
0.07
0.08
0.07
0.06
0.06
0.06
0.04
_ j\
92
-------
TABLE 17a (Cont.)
Inlet Gas Concentrations
Temp.
450
445
445
450
450
450
450
450
495
495
485
pO
NO
(atm x 106)
765
790
790
1060
1095
1105
990
1050
1020
1040
780
(atm x 106)
905
755
639
639
905
726
1331
1331
1331
1330
1235
P°2
(atm x 106)
1
1
5
5
5
5
1
5
1
5
5
Conversion
Exptl.
<*)
66
63
70
67
68
63
66
74
68
74
74
Calculated
<*)
72
71
75
67
73
71
70
75
72
69
80
T], Effec-
tiveness
Factor
0.04
0.05
0.04
0.03
0.04
0.05
0.05
0.04
0.03
0.02
u.02
Simulated flue gas contains also 12% CO2>5£ HgO in N .
93
-------
TABLE 17b. EXPERIMENTAL AND CALCULATED CONVERSION OF NO ON
Fe-Cr (9/1) BASED ON INTRINSIC RATE EXPRESSION (10.000 hr-1)
Inlet Gas Concentrations
Temp
<°C)
250
250
250
350
350
350
400
400
400
310
310
350
350
400
po
NO
(atm x 106)
1080
1065
1120
940
900
840
940
950
930
1055
1060
1060
1090
1075
po
NH3
(atm x 106)
1005
1005
1105
944
940
944
944
944
944
847
1095
1065
753
1116
P°
°2
(atm x 106)
3
5
1
1
3
5
1
3
5
3
3
3
3
3
Conversion
Exptl.
<*)
33
34
32
69
69
71
76
78
78
58
58
72
66
78
Calculated
(*)
41
44
37
68
74
74
80
85
87
60
61
73
71
84
T), Effec-
tiveness
: Factor
0.31
0.29
0.37
0.12
0.10
0.09
0.08
0.06
0.04
0.16
0.16
0.11
0.12
0.06
Simulated flue gas contains also 12£ CO2,5gH2O in N
94
-------
TABLE 18. DURABILITY TEST RESULTS - V2*
(ppm)
4)
703
703
0
1035
1035
0
0
500
0
1489
0
1982
0
1000
0
917
0
1000
0
1450
0
0
703
0
*>»
(ppm)
0
0
0
0
0
0
0
0
0
0
0
—
0
90
0
71
0
0
0
—
0
0
0
0
0
e
NH3
(ppm)
1160
1160
1160
1089
1089
1089
1065
1041
1041
1065
1065
1065
1114
1114
1065
1065
1100
1100
1100
1100
1020
914
1065
1162
1162
1089
Outlet Gas Concentration Conv. of
NO
X
(ppm)
145
180
105
160
115
130
160
110
115
105
105
100
110
175
130
90
145
140
140
230
115
140
115
145
105
160
S°2
(ppm)
0
691
—
0
e
0
—
0
1425
0
0
0
0
0
1320
0
0
691
0
S°3
(ppm)
0
—
—
0
—
—
0
0
—
0
113
0
—
0
—
0
—
0
—
0
42
0
0
—
4)
NH3
(ppm)
372
144
86
253
266
291
242
411
0
0
290
109
470
372
144
NO
<*)
86
84
91
86
88
88
86
89
89
90
90
90
90
84
87
92
86
87
87
87
89
87
89
86
91
86
95
-------
TABLE 18 (cont.)
Accumulated Inlet Gas Concentration
Outlet Gas Concentration Conv. of
Time
(hr)
112.0
Reference
Beference
118.5
Reference
128.5
Reference
137.5
145.0
Reference
163.0
Reference
172.0
Reference
176.5
204.5
Reference
313.0
480.0
552.0
599.0
628.0
641.0
648.0
NO
X
(pom)
1060
1140
940
1090
975
1150
.900
975
1125
1050
1050
970
1050
980
1110
1070
1070
715
1065
1070
940
1180
1020
1005
*>*
(ppm)
1035
0
0
1011
0
892
0
1977
2583
0
906
0
974
0
1087
1086
0
875
583
620
595
553
0
0
S°3
(ppm)
0
0
0
0
0
0
0
42
0
0
0
0
61
0
0
0
0
31
52
208
219
94
0
0
NH3
(ppm)
1090
1065
1286
1113
1126
1113
1204
918
1113
1574
1586
786
858
1145
1109
747
747
1225
706
716
884
1780
980
710
NO
X
(ppm)
130
160
165
175
175
230
145
185
150
85
135
260
195
145
145
120
145
60
130
30
50
70
130
215
S°2
(ppm)
-
0
0
1010
0
820
0
2065
2414
0
815
0
1073
0
994
1088
0
890
554
628
658
407
0
0
K3
(ppm)
-
0
0
51
0
50
0
31
52
0
48
0
52
0
28
26
0
42
42
52
219
188
0
0
NH3
(ppm)
86
253
310
97
303
153
315
250
152
508
303
61
60
232
97
30
145
318
93
—
319
671
436
—
NO
X
<*)
88
86
83
82
82
79
84
81
84
92
88
73
81
88
87
88
86
89
87
97
97
94
87
79
S. V. = 20,000 hr"1. Simulated flue gas contains also 12$ CO^
5$ H2O in N£.
96
-------
the Orion specific ion electrode was experienced. The erratic operation, which was
traced to a faulty electrometer used to measure the probe output, was corrected.
For the first 54 hours the usual procedure, as mentioned above, was to conduct
a single run of 9 hours or less. During the overnight periods, the catalyst was ex-
posed to flowing air at 400°C. Since these "rest" periods might obscure durability : '
data by providing intermittent catalyst rejuvenation, longer test runs were conducted
in subsequent stages. Catalyst deterioration was not observed for test periods up to
32 hours in length.
It should be noted that NO and NH« concentrations were not precisely the same
for reference and durability runs. Data for the durability tests were representative
of conditions near the end of a test period. Over extended periods, slight shifts in
concentrations occurred, particularly with NH~, the flow rate of which was subject
to the influence of the ambient temperature on the vaporization rate of the liquid
NH,,. Nevertheless, the data obtained at reference and run conditions indicate
that SOX did not affect NO conversion, which was maintained close to 90£ for excess
NH3.
The data indicate reasonable agreement within experimental error between inlet
and outlet total SO concentrations indicating, based only on these results, that solids
formation in the system was either negligible or had, in each case, reached an equili-
brium level. On the other hand, the outlet ammonia concentration invariably was
lower in the presence of SOX than in its absence. In most cases, the additional NH
usage could not be correlated with corresponding decreases in effluent SO . The fac-
tors influencing the increased usage of NH~ in the presence of SOX have not been re-
solved, but it is clear that the effect on NO_ conversion is negligible.
ji
It was of interest to determine if operation at lower temperatures would lead to
significant catalyst poisoning or salt deposition. Several runs were performed at
temperatures as low as 250°C in the presence and absence of SOX. Table IS shows
typical results with the concentration data given representative of those determined
near the end of the test periods. As observed at 400°C, NO conversion at lower
temperatures was not significantly altered by the presence of SOX« The results at
25QOC were surprising in that the anticipated formation of sulfites and sulfates was
expected to "poison" the ¥2 05 catalyst as observed with the platinum catalyst in our
earlier EPA program with TRW. The present data implies that classical sulfur
poisoning of the Pt catalyst rather than mere salt blockage may have actually occurred
in the earlier study although the Pt catalyst could be rejuvenated by heating in air,
at least after short exposure to SO^.
At the lower temperatures, significant oxidation of SO2 to SO3 on V2O occur-
red, but it is not certain if the effect is catalytic or homogeneous. Formation of
SO3 is thermodynamically favored over the entire temperature range employed and
for the reaction,
97
-------
TABLE 19. DURABILITY TEST BESULTS - V2O5 CATALYST INTHE PRESENCE
OF SOX AT TEMPERATURES BELOW 400°C.
Accumulated
Time
(hr)
204.5
Reference
220.5
232.0
Reference
236.0
Reference
238.0
243.5
267.0
272.0
Reference
Inlet Gas Concentration
Temp.
rc)
NO
X
(ppm)
S02
(ppm)
Accumulated
255
250
250
300
300
255
255
300
350
350
355
880
955
980
865
870
1035
1075
1085
1000
840
890
0
1188
1188
0
1024
0
1100
1100
1100
1100
0
S°3
(ppm)
*"»
(ppm)
Outlet Gas Concentratioi
NO
X
(ppm)
to start of series of
0
0
0
0
0
0
0
0
0
0
0
862
859
859
820
845
770
858
858
858
858
768
410
440
400
155
130
470
500
295
140
90
170
S02
(ppm)
tests
0
702
0
575
0
567
0
^3
(ppm)
0
528
0
539
0
507
0
NH,
*
(ppn
404
153
147
140
323
28
27
s.v. = 20,000 hr'1. Simulated flue gas contains also 12$ COg, 3$ O
NO
x
<*)
53
54
59
82
85
55
53
73
86
89
81
in N2.
98
-------
so2 + J02
K increases approximately by two orders of magnitude when temperature is de-
c?eased from 400 (Kp = 600) to 250OQ (K = 85,000). The failure to observe signifi-
cant SO- at the reactor inlet when the mixer-vaporizer temperature was reduced to
250°C (data not shown) suggests that below 400°C, the oxidation may be catalyzed on
the V2O5.
Immediately after introduction of SOX, NO conversion decreased (10$or less).
Recovery of initial activity appeared to be a function of temperature; at 250°C re-
covery took 2 to 5 hours while at 400°C recovery occurred in a matter of minutes.
The data in Tables 18 and 19 are steady-state results for each test period. Additional
data other than NOX conversion were not obtained during the recovery period. Tenta-
tively, the observed induction period for the recovery of activity implies that, initially,
formation of salts somewhere in the test system may have occurred, depleting the NH_
supply. Recovery indicates the attainment of a steady-state or equilibrium quantity of
the salt in accord with the satisfactory balances between steady-state inlet and outlet
SO as discussed earlier.
A
After about 200 hours, the gas handling capabilities of the laboratory were ex-
panded to enable long periods of continuous runs. During the overnight periods, the
catalysts were exposed to simulated flue gas containing 500 ppm NO, 500 ppm NH and
350 ppm SOX at 400°C.
Figure 31 shows that during the SOX exposure period the conversion of NOX was
consistent with pre-exposure data (the solid line is representative of pre-exposure
data). Also shown in the figure are several data points taken in the absence of SOX
after 600 hours of exposure to SOX- In general, no change in activity was evident.
The total exposure period for the durability test of the V2O5-A12O3 catalyst was 648
hours.
5.2.2.2. Fe-Cr Catalyst
As with the VoO5 catalyst, conversion data of the 9/1 Fe-Cr catalyst durability
tests were accumulated with the standard flue gas composition with either stoichio-
metric or excess NH_. The Fe-Cr catalyst was also normally exposed overnight to
simulated flue gas containing 500 ppm NO, 500 ppm NHg and 350 ppm SOX at 400°C.
Table 20 summarizes the conversion data obtained during the durability tests at
400°C. No significant degradation of catalyst performance was observed during the
1052 hours test.
The stability of the Fe-Cr catalyst is markedly different from the iron oxide-
chromium oxide catalyst studied by Matsuda et al (5-2). Their catalyst preparation
method was not specified (it may have followed the patent of Nonnenmacher and Kartte
(3-1)). In their study deterioration began immediately after exposure to 500 ppm SO0.
o
99
-------
O
O
lOOr
90
80
g70
u_
O
g
DC
LU
>
I
60
50
"40
30
20
10
ovO
O 0- 100 hrs
A 100-200 hrs
Q 300- 400 hrs
O 500-600 hrs
V S02-FREE DATA AT 648 hrs
SOLID LINE' PRE-EXPOSURE COMPOSITE DATA
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
I.I 1.2 1.3 1.4 1.5
NH3/NO INLET CONCENTRATION RATIO
^
Figure 31. Conversion of NO on VgO catalyst during SO exposure test in simulated
flue gas (1000 ppm NO) at 400°C. s. v. = 20/000 hr-1.
-------
TABLE 20. DURABILITY TEST RESULTS - Fe-Cr CATALYST IN THE PRESENCE
OF SO AT 400°C
Accumulated
Time
(hr)
reference
0..5
20
45
62
70
88
94
136
140
159
182
189
206
303
346
417
422
440
448
reference
472
478
reference
480
485
504
510
526
533
597
613
620
637
715
718
732
Inlet Gas Composition
NO
X
(ppm)
1160
1130
1060
1050
1045
1130
1110
1110
1095
1025
1025
1115
985
1070
1100
1075
1105
1090
1045
1060
995
1010
1095
1000
1030
1040
1000
1050
1085
1000
960
1000
1010
995
1050
1060
985
S°2
(ppm)
0
419
578
720
1044
570
673
704
554
673
669
0
665
0
574
377
518
449
390
589
455
953
*>»
(ppm)
0
225
173
187
62
52
52
73
41
156
61
0
61
0
61
167
52
133
167
104
37
83
NH3
(ppm)
670
670
668
1184
1106
1368
1184
1184
976
916
1036
808
976
903
916
667
736
1036
916
1183
652
634
Outlet Gas Composition Conv. of
NO
SO,
SO,
NH
NO
x 2 "3 -"3
(ppm) (ppm) (ppm) (ppm) (%)
470
480
420
415
405
440
275
265
360
340
275
260
255
230
280
315
295
300
160
160
285
245
270
310
330
320
385
320
350
350
215
155
175
150
390
380
360
000
521 159 16
549 176
673 259
764
653
634
258
474
669
600
609
0
504
340
382
83
20
52
83
83
69
21
104
0
105
192
188
58
30
33
76
91
19
43
34
112
38
0
27
31
48
380 177 127
497 31 55
653 31 71
409 57 390
1023 65 66
(continued)
60
61
60
60
63
61
75
76
67
67
74
77
74
79
75
71
73
73
85
85
71
76
75
69
69
69
62
70
68
65
78
84
83
86
63
64
64
101
-------
TABLE 20 (cont.)
cumulated Inlet Gas Composition
Time
(hr)
736
754
763
776
784
801
811
reference
873
897
923
945
997
1002
reference
1018
*1045
1050
1052
NO
X
(ppm)
980
1000
1020
1000
1045
900
940
900
930
935
940
920
1000
900
910
885
975
1115
1280
20,000 hr'1 space
5% H2O in
* 350 C
N2'
S°o
2
(ppm)
945
1430
1113
0
1251
1153
1157
967
920
1067
0
929
1185
1170
0
SO
3
(ppm>
—
187
60
52
0
94
63
59
68
89
19
0
41
84
511
0
NH
3
(ppm)
634
706
618
757
710
639
682
757
635
706
690
1077
1032
758
660
1373
velocity. Simulated
Outlet Gas Composition Conv. of
NO
X
(ppm)
360
305
310
340
320
275
280
315
315
270
250
255
235
205
125
135
280
—
280
flue gas
so0
2
(ppm)
— :
1031
1497
1051
0
1177
1158
1164
1028
966
970
0
880
1091
566
0
contains
SO
3
(ppm)
135
25
63
0
52
37
26
59
94
64
0
52
48
522
0
also 12$
NH
3
(ppm)
—
54
—
36
—
48
—
37
51
47
36
41
43
33
98
51
—
190
400
co2, :
NO
(to
63
70
70
66
69
70
70
65
66
71
74
72
77
77
86
85
71
— —
78
»^ ^"^O *"
102
-------
The catalyst recovered activity at 300 hours and then again deteriorated rapidly. At
about 800 hours the catalyst was about 654 as effective as before exposure. Matsuda
et al (5-2) attributed the deterioration of activity to the formation of iron sulfate from
the reaction of the catalyst with SO, .
In the present study, the inlet gas containing sulfur oxides was predominately
SO9 with SO concentrations roughly about 100 ppm on the average. Since the SO,
concentrations in the Matsuda study were higher (500 ppm), a direct comparison of
degradation effects may not be valid. However, there is no evidence for the direct
reaction of SO_ and FegCL on the UCLA Fe-Cr catalyst since inlet and outlet SO con-
centrations were approximately equal and total SOX balances were, in most respects,
reasonably close as shown in Table 20. Furthermore, several catalysts disclosed in
the patent literature (see Appendix A) for the removal of NO with NH involve pre-sul-
fation of the catalysts with either aqueous sulfates or oxides of sulfur. Therefore,
there is some evidence that certain metallic sulfates are active catalysts.
The degradation of the Fe-Cr catalyst in the Matsuda study may be due to SO -
carrier reaction. However, since details of the catalyst formulations in their worlc
were not provided, an external evaluation of their degradation data is precluded.
Nevertheless, SO»-alumina reaction is a possible cause for degradation of alumina-
supported catalysts. The extent and induction time for degradation should depend on
the type of active material and the ratio of active material to alumina. Such informa-
tion does not appear to be available, at least in the open literature.
Figure 32 shows that there was no overall decrease in the conversion of NO.
There was, in fact, the indication that the catalyst activity may have increased some-
what (the solid line is a composite of data for pre-SOx exposure tests), particularly at
low NH3/NO ratios (<0.65).
Typical data obtained during the overnight test periods with, nominally 500 ppm
NO, 400 ppm NH3 and 350 ppm SOX at 400°C are given in Table 21. Space velocity
was maintained at 20,000 hr~l (STP). Typical conversions ranged from 85-92$.
These percent conversions were considerably above the 400°C curve of Figure 26 for
comparable conditions studied before the catalyst was exposed to SOX.
Although Figure 32 shows, for higher NO and NH~ concentrations, a modest in-
crease in catalytic activity after initial exposure to SQ Table 21 indicates that, at
lower NO and NH concentrations, conversion of NO is markedly increased. The
third-to-last entry of the table, (SOx-free conditions) indicates that the improved
conversion over that observed prior to SOX exposure does not appear to be related to
the immediate presence of SOX itself but is a cumulative change in the catalyst.
The improvement in activity with aging in the presence of SOX for both 1000 and
500 ppm NO indicates that the rate expressions, which were based on the parametric
studies, apply to relatively fresh catalysts. For well-aged catalysts, the conversion
rates calculated from the developed rate expressions would give lower bound values.
103
-------
90
80
70
60
O
§40
V)
o:
ui ,_
> 30
o
o
20
10
O 0-100 hrs
A 300 - 400 hrs
O 500 - 600 hrs
O 700- 800 hrs
V S02-FREE DATA AT 700 hrs.
O 900-1000 hrs.
SOLID LINE'PRE-EXPOSURE COMPOSITE DATA
0.5
0.6
0.7 0.8 0.9 1.0
NH3/NO INLET CONCENTRATION RATIO
I.I
1.2
Figure 32. Conversion of NO over Fe-Cr catalyst during SOX exposure test
period in simulated flue gas (1000 ppm NO), 400°C, (s.v.=20,000 hr'l).
-------
TABLE 21. CONVERSION OF LOW CONCENTRATIONS OF NO IN PRESENCE
OF SO AT 400°C OVER Fe-Cr CATALYST
Accumulated Inlet Gas Composition
Time
(hr)
730
753
775
800
892
893
918
943
965
968
1014
NO
X
(ppm)
540
540
510
510
310
450
535
470
450
490
460
so2*
(ppm)
305
331
269
281
466
369
425
238
0
481
237
^3
(ppm)
—
—
42
—
—
84
31
44
0
83
68
m*
(ppm)
323
456
482
500
639
481
336
468
465
310
659
Outlet Gas
NO
X
(ppm)
65
100
80
105
25
65
75
75
70
75
75
S°2
(ppm)
270
262
388
0
241
Composition Conv. of
S03* NH3
(ppm) (ppm)
0
0
37
—
—
52
—
—
.0
—
52
NO
<*)
88
82
84
80
92
86
86
84
84
85
87
* Where dashes appear in SO column, the SO data include SO formed in
O £t u
in the feed system (i.e., for these cases SO actually represents SO ).
£ X
20,000hr space velocity. Simulated flue gas contains also 12$ CO ,
3% 0, 5# HOinN.
105
-------
Investigation of interaction of SOq and ALO or other carrier material is im-
portant. The concentrations of SO_ present in this project may have been too low to
induce catalyst degradation effects. Additional effort in this area either concurrently
or before advancement to demonstration scale of operation is highly desirable. Iden-
tification of the compound(s) formed and crystallinity changes during prolonged ex-
posure to higher concentrations of SO_, and methods to inhibit the degradation effects
as well as identification of carrier materials immune to the presence of SO are
particularly important.problems to be resolved.
5.2.3. Recommended Operating Conditions
Removal of large concentrations of NO (1000 ppm or greater) with NH in excess
can be achieved on both catalysts at the 80$ level or higher at a space velocity of
20,000 hr-1. Removal of approximately 90$ for lower NO concentrations has been
observed at that space velocity. At 10,000 hr-1, 90 to 100$ removal of NO is obtained.
An estimate of the capital and operating costs of non-noble metal catalysts as
adapted to an 800 MW power plant operating at 400°C and 15,000 hr-1 space velocity
has been made previously (1-2). Working capital and investment return have been
excluded. By assuming 10-year depreciation, and annual catalyst replacement, the
estimated costs (1973 dollars) are:
capital cost — $6.15/KW
operating cost — 0.088 t, I KWH
The most significant operating expense was, as expected, the cost of the NH^ feed.
Since catalyst rejuvenation/replacement was estimated to be less than 54 of both the
operating and the capital cost (initial charge), differences in the costs of the "V^O and
Fe-Cr catalysts do not change significantly the total capital and operating costs
5. 3 . Task 3 . INVESTIGATION OF NEW AND PROMISING CATALYSTS
The primary source of literature on NOX catalysis was a computerized search
provided by the UCLA library which was updated at biweekly intervals. The latter was
supplemented by compilations obtained from APTIC. Particular emphasis was placed
on selective reduction of NO with NHo, although the references were scanned for
.A *^
claims of selectivity in the presence of O2 with other reducing agents.
Applicable literature listings, as well as pertinent data (when available) such as
catalyst type, test conditions, and poisoning effects are tabulated in Appendix A along
with an overall bibliography (from which the catalyst list was assembled). Acquisition
of all the pertinent complete articles and patents was not possible during the course of
this project. Most of the tabulated data were obtained from published abstracts rather
than the complete articles.
The primary source of the literature was from patent filings and many of these
106
-------
were Japanese disclosures. Several of the patents were obtained and translated. Pre-
liminary inspection of the patent literature reveals that a large number of patents re-
lated to the basic disclosures of Nonnenmacher and Karrte (3-1) for vanadia, molyb-
dena and tungsten oxide catalysts and of Schmidt and Schulze (3-2) for iron-chromium
catalysts. It is beyond the scope of the present project to explore all the variations in
preparation of these catalyst types.
Several catalysts were of considerable interest and samples were prepared for
brief comparative studies. Two of the catalysts were reported by Hitachi Ltd. (5-3)
to be active for NO reduction with NH3 at 250°C in the absence of SO2 and at about
350°C in the presence of SO2. Both catalysts (5-4 and 5-5) apparently contain mixed
oxides of the general formula La2Cu1_xZr O4, which has a crystal structure similar
to K^NiF,. The two catalysts were prepared in our laboratory by dry pressing of the
mixed oxide with A^O (5-4) and by impregnation methods (5-5), respectively.
A third catalyst of interest was prepared by substitution of a portion of the VgO-
catalyst with an inexpensive active material in an attempt to reduce catalyst cost with-
out a loss in performance. The demonstrated high activity of iron-containing catalysts
suggested a binary mixture of VgO- and Fe-O . Consequently, a catalyst was pre-
pared by impregnation of A^O (Filtrol 86) with a solution of Fe(NO ) • 9 H2O and
NH^VCL with oxalic acid addea to increase the solubility of the latter (probably by
reduction of V+^ to V4^). The impregnated material was then calcined at 500°C. Final
total oxide concentration (Fe: T ratio of 1/1) was 155? •
A fourth catalyst was prepared by impregnating AL>O (Filtrol Grade 86) with a
solution containing NH^VOg and H2C2O (2:1 molar ratio),
-------
lOOr
oo
—-O
\
O HITACHI #1
V HITACHI #2
A A 10% Fe-Cr (9/1)
• O 15%
+ 15% Fe-V (I/I)
O 10% Fe-Cr-V (18/1/I)
CLOSED POINTS-20,000 hr'l S.V.
OPEN POINTS-10,000 hr'1 S.V
\
\
\
\
200
300
400
TEMPERATURE (PC)
500
Figure 33. Comparison of several active catalysts for NO reduction with NH
In simulated flue gas. 1000 ppm NO, 1200 ppm
-------
of SO increased activity for removal of NO with NHg in simulated flue gas. For the
duratfon of the test (186 hours), dsgradation of the catalytic activity was not observed.
TABLE 22. DURABILITY TEST RESULTS - 10^6 Fe-Cr-V (18/1/1) CATALYST IN
THE PRESENCE OF SO_ AT 400°C.
Accumulated
Time
(hr)
reference
56
80
100
128
133
163*
186
Inlet
NOx
(ppm)
1055
950
990
580
1240
1040
740
1120
Gas Composition
S02 S03 NH3
(ppm) (ppm) (ppm)
0
275
828
280
420
905
35
233
0
110
78
104
590
30
43
136
1257
1450
952
494
884
1347
957
822
Outlet Gas
N0x S02
(ppm) (ppm)
50
10
60
10
—
20
190
20
0
320
755
320
—
—
35
222
Composition
S03 NH3
(ppm) (ppm)
0
96
92
140
—
—
43
153
—
671
591
206
—
—
629
— —
Conv.
of NO
<*)
95
99
94
98
—
98
74
98
s.v. * 10,000 hr-1. Simulated flue gas contains also 12$ COg, 3$ O , 5$ H2O in Ng.
* Catalyst taken out of reactor and exposed to air for two days after 142 hours exposure
time.
A very brief durability test of the 15^ Fe-V (1/1)-A12O catalyst in simulated
flue gas (s.v. = 10,000 hr"1) containing SOX (420 ppm SO2> 110 ppm 303 ) was
conducted at 400°C. Concentrations of NOX and NH3 were 1040 and 1210 ppm,
respectively. At the end of the 26 hour exposure test, 99^ conversion of NOX was
obtained.
The promising results for the Fe-Cr-V and the Fe-V catalysts indicate that fur-
ther tests are warranted including modification of catalyst composition and catalyst
loading to improve activity and to reduce costs. In addition, parametric studies and
long term durability tests in the presence of SO (including concentrations of 803 >
500 ppm) are recommended.
109
-------
REFERENCES
The reference numbers are prefixed with the chapter of this report in which
they first occur.
1-1. Bartok, W. et al, "Systems Study of Nitrogen Oxide Control Methods for Station-
ary Sources," Esso Res. and Engr. Co. Final Report, Vol. 2, Pub. No.
GR-2-M, PS-69, Nov. (1969).
1-2. Koutsoukos, E.P., et al. "Assessment of Catalysts for Control of NOX from
Stationary Power Plants, Phase I. Volume I — Final Report.tf Environmental
Protection Technology Series, EPA - 650/2-75-001-a, Jan. (1975).
3-1. Nonnenmacher, H., and K. Kartte. "Selective Removal of Oxides of Nitrogen
from Gas Mixtures Containing Oxygen." U.S. Patent 3,279,384. October 18
(1966). 4 pp.
3-2. Schmidt, K. andV. Schulze. "Method for Removing Nitrogen Oxides from
Gases through Catalytic Reduction of these Substances to Nitrogen." West
German Patent 1,259,298. Jan. 25 (1958). 2 pp. (German).
3-3. Andersen, H. C., W. J. Green, and D. R. Steele. Catalytic Treatmeat of Nitric
Acid Plant Tail Gas. fad. Eng. Chem., 53; 119-204 (1961).
4-1. Seidman, E.B. Determination of Sulfur Oxides in Stack Gases. Analytical
Chemistry, 30: 1680-2 (1958).
4-2. Aris, R. "On Shape Factors for Irregular Particles," Chem. Eng. Science,6
262-269 (1957).
4-3. Wheeler, A., Reaction Rates and Selectivity in Catalyst Pores," Adv. in Cat-
alysis, 3_, 249-327 (1951).
4-4. Caretto, L.S. and Ken Nobe. "Effects of Pore Diffusion in the Catalytic Oxida-
tion of Ethylene." A.LCh.E. J,, .15, 18-24 (1969).
4-5. Bazes, Joe G.I., L.S. Caretto and Ken Nobe. "Catalytic Reduction of Sulfur
Dioxide with Carbon Dioxide on Cobalt Oxides." Ind. Enfi. Chem. Prod. Res.
Develop., 14_, 264-268 (1975).
110
-------
5-1. Bauerle, G. L., S.C. Wu and Ken Nobe. "Catalytic Reduction of Nitric Oxide
with Ammonia on Vanadium and Iron-Chromium Oxide," Ind. Eng. Chem.
Prod. Res. Dev., 14, 268-73 (1975).
5-2. Matsuda, S. et al. "Selective Reduction of Nitrogen Oxides in Combustion Flue
Gases." presented at Air Pollution Control Association Meeting, Portland,
Oregon, June (1976).
5-3. Kudo, T., T. Manabe, T. Gejo, M. Seki and K. Yoshida. "New Oxide Catalyst
with Perovskite-Related Structure for Reduction of NO with NH_," presented at
167th meeting of Am. Chem. Soc., Los Angeles, CA, April (1974).
5-4. Kudo, T., etal. Japanese patent Kokai 75-24181, (13(9)glll, 13(7)A11, 14dl2)
March 15, 1975.
5-5. Kudo, T., et al. German patent Offen 2,347 (Cl. BOlj) April 11, 1974,
CA0810841064Q.
Ill
-------
APPENDIX A
Specific references of direct pertinence to this project have been examined and
are listed in Table A-l which includes, in addition to the normal bibliographic nota-
tions, the institution or company affiliations and the specific Chemical Abstracts
reference number. Data, which are pertinent to NOX catalysis, obtained from these
abstracts and/or papers have been assembled and presented in Table A-2. Specific
information presented is catalyst type and composition, test conditions, conversion
of NO or outlet concentrations, selectivity in the presence of O2, resistance to
sulfur oxides and the extent of durability tests, if reported. Data for reducing agents
other than NHg (these are predominantly concerned with automotive NOX abatement
systems or, in a few cases, with HNO -plant tail-gas treatment) are also listed in
Table A-2. The listings suggest that much of the activity in NO_ catalysis is by Jap-
anese workers and indicate, surprisingly, a lesser interest in the field by U.S. indus-
try and governmental agencies. The bibliographical listing covers the approximate
period from June 1974 to the present and can be considered to be an update of the
previous survey (1-2).
113
-------
TABLE A-l. NOX CATALYSIS REFERENCES
1. Sakano, T., K. Fujiyama and Y. Hottai.
Mitsubishi Metal Mining Co. Ltd.
" Catalyst for Removal of Nitrogen Oxides" (Patent). Japan, Kokai 73 90986
(13(9)G11), 27 Nov 1973, Appl : 7 Mar 1972, 3 pp.
CA08016087114P.
2. Morita, Y. andM. Takayasu.
Sen. Sci. Eng., Waseda Univ., Tokyo, Japan.
" Catalytic Reduction of Nitrogen Oxides " (Article). Nenryo Kyokai-Shi
(Nenka), 1973, 52 (10), 757-65 (Japan).
CA08016086953Z.
3. Oodan, K., H. Sasaya, K. Yoshida and H. Otsuka.
Kaneguchi Chemical Industry Co., Ltd.
" Catalytic Decomposition of Nitrogen Oxides" (Patent). Japan, Kokai 73 55870
(13(7)A11), 6 Aug 1973, Appl: 18 Nov 1971, 4 pp.
CA08008041321A.
4. Usol'Tseva, L.M., E.P. Mikheeva and N.P. Keier.
Inst. Katal., Novosibirsk, USSR.
" Oxidation of Carbon Monoxide, Reaction of Carbon Monoxide and Nitric
Oxide, and Decomposition of Nitric Oxide on Titanium Dioxide Films Studied
by the Field EJect Method" (Article). Kinet. Katal. (Knkta), 1973, 14 (5),
1350-1 (Russ).
CA08008041247F.
5. Watanabe, S., Y. Kori, A. Kawakami, O. Okamoto, and S. Yamaguchi.
Hitachi Makuseru Co., Ltd.
" Catalyst for Reduction of Nitrogen Oxides " (Patent). Japan, Kokai 73
71386 (13(9)G111), 27 Sep 1973, Appl: 28 Dec 1971, 4 pp.
CA08008040740Z.
6. Matshushita, Kunichi.
Mitsubishi Chemical Industries Co., Ltd.
" Decomposition of Nitrogen Oxides " -(Patent). Japan. Kokai 73 61362
(13(7)A11), 28 Aug 1973, Appl: 22 Nov 1971, 3 pp.
CA08008040735B.
7. Glazneva, G.V., I.S. Sazonova and N.P. Keier.
Inst. Katal, Novosibirsk, USSR.
"Reduction of Nitrogen Oxide by Carbon Monoxide on Metal Oxides" (Article).
Dokl. Akad. Nauk SSSR (Danka), 1973, 213 (2), 364-7 (Phys. Chem.) (Russ).
CA08010052670Q. (cont.)
114
-------
8. Kolomoiskaya, R.M., G.A. Skvortsov andS.N. Ganz.
Dneprodzerzhinsk. Fil-, Gos. Nauchno-Issled. Proekt. Inst. Azotn. Prom.
Prod. Org. Sint., Dneprodzerzhinsk, USSR.
"Selective Catalytic Removal of Oxygen from Gas Mixtures Containing
Nitrogen Oxides" (Article). Zh. Prikl. Khim. (Leningrad) (Zpkha), 1973,
46 (8), 1659-63 (Russ).
CA08010049829T.
9. Bernstein, L.S., A.K. Raman and E.E. Wigg.
Esso Research and Engineering Co.
"Nitrogen Oxide Conversion Using Reinforced Nickel-Copper Catalysts"
(Patent). U.S. 3773894 (423-213.5; B 01J), 20 Nov 1973, Appl: 22 Jul
1971, 5 pp.
CA080120S3441S.
10. Endo, A., T. Takeyama and K. Shoda.
Toray Industries, Inc.
"Removal of Nitrogen Oxides from Nitrogen Oxide-Containing Exhaust
Gases" (Patent). Japan. 72 50981 (B 01J), 21 Dec. 1972, Appl: 26 Dec 1970,
3 pp.
CA03012033436U.
11. Zasorin, A.P., V.I. Atroshchenkoand O.N. Kulish.
Kharkov Polytechnic Institute.
" Catalyst for the Selective Removal of Nitrogen Oxides from Gases " (Patent).
U.S.S.R. 366661 (B 01J), 21 Jun 1973, Appl: 27 Mar 1970. From:
Otkrytiya, Isobret., Prom. Obraztsy, Tovarnye Znaki 1973, 50 (27), 16-17.
CA08012063424P.
12. Kobylinski, P. and B.W. Taylor.
Gulf Research and Development Co.
"The Nitrogen Oxides of Internal-Combustion Engine Exhaust Gases" (Patent).
Fr. Demande 2148137 (B 01DJ, F 01N), 20 Apr 1973, US Appl: 2 Aug 1971,
34 pp.
13. Bauerle, G.L., L. L. Sorensen and K. Nobe.
Sch. Eng. Appl. Sci., Univ. California, Los Angeles, CA.
"Nitric Oxide Reduction on Copper-Nickel Catalysts" (Article). Ind. Eng.
Chem., Prod. Res. Develop. (IEPRA), 1974, _13 (1), 61-4 (Eng).
CA08018100618C.
14. Stephens, Ruth E.
Ethyl Corp.
" Decomposing Nitrogen Oxides " (Patent). U. S. 3787560 (423-239 ; B 01D),
22 Jan 1974, Appl: 22 Dec 1967, 3 pp., CA08018099786X.
(cont.)
115
-------
TABLE A-l (cont.)
15. Saeufferer, H.
Daimler-Benz A.-G.
" Catalytic Removal of Nitrogen Oxides, Hydrocarbons, and Carbon Monoxide
from Exhaust Gases " (Patent). Ger. 1594699 (F 01N), 11 Oct 1973, Appl:
23 Oct 1964, 2 pp.
CA08018099774S.
16. Kudo, T., H. Obayashi, T. Gejyo, K. Yoshida and M. Seki.
Hitachi, Ltd.
"Removal of Nitrogen Oxide from Waste Gases " (Patent). Ger. Offen.
2310072 (B 01D, F 01N), 20 Sep 1973, Japan. Appl: 1 Mar 1972, 25 pp.
CA08018099764P.
17. Seto, H., M. Shimada, H. Yamagishi and H. Wada.
Nissan Engineering Co. Ltd.
" Removing Nitrogen Oxides from Waste Gas " (Patent). Japan, Kokai 73
84796 (15 B251), 10 Jan 1973, Appl: 15 Feb 1972, 3 pp.
CA08024136994M.
18. Kawakami, A., O. Okamoto, Y. Koori and H. Honda.
Hitachi Maxell Ltd.
" Catalyst for Reduction of Nitrogen Oxides in Waste Gases" (Patent). Japan,
Kokai 74 03891 (13(9)G32, 13(7)A11, 51 D51), 14 Jan 1974, Appl: 2 May
1972, 3 pp.
CA08 02413 6993K.
19. Matsushita, K.
Mitsubishi Chemical Industries Co., Ltd.
"Alumina Catalysts Containing Sodium, Potassium, and Cesium Oxides for
Decomposing Nitrogen Oxides " (Patent). Japan, Kokai 74 07185 (13(9)G111,
14 D12, 13(7)A11), 22 Jan 1974, Appl: 11 May 1972, 6 pp.
CAQ8 02413 6990G.
20. Shelef, M. andH.S. Gandhi.
Ford Motor Co., Dearborn, Mich.
"Reduction of Nitric Oxide in Automobile Emissions. Stabilization of Catalysts
Containing Ruthenium" (Article). Platinum Metals Rev. (PTMRA), 1974,
18 (1). 2-14 (Eng).
CA08024136915M.
21. Fuller, M. J. andM.E. Warwick.
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51. Watanabe, O., N. Odani, H. Hosoda and Y. Koorl.
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72. Kudo, T., T. Manabe, K. Yoshida, T. Gejo and M. Seki.
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74. Santala, T.J.
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75. Ashmead, D.R., J.S. Campbell, P. Da vies and K. Farmery.
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80. Inaba, H. and S. Onizuka.
Hitachi Shipbuilding and Engineering Co., Ltd.
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86. Komofuchi, Y., and Y- Takahashi.
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" Nitric Oxide Reduction with Hydrogen on Mixed Metal Oxide Catalysts "
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96. Sood, A. and J.R. Kittrell.
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100. Winter, E.R.S.
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Tech. Lab., Kurashiki Boseki Co., Ltd., Neyagawa, Japan.
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139. Bartholomew, Calvin H.
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144. Oshimura, M., Y. Kori, A. Miyamoto, H. Hosoda, A. Kawakami, O.Okamoto,
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145. Nishino, A., H. Kumano, K. Sonetaka and H. Nakamura.
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Sumitomo Chemical Co., Ltd.
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150. Kudo, T., T. Manabe, K. Yoshida, T. Gejo and M. Seki.
Hitachi, Ltd.
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Hitachi, Ltd.
" Catalyst for Removal of Nitrogen Oxides" (Patent). Japan. Kokai 74113792
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Hitachi, Ltd.
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157. Oshimura, M., Y. Kori, A. Miyamoto, A. Kawakamu, H. Hosoda, O. Okamoto,
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158. Oshimura, M.,Y. Kori, A.Miyamoto, A. Kawakami, H. Hosoda, O. Qkamoto,
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" Catalyst for Reduction of Nitrogen Oxides " (Patent). Japan. Kokai 74119888
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159. Oshimura, M., Y. Kori, A. Miyamoto, A. Kawakami, H. Hosoda, O. Okamoto,
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160. Oshimura, M., Y. Kori, A. Miyamoto, A. Kawakami, H. Hosoda, O. Okamoto,
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267. Mori, T., M. Takeuchi, O. Hitomi, S. Uno, H. Okada, J. Imahashi and
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273. Takeuchi, M., T. Mori, S. Uno, H. Okada, J. Imahashi, F. Nakajima and
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335. Mehalchick, E.J., J.J. Cleveland, R.A. Long, H.O. Schulze and P.K. Marshall.
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337. Berrebi, G., P. Courty and D. Lucesoli.
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338. Ceballos, A., S.J. Pajares and P.A. Ruiz.
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339. Watanabe, S.
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341. Ganz, S.N., L.E. Rakhmanova, S.A. Aleshkevich, I.D. Misyuk and R.E.
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343. Yamada, K., H. Sawamura, T. Ayabe and N. Hashimoto.
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346. Umemura, S., J. Takeuchi, R. Kito, S. Ito, Y. Arima and K. Ito.
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348. Ninomiya, N., H. Nishino, T. Aibe and K. Itoga.
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349. Fukui, S., Y. Nishimoto, N. Yokoyama and R. Masuko.
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350. Nishimoto, Y., N. Yokoyama, H. Ogawa and M. Hino.
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351. Watanabe, S., K. Hashimoto and H. Watanabe. Toyo Engineering Corp.
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352. Watanabe, Y. and H. Kurokawa.
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353. Todo, N., M. Kurita, H. Hagiwara, A. UenoandT. Sato.
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354. Ishii, T., S. Matsumoto, M. Nakatani and K. Usui.
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355. Ito, H.
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356. Oshimura, M., Y. Koori, H. Hosoda, S. Fujii, O. Watanabe, A. Kawakami,
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357. Oshimura, M., Y. Koori, H. Hosoda, O. Watanabe, S. Fujii, A. Kawakami,
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358. Nagai, S., H. MizunoandA. Kashiwagi.
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359. Ohtaki, N. and A. Wagai .
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360. Komatsu, N., O. Kamigaito, T. Suzuki, N. Yamamoto, H. Doi, K. Sano,
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361. Yamauchi, S., K. Harie, T. Ono and T. Ohhara.
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362. Voorhoeve, R.J., C.K. Patei, L.E. Trimble and R.J. Kerl.
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363. Orsini, R.A., S.A. Tunick, G. L. Bauerle and K. Nobe
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364. Gandhi, H.S., M. Shelef and T.F. Strow.
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365. Niiyama, H., T. OokawaandE. Echigoya.
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366. Ohshima, H. and K. Saiki.
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" Catalyst for Removal of Nitrogen Oxides " (Patent). Japan. Kokai 75145383
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367. Ichiki, M. and H. Inaba.
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368. Takeuchi, J., S. Ito, K. Ito , K. Egoshi and M. Kashibe.
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369. Abe, K.
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370. Doi, Y.
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371. Sakurai, Y., M. Nishioka, A. Takahashi and T. Takeyama.
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372. Matsushita, K., H. Sakurada, K. Onuma and S. Fujii.
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373. Ohhara, T., T. Ono, K. Horie and S. Ya-mauchi.
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374. Adachi, S., T. Miyakoshi and M. Hattori.
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375. Watanabe, Y., M. Imanari, M. Takeuchi, S. Matsuda, S. Uno, T. Mori
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376. Nishino, H., T. Aibe, A. Kobayashi, K. Fujinami, K. Ogino, I. Furuoya
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377. Hirokawa, K., T. Takahashi and T. Nagayama.
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378. Adachi, S., T. Miyakoshi and M. Hattori. TDK Electronics Co., Ltd.
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379. Yokomizo, M., T. Takahashi and K. Hirokawa. Mitsui Toatsu Chemicals, Inc.
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167
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TABLE A-l (cont.;
380. Kobylinksi, T.P. andB.W- Taylor.
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381. Uchino, T., K. Sato, H. Kijimuta and M. Ikemura.
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" Catalytic Treatment of Nitrogen Oxides in Waste Gas " (Patent). Japan.
Kokai 75108169 (B01DJ), 26 Aug 1975, Appl: 5 Feb 1974, 4 pp.
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382. Kudo, T., M. Takeshi ta and T. Gejyo.
Hitachi, Ltd.; Babcock-Hitachi K.K.
" Catalyst for Reduction of Nitrogen Oxides " (Patent). Ger. Offen. 2501810
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383. Fleming, Donald K.
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384. Uchino, T., K. Sato, H. Kijimuta and K. Terase.
Asahi Glass Co., Ltd.
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385. Inaba, H., Y. Kamino and S. Onitsuka.
Hitachi Shipbuilding and Engineering Co., Ltd.
"Reduction Catalysts for Nitrogen Oxide Removal from Waste Gases" (Patent).
Japan. Kokai 75 57953 (B01DJ), 20 May 1975, Appl: 25 Sep 1973, 9 pp.
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386. Oshimura, M., Y. Kori, A. Kawakami, H. Hosoda, O. Okamoto, N. Qtani,
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" Catalysts for Reduction of Nitrogen Oxides in Exhaust Gas " (Patent).
Japan. Kokai 75 45797 (B01JD, F01N, C01B), 24 Apr 1975, Appl: 27 Aug
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387. Oshimura, M., A. Kawakami, H. Hosoda, O. Okamoto, O. Watanabe,
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"Reduction Catalyst for Nitrogen Oxide Removal from Exhaust Gas " (Patent).
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388. Miyasaki, K- and K. Abe.
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389. Yamashita, H.: S. Kubota, Y. Nishimura and F. Nakajima.
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390. Gandhi, H.S., H.K. Stepien and M. Shelef.
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"Durability Testing of Stabilized Ruthenium-containing Catalysts" (Article).
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391. Kasaoka, S., H. Kobayashi, H. Nagi, S. Inoue, H. Tsumaki and T. Kitamura.
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" Catalytic Reduction of Nitric Oxide with Carbon Monoxide" (Article).
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392. Ku, R., Gjostein, N.A. andH.P. Bonzel.
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393. Shelef, M., R.A. Dalla Betta and K. Otto.
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395. Matsushita, K., H. Sakurada and K. Onuma.
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396. Matsushita, K., H. Sakurada and K. Onuma.
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"Reduction of Nitrogen Oxides" (Patent). Japan. Kokai 75126572 (B01DJ,
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397. Matsushita, K., H. Sakurada, K. Onuma and S. Fujii.
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398. Komatsu, N., T. Suzuki, N. Yamamoto, K. Morimoto, Y. Tsuzuki, M. Hoki
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" Catalysts for Exhaust Gas Treatment " (Patent). Japan. Kokai 75124890
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399. Kobylinski, T.P. and B.W. Taylor.
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400. Compton, W.A., J.F. Nachman and M.I. Seegall.
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402. Ishizaki, K.
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404. Nakajima, F., M. Takeuchi, S. Matsuda, S. Uno, T. Mori, Y. Watanabe
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405. Kearby, K.K.
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407. Inone, K.
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" Catalyst for Removing Nitrogen Oxides from Waste and Exhaust Gases "
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" Catalytic Removal of Nitrogen Oxides in Flue Gas from Sintering Plants
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409. Klimisch, R.L. andJ.G. Larson, Editors.
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411. Echigoya, E-, H. Niiyama, A. Ebitani, H. lida and T. Ookawa,
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Bull. Jpn. Pet. Inst., 1975, 17(2), 232-5 (Eng).
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412. Takayasu, M., H. Tomono, Y. AnnenandY. Morita.
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"Catalytic Reduction of Nitric Oxide with Hydrogen or Methane" (Article).
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413. Morikawa, K., F. Nishida, T. Yamada, N. Suzuki, T. Takeda, T. Yanagihara,
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"Separation of Nitrogen Oxides from Waste Gases " (Patent). Ger. Offen.
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414. Abe, K., T. Chikazawa, H. Noguchi and I. Shimizu.
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416. Barker, G.E.
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417. Matsuda, S., F. Nakajima and S. Okazaki.
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418. Hishinuma, Y., H. Akimoto, R. Kaji and F. Nakajima.
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"Removal of Nitrogen Oxides by Catalytic Reduction" (Patent). Japan.
Kokai 75102566 (B01D), 13 Aug 1975, Appl: 16 Jan 1974, 4 pp.
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419. Ishizaki, K.
Kobe Steel, Ltd.
"Nitrogen Oxide Removal from Waste Gases " (Patent). Japan. Kokai 75
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420. Yamaji, K., K. Konishi, Y. Koori and O. Okamoto,
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"Supports for Catalysts for Automobile Exhaust Gas Treatment" (Patent).
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421. Matsushita, K., H. Sakurada, K. Onuma and S. Fujii.
Mitsubishi Chemical Industries Co., Ltd.
" Catalytic Reduction of Nitrogen Oxide in Waste Gas " (Patent). Japan.
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422. Matsushita, K., H. Sakurada, K. Onuma and S. Fujii. Mitsubishi Chemical
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(Patent). Japan. Kokai 75 62861 (B01DJ), 29 May 1975, Appl: 9 Oct 1973,
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423. Matsushita, K., H. Sakurada, K. Onuma and S. Fujii.
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" Catalytic Reduction of Nitrogen Oxides in Waste Gas" (Patent). Japan.
Kokai 75 62862 (B01DJ), 29 May 1975, Appl: 9 Oct 1973, 3 pp.
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424. Matsushita, K., H. Sakurada, K. Onuma and S. Fujii.
Mitsubishi Chemical Industries Co., Ltd.
" Catalytic Reduction of Nitrogen Oxides in Waste Gas " (Patent). Japan.
Kokai 75 62863 (B01DJ), 29 May 1975, Appl: 9 Oct 1973, 3 pp.
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425. Matsushita, K., H. Sakurada, K. Onuma and S. Fujii.
Mitsubishi Chemical Industries Co., Ltd.
" Catalytic Reduction of Nitrogen Oxides in Waste Gas " (Patent). Japan.
Kokai 75 62864 (B01DJ), 29 May 1975, Appl: 9 Oct 1973, 3 pp.
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426. Theobald, Heinz.
Duengemittel-Prod., BASF, Ludwigshafen, Ger.
"Industrial Testing of a New Process for Catalytic Decomposition of Nitrous
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427. Muraki, R., M. Endo and N. Aoki.
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"Regeneration of Catalyst for Purging of Nitrogen Oxides " (Patent). Japan.
Kokai 75153789 (B01JD, F01N, C01B), 11 Dec 1975, Appl: 31 May 1974,
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428. Endo, A., S. Takeyama and E. Masuda.
Toray Industries, Inc.
"Removal of Nitrogen Oxide " (Patent). Japan. 75 23665 (B01DJ), 9 Aug
1975, Appl: 28 Dec 1970, 3 pp.
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429. Inaba, H., Y. Kamino and S. Onitsuka.
Hitachi Shipbuilding and Engineering Co., Ltd.
"Catalyst for Purging Nitrogen Oxides" (Patent). Japan. Kokai 75110993
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174
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430. Taniguchi, K., Y. Kawamura and T. Yoshioka.
Mitsui Petrochemical Industries, Ltd.
"Removal of Nitrogen Oxides from Waste Gases using Catalysts containing
Copper and Iron Sulfates " (Patent). Japan. Kokai 75121161 (B01DJ), 22 Sep
1975, Appl: 12 Mar 1974, 4 pp.
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431. Moriguchi, S., H. Abe, T. Nishida, J. Takenaka and M. Miyazawa.
Nippon Kokan K. K.
"Separation of Nitrogen Oxides from Waste Gases " (Patent). Ger. Offen.
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432. Nakajima, F., M. Takeuchi, S. Matsuda, S. Uno, T. Mori, Y. Watanabe
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Hitachi, Ltd.
" Catalyst for Reduction of Nitrogen Oxides " (Patent). Japan. Kokai 75
89287 (B01JD, C01B, F01N), 17 Jul 1975, Appl: 12 Dec 1973, 11 pp.
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433. Shin, S.S.
Purdue Univ., Lafayette, Indiana.
"A Simultaneous Infrared and Kinetic Study of the Reduction of Nitric Oxide
by Carbon Monoxide over Chromia-Silica Catalysts" (Dissertation). Avail:
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174 pp. (Eng).
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434. Zhuravskaya, V.S., V.I. Atroshchenko and V.I. Konvisar.
USSR.
"Oxidation of Nitrogen Oxide on Heterogeneous Catalysts " (Article). Vestn.
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-- CA08420141194N.
435. Tauster, S.J. andL.L. Murrell.
Corp. Res. Lab., Exxon Res. and Eng. Co., Linden, N. J.
"The Nitric Oxide-Carbon Monoxide Reaction in the Presence of Excess
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41(1), 192-5 (Eng).
CA08420141190H.
436. Nagai, S., H. Mizuno and T. Ogawa. Ube Industries, Ltd.
"Nickel Catalyst for Reduction of Nitrogen Oxides Resistant to Sulfur Poison"
(Patent). Japan. Kokai 75153786 (B01JD, F01N, C01B), 11 Dec 1975,
Appl: 4 Jun 1974, 5 pp. CA08420140261V. (cont.)
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437. Fukuzawa, H. and Y. Ishihara.
Central Research Laboratories for the Electric Power Foundation.
" Catalyst for Reduction of Nitrogen Oxides " (Patent). Japan. Kokai 75155491
(B01JD, F01N, C01B), 15 Dec 1975, Appl: 8 Jun 1974, 5 pp.
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438. Lauder, A.
Du Pont de Nemours, E.I., and Co.
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439. Lauder, A.
Du Pont de Nemours, E.I., and Co.
"Catalytic Composition with Perovskite Crystal Structure" (Patent). Ger.
Offen. 2518537 (B01J), 30 Oct 1975, US Appl: 25 Apr 1974, 32 pp.
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440. Sermon, P.A.
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441. Todo, N., M. Kurita, H. Hagiwara, A. UenoandT. Sato.
Agency of Industrial Sciences and Technology.
" Catalytic Reduction of Nitric Oxide in Combustion Flue Gas with Ammonia "
(Patent). Japan. Kokai 75 41764 (13(7)A11), 16 Apr 1975, Appl: 17 Aug
1973, 6 pp.
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442. Shiraishi, T-, S. ShimizuandT. Shindo.
Sumitomo Chemical Co., Ltd.
" Catalyst for Selective Separation of Nitrogen Oxides from Waste Gases "
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443. Meyer, C.D. and R. Eisenberg.
Dep. Chem., Univ. Rochester, Rochester, N.Y.
"The Catalytic Reduction qf Nitric Oxide by Carbon Monoxide using Dichluro-
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CA08420140197D. (cont.)
176
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444. Clay, D.T. and S. Lynn.
UniVrf California, Berkeley, CA.
'Iron-Catalyzed Reduction of Nitrogen Oxide by Carbon Monoxide and Hydrogen
in Simulated Flue Gas" (Conference). Catal. Chem. Nitrogen Oxides, Proc.
Symp. 1974, Pub: 1975, 249-62 (Eng.) Edited by: Klimisch, R.L. and J.G.
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CA08420140082N.
445. Klimisch, R.L. and J.M. Komarmy.
Gen. Mot. Res. Lab., Warren, Mich.
"Approaches to Catalytic Control of Automotive NOX Emissions" (Conference).
Catal. Chem. Nitrogen Oxides, Proc. Symp. 1974, Pub: 1975, 305-18 (Eng).
Edited by: Klimisch, R.L. and J.G. Larson. Plenum, New York, N.Y.
CA08420139981Y.
446. Wise, H.
Stanford Res. Inst., Menlo Park, CA.
"The Ammonia Route to NO Conversion into Auto Exhaust Catalysis" (Confers
ence). Catal. Chem. Nitrogen Oxides, Proc. Symp. 1974, Pub: 1975,235-46
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CA08420139980X.
447. Hightower, J.W. and D.A. Van Leirsburg.
Rice Univ., Houston, Tex.
"Current Status of the Catalytic Decomposition of Nitric Oxide" (Conference).
Catal. Chem. Nitrogen Oxides, Proc. Symp. 1974, Pub: 1975, 63-93 (Eng).
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448. Callighan, R.H. and J.O. Hawthorne.
United States Steel Corp.
"Iron Oxide Catalysts" (Patent). U.S. Publ. Pat. Appl. B390979 (252-455R,
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CA 08422156262G.
449. Solymosi, F. and J. Kiss.
Gas Kinet. Res. Group, Univ. Szeged, Szeged, Hung.
"Adsorption and Reduction of Nitric Oxide on Tin (TV) Oxide Catalysts" (Article).
J. Catal., 1976, 41/2), 202-11 (Eng).
CA08422156198R.
450. Nekrich, E.M., G.V. Khrapal and N.G. Grebinlchenko.
Vses. Nauchno-Issled. Inst. "Chermetenergoochistka," Khar'kov, USSR.
"Concerning the Heterogeneous Interaction of Carbon Monoxide, Hydrogen, and
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Izv. Akad. NaukKaz. SSR, Ser. Khim., 1975, .25(6), 23-7 (Russ).
CA08422156185 f.
(cont.)
177
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TABLE A-l (cont.)
451. Ohki, K., N. Tamura, T. Yamamoto, H. Obana and T. Inoue.
Asahi Chemical Industry Co., Ltd.
"Nitrogen Oxide Removal from Flue-Gases" (Patent). Japan. Kokai 76
20770 (B01DJ, C01B), 19 Feb 1976, Appl: 14 Aug 1974, 4 pp.
CA08422155163P-
452. Sakurai, Y., M. Nishioka, A. Takahashi and T. Takeyama.
Toray Industries, Inc.
"Removal of Nitrogen Oxides from Waste Gas by Catalytic Reduction" (Patent).
Japan. Kokai 76 11063 (B01DJ, C01B), 28 Jan 1976, Appl: 18 Jul 1974,
5 pp.
CA08422155159S.
453. Takahari, T., A. Kawamura, M. Uchiyama, Y. OhkataandT. Ishiguro.
Nippon Steel Corp.
"Removal of Nitrogen Oxides from Waste Gas by Catalytic Reduction with
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Appl: 3 Jul 1974, 4 pp.
CA08422155158R.
454. Abe, K., T. Sakuma, I. Shimizu and H- Noguchi.
Fujikura Cable Works, Ltd.
11 Catalyst for Waste Gas Purification" (Patent). Japan. Kokai 76 03390
(B01JD, F01N, C01B), 12 Jan 1976, Appl: 28 Jun 1974, 3pp.
CA08422155156P.
455. Hiroe, Y., H. Yoshitani, N. Oka, T. Mitani and M. Sato.
Idemitsu Kosan Co., Ltd.
"Removal of Nitrogen Oxides from Flue Gas by Catalytic Reduction" (Patent).
Japan. Kokai 76 17193 (B01JD), 10 Feb 1976, Appl: 5 Aug 1974, 5 pp.
CA08422155153K.
456. Kurita, S., K. Takahashi, T. Watanabe, S. Morikawa and T. Watanabe.
Ishikawajima-Harima Heavy Industries Co., Ltd.
"Removal of Nitrogen Oxide from Waste Gas" (Patent). Japan. Kokai
76 03365 (B01DJ, C01B), 12 Jan 1976, Appl: 27 Jun 1974, 4 pp.
CA08422155145J.
457. Ohki, K., H. Obana, T. Baoue, M. Katsura and H. Nakajima.
Asahi Chemical Industry Co., Ltd.
" Removal of Nitrogen Oxidie " (Patent). Japan. Kokai 76 03366 (B01D, C01B),
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178
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444. Clay, D.T. and S. Lynn.
Univw California, Berkeley, CA.
'Iron-Catalyzed Reduction of Nitrogen Oxide by Carbon Monoxide and Hydrogen
in Simulated Flue Gas" (Conference). Catal. Chem. Nitrogen Oxides, Proc.
Symp. 1974, Pub: 1975, 249-62 (Eng.) Edited by: Klimisch, R.L. and J.G.
Larson. Plenum, New York, N.Y.
CA08420140082N.
445. Klimisch, R.L. and J.M. Komarmy.
Gen. Mot. Res. Lab., Warren, Mich.
"Approaches to Catalytic Control of Automotive NOX Emissions" (Conference).
Catal. Chem. Nitrogen Oxides, Proc. Symp. 1974, Pub: 1975, 305-18 (Eng).
Edited by: Klimisch, R.L. and J.G. Larson. Plenum, New York, N.Y.
CA08420139981Y.
446. Wise, H.
Stanford Res. Inst., Menlo Park, CA.
"The Ammonia Route to NO Conversion into Auto Exhaust Catalysis" (Confer**
ence). Catal. Chem. Nitrogen Oxides, Proc. Symp. 1974, Pub: 1975,235-46
(Eng). Edited by: Klimisch, R.L. and J.G. Larson. Plenum,New York, N.Y.
CA08420139980X.
447. Hightower, J.W. and D.A. Van Leirsburg.
Rice Univ., Houston, Tex.
"Current Status of the Catalytic Decomposition of Nitric Oxide" (Conference).
Catal. Chem. Nitrogen Oxides, Proc. Symp. 1974, Pub: 1975, 63-93 (Eng).
Edited by: Klimisch, R.L. and J.G. Larson. Plenum, New York, N.Y.
CA08420139979D.
448. Callighan, R.H. and J.O. Hawthorne.
United States Steel Corp.
'Iron Oxide Catalysts" (Patent). U.S. Publ. Pat. Appl. B390979 (252-455R,
B01J), 23 Mar 1976, Appl: 4 Oct 1971, 4 pp.
CA08422156262G.
449. Solymosi, F. and J. Kiss.
Gas Kinet. Res. Group, Univ. Szeged, Szeged, Hung.
"Adsorption and Reduction of Nitric Oxide on Tin (TV) Oxide Catalysts" (Article).
J. Catal., 1976, 41^(2), 202-11 (Eng).
CA08422156198R.
450. Nekrich, E.M., G.V. Khrapal and N.G. Grebinichenko.
Vses. Nauchno-Issied. Inst. "Chermetenergoochistka," Khar'kov, USSR.
"Concerning the Heterogeneous Interaction of Carbon Monoxide, Hydrogen, and
Methane with Nitrogen Oxides in Highly Diluted Vapor-Gas Mixtures" (Article)
Izv. Akad. NaukKaz. SSR. Ser. Khim., 1975, .25(6), 23-7 (Russ).
CA08422156185J".
(cont.)
177
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TABLE A-l (cont.)
451. Ohki, K., N. Tamura, T. Yamamoto, H. Obana and T. Inoue.
Asahi Chemical Industry Co., Ltd. (
"Nitrogen Oxide Removal from Flue-Gases" (Patent). Japan. Kokai 76
20770 (B01DJ, C01B), 19 Feb 1976, Appl: 14 Aug 1974, 4 pp.
CA08422155163P.
452. Sakurai, Y., M. Nishioka, A. Takahashi and T. Takeyama.
Toray Industries, Inc.
"Removal of Nitrogen Oxides from Waste Gas by Catalytic Reduction" (Patent).
Japan. Kokai 76 11063 (B01DJ, C01B), 28 Jan 1976, Appl: 18 Jul 1974,
5 pp.
CA08422155159S.
453. Takahari, T., A. Kawamura, M. Uchiyama, Y. OhkataandT. Ishiguro.
Nippon Steel Corp.
"Removal of Nitrogen Oxides from Waste Gas by Catalytic Reduction with
Ammonia" (Patent). Japan. Kokai 76 05262 (B01DJ, C01B), 16 Jan 1976,
Appl: 3 Jul 1974, 4 pp.
CA08422155158R.
454. Abe, K., T. Sakuma, I. Shimizu and H. Noguchi.
Fujikura Cable Works, Ltd.
"Catalyst for Waste Gas Purification" (Patent). Japan. Kokai 76 03390
(B01JD, F01N, C01B), 12 Jan 1976, Appl: 28 Jun 1974, 3 pp.
CA08422155156P.
455. Hiroe, Y., H. Yoshitani, N. Oka, T. Mitani and M. Sato.
Idemitsu Kosan Co., Ltd.
"Removal of Nitrogen Oxides from Flue Gas by Catalytic Reduction" (Patent).
Japan. Kokai 76 17193 (B01JD), 10 Feb 1976, Appl: 5 Aug 1974, 5 pp.
CA08422155153K.
456. Kurita, S., K. Takahashi, T. Watanabe, S. Morikawa and T. Watanabe.
Ishikawajima-Harima Heavy Industries Co., Ltd.
"Removal of Nitrogen Oxide from Waste Gas" (Patent). Japan. Kokai
76 03365 (B01DJ, C01B), 12 Jan 1976, Appl: 27 Jun 1974, 4 pp.
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457. Ohki, K., H. Obana, T. Inoue, M. Katsura and H. Nakajima.
Asahi Chemical Industry Co., Ltd.
" Removal of Nitrogen Oxide " (Patent). Japan. Kokai 76 03366 (B01D, C01B),
12 Jan 1976, Appl* 29 Jun 1974, 3 pp.
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458. Sonoda, T., K. Edogawa and M. Kato.
To ray Industries, Inc.
"Removal of Nitrogen Oxide from Flue Gases by Catalytic Reduction" (Patent).
Japan. Kokai 76 06173 (B01DJ, C01B), 19 Jan 1976, Appi: 8 Jul 1974, 5 pp.
CA08422155140D.
459. Akimoto, H., Y. Hishinuma and R. Kaji.
Hitachi, Ltd, Babcock-Hitachi K. K.
" Catalytic Reduction of Flue Gas containing Nitrogen Oxide" (Patent).
Japan. Kokai 76 06169 (B01D, C01B), 19 Jan 1976, Appl: 5 Jul 1974, 4 pp.
CA08422155138J.
460. Sonoda, T., K. Edogawa and M. Kato.
Toray Industries, Inc.
"Removal of Nitrogen Oxides from Flue Gases by Catalytic Reduction" (Patent).
Japan. Kokai 76 06174 (B01DJ, C01B), 19 Jan 1976, Appl: 8 Jul 1974,
5 pp.
CA08422155135F.
461. Matsushita, Y., T. Watanabe, F. YoshidaandT. Takeyama.
Toray Industries, Inc.
"Removal of Nitrogen Oxides from Exhaust Gas by Catalytic Reduction"
(Patent). Japan. Kokai 76 06175 (B01DJ), 19 Jan 1976, Appl: 8 Jul 1974,
3 pp.
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462. Taniguchi, K., Y. Kawamura, T. Yoshioka, Y. Morita and K. Kauchi.
Mitsui Petrochemical Industries, Ltd.
"Removal of Nitrogen Oxide from Waste Gas" (Patent). Japan. Kokai
75159867 (B01DJ, C01B), 24 Dec 1975, Appl: 17 Jun 1974, 5 pp.
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463. Takei, T.
Inoue-Japax Research Inc.
"Decomposition of Nitrogen Oxide and Sulfur Dioxide" (Patent). Japan.
Kokai 75159461 (B01DKJ), 24 Dec 1975, Appl: 14 Jun 1974, 3 pp.
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464. Ayusawa, S. and K. Tsuchiya.
Nippon Steel Corp.
"Manganese Dioxide Catalyst for Nitrogen Oxide Reduction" (Patent). Japan.
Kokai 76 02690 (B01JD, F01N, C01 ), 10 Jan 1976, Appl: 26 Jun 1974, 3 pp.
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179
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465. Matsumoto, R., I. Taguchi, T. Ishiguro and F. Kurosawa.
Nippon Steel Corp.
"Removal of Nitrogen Oxides from Waste Gas by Catalytic Solution" (Patent).
Japan. Kokai 75160165 (B01DJ, C01B, F01N), 25 Dec 1975, Appl: 19 Jun
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466. Miyoshi, H. and N. Kuwahara.
Chiyoda Chemical Engineering and Construction Co., Ltd.
"Removal of Nitrogen Oxides from Waste Gas by Catalytic Reduction" (Patent).
Japan. Kokai 75160166 (B01DJ, C01B, F01N), 25 Dec 1975, Appl: 20 Jun
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CA08422155124B.
467. Inamura, Y-, M. Yoshida, M. Yamada, T. Yoshikawa, R. Nagasawa, S.
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Niigata Engineering Co., Ltd.
"Removal of Nitrogen Oxides from Waste Gases by Catalytic Reduction"
(Patent). Japan. Kokai 75159888 (B01JD), 24 Dec 1975, Appl: 17 Jun 1974,
4 pp.
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468. Nagai, S., H. Mizuno, T. Ogawa and M. Iwamoto.
Ube Industries, Ltd.
"Sulfur-Resistant Nitrogen Oxide Reduction Catalyst" (Patent). Japan.
Kokai 76 04092 (B01JD), 13 Jan 1976, Appl: 2 Jul 1974, 3 pp.
CA08422155119D.
469. Japan Gasoline Co., Ltd.
"Removal of Nitrogen Oxides from Waste Gases " (Patent). Neth. Appl.
75 01171 (B01JD), 4 Aug 1975, Japan. Appl: 31 Jan 1974, 15 pp.
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470. Atroshchenko, A.V.-andA.N. Tseitlin.
USSR.
"Study of a Series of Metal Oxides as Catalysts for the Reduction of Nitric
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CA08422155015S.
471. Bernhardt, W.E. ,
Yolkswagenwerk A.-G., Wolfsburg, Ger. :
"Studies on NOX Reduction and Three-Component Catalysts " (Confere.nce).
Catal. Chem. Nitrogen Oxides, Proc. Symp. 1974, Pub: 1975, 297-304
(Eng). Edited by: Klimisch, R.L. and J.G. Larson. Plenum, New York,N.Y.
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472. McArthur, D.P.
Union Oil Res., Brea, CA.
"NOX Catalyst Degradation by Contaminant Poisoning" (Conference). Catal.
Chem. Nitrogen Oxides, Proc. Symp. 1974, Pub: 1975, 263-82 (Eng).
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CA08422154932B.
473. Ohara, T.
Japan. Catal. Chem. Ind. Co., Ltd., Osaka, Japan.
"The Catalytic Reduction of Nitric Oxide over Supported Rhodium and Copper
Nickel Catalysts" (Conference). Catal. Chem. Nitrogen Oxides, Proc. Symp.
1974, Pub: 1975, 191-213 (Eng). Edited by: Klimisch, R.L. and J.G. Lars on.
Plenum, New York, N. Y.
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474. Taylor, K. C.
Gen. Mot. Res. Lab., Warren, Mich.
"Simultaneous Nitric Oxide and Carbon Monoxide Conversion over Rhodium"
(Conference). Catal. Chem. Nitrogen Oxides, Proc. Symp. 1974, Pub:
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Plenum, New York, N. Y.
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475. Petersen, E.E., J. Landau and E. Saucedo.
Univ. California, Berkeley, CA.
"Micro and Macro Changes in a Stainless Steel Catalyst during Reduction of
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1974, Pub: 1975, 119-31 (Eng). Edited by: Klimisch, R.L. and J.G. Larson.
Plenum, New York, N.Y.
CA08422154929F.
476. Takayasu, M., Y. Annen, K. Kanzaki and Y. Morita.
Sen. Sci. Eng., Waseda Univ., Tokyo, Japan.
" Catalytic Nitric Oxide Oxidation on Platinum and Metal Oxides and the Effect
of Carbon Monoxide on the Catalysis" (Article). Nenryo Kyokai-Shi, 1975,
54(577), 314-20 (Japan).
CA08422154864F.
181
-------
TABLE A-2. PERTINENT DATA IN REFERENCES ON NOY CATALYSIS
A
Catalyst
Company /Institution Reductant
Operating Conditions
CuO 95-10
5-90 on
, NiO
A12°3
Mitsubishi Metal
Mining Co.
CO/butane 1200 ppm NO, 350 ppm
C4Hio> 1.9$ CO, 0.65^0 ,
5.85! CO2, 8$N2 onN2.
12000hr-lS.V., 500-52QOC.
> 0.1 Ta or Nb
on ZrO2
Kaneguchi Chemical
None
20000 ppm NO. 800°C.
Srx(R.E.)1_x
NiOg on SiO2
R.E. = Rare Earth
x= 0.01 - 0.9
Hitachi Makuseru
N.R.
N.R.
WO,
Mitsubishi Chemical
None
> 500°C
4th Period Metal
Oxides
Inst. Katal., Novosi- CO
birsk, USSR
Above 140°C.
Ni 40-95, Cu 5-60
on Cr - Stainless
Steel
Esso Research
CO
Auto Exhaust
Cu, Cr.Mn, Fe, Co
Oxides on C
Toray Industries
None
0.47$ NO in N2
K, Na, Cu, Zn (1-20$) Kharkov Polytechnic
on Fe2O3 USSR
N.R.
N.R.
Ru on ceramic
Gulf Research
CO, H2, HC 204 - 816 °C Auto Exhaust
Ba, Nd(Ba/Nd =1:10 Ethyl Corp.
- 1: 100) on ZrO0
None
> 400°C
Ba - Cu Chromate Daimler Benz
CO, HC, H2
Auto Exhaust
R.E.2_X BxNiO4 Hitachi Ltd.
on various supports
CO 1000 ppm NO, 4000 ppm CO
500eC
Cu, Ni, Cr, Mn, Mo Nissan Engr.
on Carbon
60,000 ppm NO, low tem-
perature in a column con-
taining water or HNO3.
182
-------
Conversion or _ , ^
Outlet Cone. Selective SO2 Resistant Duration NQ
Kemarks
94$
65 ppm
NR
NR
^^ —
NR
< 90$
NR
NR
NR
NR
100$
NR
NR
NR
NR
NR
NR
NR
yes
NR
NR
NR
No
NR NR 1
NR NR 3
NR NR 5
NR NR 6
NR NR 7 Activity order: Co3O4 >
SnOo ^ Cr2Og > Fe2Oq >
NiO ~Mn2O3 > ZnO»TiO2
O2OR, MgO.
NR NR 9
NR NR 10 Probably the reaction
involved the carbon
carrier.
NR NR 11
NR NR 12
NR NR 14
NR NR 15
NR NR 16
1200 ppm
NR
NR
NR 17 Concentration of HNO3
3 -phase, heterogeneous
system. (cont. )
183
-------
TABLE A-2 (cont.)
Catalyst
Company/Institution Reductant
Operating Conditions
Ce/Ni on ZrCv
Hitachi Maxell
CO 0.5$ NO, 2% CO in "waste
gas, 300°C at 20,000 hr
,-1
Na2O or KgO or Mitsubishi Chemical CO,HC, H2
Cs2O on A12O3
HNOo plant tail gas or auto
exhaust 700°C.
SnO2 - CuO Tin Res. Inst.
(Cu: Sn= 0.5-0.6: 1) England
CO
150°C
50% Cu - exchanged
mordenite + 50$ Ni-
exchanged mordenite
CO, HC, H2 400 - 480°C in auto exhaust
Steel with Cu + Toyota Motor Co.
outer layer
Auto Exhaust
CO, H2 2000 ppm NO, 12$ CO, 5$
H2, 1$ O2, 7$ H2O, 68$
at 100,000 hr'1
Copper-Nickel
Alloy
Ube Industries
Copper - A19O3 Esso Research
(8$ CuO) " and Engr.
Copper - Al2Og Esso Research
(1.45$ Cu) and Engr.
Ag x Zeolite USAEC
NH 1000 ppm NOX, 2700 ppm SO2
3-5$ O2, 5000 hr'1
NH3/NO= 0.7 - 0.8.
NH3 553 ppm NOX, 0.25 - 0.3$
SO2, 6.8$ O2, fly ash,
2000hr~1, NH3/NO= 3.3
1$ NO2, 1.9$ NH3 in air
0.15 sec residence time
La2 _ x AX Cuj _ y - Hitachi, Ltd.
ByO4 (See remarks)
on ceramic oxides
CO,
" combustion " exhausts
Rh (.001-5$) on Imperial Chemical CO,
refractory
Exhaust gas with A/F ratio
of 0.95-1, 20,000-200,000 hr
-1
184
-------
Conversion Selective SO9 Resistant Ref.
or Outlet Cone. Duration ^
Remarks
500 pom
NR
NR
NR 18
76$
NR
NR
NR 19
High
NR
NR
NR 21
High
NR
NR
NR 25
NB NR NR
(300°C)84$ No NR
(350) 99^
(400) 100*'
(450) 100^
(399°C) 100 * Yes Yes
NR 26
NR 27
NR 28
(360°C) 15 ppm Yes
Yes
NR 29 Catalyst absorbs SO2
and is regenerated
by reduction in HO
(200-250°C) 99 $ Yes
NR
NR 30
(700-800°C)
High
NR
NR
NR 33 A = Y, alkaline earth or
lanthanide B=Li,Al,Ti,
V, Cr, Mn, Fe, Co, Ni, Zn,
Ga,Zr,Sn,Moor W
NR
NR
NR
NR 34
(cont.)
185
-------
TABLE A-2 (cont.)
Catalyst
Company/Inst itution Reductant Operating Conditions
Re, _VMVM'O7
-I J\ 4X »J
(see remarks) on
Western Electric
Auto Exhaust
AxBl-xM03
(see remarks) on
ZrO0
Hitachi Maxell
NR
Waste Gas Cleaning
CeO2 - Co2O4 on Hitachi Maxell
ZrO,
NR
NR
BxCol-y-
-d
(see remarks)
Hitachi, Ltd.
NR
NR
SrLaNiO,
Hitachi Maxell
NR
NR
CuO (0.1 - 10# as Hitachi, Ltd.
Cu) La2O3 (0.1 -
20% as La) ZrO2
(0.01 - 20 as Zr)
on ceramic carrier
CO, H2
(also can add NH3) Exhaust Gas
Pd, Pt or Rh doped Hitachi Maxell
Ni or CeO9 on Z rO«
CO
2000 hr
NO , 2% CO,
~L
Ag x Zeolite
Pence & Thomas
NH
NOg, 1.9^NH3 in air
Cu, Pt, Pd, Ru or Hitachi Shipbuilding
other transition ele-
ments on oxides of
alkaline earths or
alkalis or AO^
CO
400-500 ppm NOX> 1.1 ^ CO,
O2, 1.
H2O, 10,000 hr
'1
CO,
Ni and CeO2 on NiO Hitachi Maxell
+ ZrO2 carrier
CO 0.5$ NOX, 2jf CO, 3# H2O,
20,000 hr'1
186
-------
Conversion Selective SO2 Resistant
or Outlet Cone.
Duration
Ref.
No.
Remarks
(100$ at T >
300'C) NR
NR
NR
NR 35 Re = Rare Earth, M =
Ba, Ca, Pb and/or Sr,
M1 = transition metal,
x= 0.05 - 0.7
NR
NR
NR
NR 39 A=Alk. Earth, B =
Rare Earth, M = Co,
Mn or Ni,
x = 0.01 - 0.9
NR
NR
NR
NR
40
NR
NR
NR
NR 41 0.1
-------
TABLE A-2 (cont.)
Catalyst Company/Institution Reductant Operating Conditions
Ni, CeO2 and LigO
on ZrO«
Hitachi Maxell
CO 0.5$NOV, 2$ CO, 20,000 hr
X
-1
CeO2 or C1O3 (10$) Mitsubishi Chemical NH3 2000 ppm NOX, 3000 ppm NHg
r\n Al_f4 i f\ <4 f\ A n nnt\ u_ ~1
on
L2^3
10$ O2, 40,000 hr'
Pd and Rh - doped NiO W.R. Grace
on cordierite
CO 1000 ppm NO, 250 ppm CgHg,
2$ CO, 0.2-1$ O2, 10$ CO2,
10$H2O 100, 000 hr'1
Polyacrylonitrile on
SiOo
British Ley land
CO 1000 ppm NO, 250 ppm C Hg,
2$ CO, 0.2 - 1$ O2,10$CO2,
10$ H2O 100,000 hr"1
Cu wool containing Fujikura Cable Works CO 900 ppm NO, 4.5$ CO, 25$ Or
A1203 and C
on porous
oxide
Hitachi, Ltd.
NH 730 ppm NO, 950 ppm
,
^ — _ j_ t _ _ , _ ;-1 — X
6 490 ppm NH3, 1$ O2, 12$CO2,
12$ H2O 23,000 hr"1
Cu or Ni oxides on
Cu alloy
Fujikura Cable Works CO 700 ppm NO, 2$ CO, 0.5$ O2
Ni- CeO2 -Bi on ZrO2 Hitachi Maxell CO,H9 1500 ppm NO, 700 ppm HC,
1.5$ CO, 1.5$H9, 0.5$O2,
12$ C02, 12$ H20,
Temp, not reported
Fe~O, (5$) and MnO2 Toray Industries Oxida- 0.43$ NO, 2.01$ O2, 1.6$
(95$) tion
CuO
Esso Research and NH3 553 ppm NO, 0.25 - 0.30$ SO2,
Engr. trace SO3 in stack gas, 2000
hr'1
CuO (2.8$) on A12O3 Hitachi, Ltd.
NHo 735 ppm NO, 800 ppm SO2, 570
ppm NH3, 1$02, 12$H20,
CO2, 350°C.
188
-------
Conversion Selective
or Outlet Cone.
(300°C) 300 ppm MB
N0x
(360 °C) 94 # yes
(593 °C) 95 % no
(600°C) 90-98$ no
91$ see
remarks
(300-500°C) 100^ yes
(6803C) 90^ no
150 ppm NO no
Performance
not reported
15 ppm NO yes
SO9 Resistant _
* Duration
NR NR
NR NR
NR NR
NR NR
NR NR
yes NR
NR NE
NR NR
*
NR NR
yes NR
Ref.
Remarks
No.
51
62
63
64
65 Apparent selectivity may
be due to reaction of
O2 with C.
66
67
68 Produced 450 ppm NH
O
69
70 Process description in-
volviag multiple beds of
decreasing CuO content
absQrbed on catalyst.
100$
yes
yes
NR 72
(cont.)
189
-------
TABLE A-2 (cont.)
Catalyst
MnO9 - CoQO,
£ o 4
(95:5)
Company/Institution Reductant
Operating Conditions
Toray Industries Oxidation 0.43$ NO, 2.01$O2> 1.
N2O 7500 hr'1
Zeolites
Khar'k. Politekh. Inst.
Im. Lenina
NH
0.3$ NO, 3-3.8$ NHg, 3-3.8
$O2J.600 to 10,000 hr
Cu + alkaline earth Hitachi Shipbuilding
or alkali on Al O
2 3
7.3 Cu/3.5 Ni/89.1 Esso Research & Engr
A12°3
SnO2 and/or CeO2 Asahi Glass Co.
V-doped Cu-Ni alloys Texas Instruments
CO
CO,H2
NH3
CO/H2
530-570 ppm NO, 1.1 - 1.2$
CO, 0.4-0.5$O2, 13$CO2,
10$ H20, 10,000 hr"1
1400 ppm NO, 1.5$ CO, 0.5^
H2, 12$H20, 12$C02, 0-
0.8$O2, 600 ppm C^H10,
100. 000 hr'1.
750 ppm NO, 1000 ppm NIL,
44,000 hr"1 370°C
1700 ppm NO, 500 ppm 04% 0
11$ CO2, 1.2$O2, 1.5$ CO,
1.5$ H2O, 0.5$ Ho, 50,000
hr'1, 1175°F.
CuO or Fe9O3 (5
40$) and Cr2O3 (1
10$) onA!2O3
Agency Ind. Sciences NH
and Technol.
800 ppm NO, 1000 ppm
4$ O2, 200-350°C
Cu (7.6$) and Co
(5.8$) on ALjOg
Magnetite (Fe3O4)
on A12O3
Hitachi Shipbuilding
Kanebo Ltd.
CO
CO
500 ppm NO, 0.4$ O2, 1$ CC
13$ CO2, 10,000 hr-1, 45000: «
2000 ppm NO, 2«J CO, 10$
C02, lljOOOhr"1, 400°C.
Fe oxides
Khar'k Politekh. Inst. NH,
Karkov, USSR
NO/NH 1.15-1.25, 6-8$O2
2-4$ HgO 5000-13,200 hr'1,
250-310°C
CuO (2.8$) on A12O3 Hitachi, Ltd.
NH3 735 ppm NO, 800 ppm SO2,570
ppm NH3, 1$ O2, 12$ H2O,
12$CO2 350°C
190
-------
Conversion Selective SO' Resistant Ref.
or Outlet Cone. 2 . Duration Remarks
(250 °C)
88 % oxidation
(300°C) 100$
(450°C) 100$
(1100-1400°F)
84-99$
15 ppm
> 85 $
> 80$
100$
100$
50 ppm
100$
yes
NR
no
NR
NR
yes
no
no
yes
yes
NR NR 73
NR NR 78 Zeolites studied were
A-erionites (A = H,Ni,
Mg.>
NR NR 80
NR NR 87
NR NR 91
NR NR 111
yes NR 114
NR NR 115
NR NR 124
NR NR 129
yes NR 130
(cont.)
191
-------
TABLE A-2 (cont.)
Catalyst Company/Institution
Reductant
Operating Conditions
Cu-Ni-AL with Al
removed from
surface layer
Hitachi Shipbuilding
CO 700 ppm NO, 2% CO, 0.3$
CO 15, 000-20, 000 hr
'1
Pt group on CeO2 - Hitachi Makuseru
impregnated Al20o
CO/H 1500 ppm NO, 700 ppm HC,
1.5$ CO, 1% H2, 0.556 O2,
12% CO2, 3# H20,20,000 hr'1
Ni, Fe and Cr
(5-50%)
Nippon Oil Co.
CO/H
3000 ppm NO, 2.0% CO,11.
H2O, 0.3% O2, 0.4$ H2,
n f\ f\f\f\ u «"""•!•
30,000 hr
V^AyO (see re- Sumimoto Chemical NH
marks) on A12O-
Fe2°3~ CuO-Ag2O Asahi Chemical CO/H
on A1203
CuO (0.5 - 20 % as Hitachi Ltd NH
Cu) on A12O3
CuO-Al9O3 Hitachi Ltd NH
Synnel (1-10% Cu)
Pt or Pd - A10O0 Toyoto CO/H.
^ O "
275 ppm NO, 594 ppmNH3,ILl
#H2O,2.6$O2, IS.OOOhr"1
250- 300°C
300 ppm NOX, 4.351 CO, 1.6
$O , 1000 ppm HC, 20,000
hr-*, 600° C.
330 ppm NO , 21 ppm SO ,
250-50QOC.
735 ppm NO, 800 ppm SO2 570
ppm NH3, 1$O2, 12$ H2O,
12% CO2, 350°C
Auto exhaust, 30,000 hr~
500°C
La-Cu-Zr on
Hitachi Ltd
NH 735 ppm NO, 800 ppm SO9,570
-X * A ™* rf r*.
ppm NH3m
300°C
Ru and optionally Rh
or Pt on Co - ZrO2
Hitachi Makuseru CO/H0 1500
1500 ppm NO, 700 ppm HC,
1.5$ CO, 1$ H2, 0.5$ 02,
12$ CO2, 3$ H2O, 20,000^
Ru and optionally Rh Hitachi Makuseru CO/H 1500 ppm NO, 700 ppm HC
-r^i. »T5 mr\ 1 c.4L r>r\ 1 <3L tr n K.et n
or Pt on Ni-ZiO
150U ppm NO, YOU ppm HC,
1.5$ CO, 1$ H2, 0.5$O2,
12$ CO2, 3$ HgO rest N2
20,000 hr'1
192
-------
orTuTleTconc. S°luti°n SO2 Resistant Duration No!" Remarks
no
NR
NR
131
110 ppm
no
NR
NR
144
8.9$
no
NR
81* at 147
100 hrs
reported
Ni:Fe:Cr = (50-90) :
(3-40) : (3-40)
yes
NR
NR 148 A= Cu.Zn, Sn,Pb,Ti,
P. Cr, Fe, Co or Ni;
x,y = 0.5-12 z = 1-60
example: VCrO-
904
no
NR
"long
life" 149
3.2 ppm
yes
yes
NR 150 Catalyst activated in
SC-2 or S-containing
solution.
yes
yes
NR
151
92$
no
NR
NR
153
99.74
yes
yes
NR 156 Activated in SOr
or S-containing
solution.
115 ppm
no
NR
NR
157
110 ppm
no
NR
NR
158
(cont.)
193
-------
(cont.j
Catalyst
Company/Institution Reductant Operating Conditions
Ru and optionally Rh Hitachi Makuseru
or Pt on Ni-CeO -
Zr-02
CO/H 1500 ppm NO, 700 ppm HC,
1.5$ CO, 1$H , O.S^O , 12
CO2, 35*H0, 20.0007 hr.
Ru and optionally
Rh or Pt on
Co-CeO0-ZrO0
u 2t
Hitachi Makuseru
C0/Hr
1500 ppm NO, 700 ppm HC,
1.5$ CO, l^H , 0.5^0 ,
12#CO_, 3faJ3, 20,000/hr.
z, &
Metal powder ob-
tained by thermal
dissach of metal
carbonyl and/or
its oxide
Pt-Rd
Mitsui Mining
and Smelting Co.
Ltd.
CO 1000 ppm NO , 1.7$ CO,
1-2#0 X
1.) 35 x 103 hr'1 3.) 20xl(T/hr
2.) 25 xlO3 hr-1
Ru and Rh on Hitachi Ltd.
A12°3
CO 2500-3000 ppm NO,
2.5-3.0f.CO, 0.8-1.
f\
350°C-
500-900HC
2
Mitsubishi
Heavy Industries
GEL
CH4(240 m3/hr), air
(360m2/hr) mixed with
UFTfd /"\ f! ~\& f~\f\ O Q{£. TJf f\
* (Jb\J , D. 17>UH «>• y/3 ttn*"'
700 ppm SO , 1200 ppm NO
(3000 m3/hr).
Pt, Pd, Rh or
Ni
Ce, U
A12°3
Fe-Cr oxide
1.) Cu-Ni-C
(4:1:5)
2.) Cu-Ni
Sumitomo Chemical Ey, CH
Co. Ltd. C^H2,C^
Sumitomo Chemical NH
Co. Ltd.
Katsumata, Tsuyoshi NH
Seo, Tateo
Fujikura CO/H
Cable Works
H9O (0.5 m3/hr) added to
X m3/hr) and 5-7f.H , 45-55^
CH 4,15-25^ C2H4,1.2fC2H4
15-25^-C4 components (.25 -
.27 m3/hr, 43-40 vol % .
2000 ppm NO ,3 000 ppm NIL
10 f.O2 (vol)
420°, 40,000 hr"1
72^ N2, 3#O2, 10^H2O, 13%
CO2, 250 ppm NOX, 600 ppm
SO2 and NHg (NHg/NO = 2)
450°, 13,000 hr-1
800-950 ppm NO , 4-6$CO
300-400 ppm Hydrocarbons
.5-.9#.O2- 20,000hr~1
194
-------
Conversion Selective SO9 Resistant Ref.
or Outlet Cone. - 2 Duration NQ Remarks
100 ppm no NR NR 159
90 ppm no NR NR 160
1.) 65$ no NR NR 161
2.) 854
3.) 85$
100$ no NR NR 162
30 ppm yes NR NR 163
50-70 ppm NO no NR NR 164
75.5$ yes NR NR 165 Effectiveness increased
by treating support with
H2SO4 or HCl.
80 $ yes yes NR 169
90$ no NR l.)~1100hr 172 In reduction of NOx in
2.)~250 hr waste gas, Ni was more
effective than Cu.
_ ___^ (contQ
f—
195
-------
(cont.) catalyst
Company/Institution Reductant
Carbonaceous mater-
ials (Petroleum coke,
coal coke)
Ru and Rd
CoO-a- Fe203
Pt impregnated
A12°3
Pt
Fujikura Cable Works
Hitachi Makuseru
Co. Ltd.
Kanebo Ltd.
Mitsubishi
Heavy Industries
Environics Inc.
^/Hy-
drocar-
bons
Hydro-
carbons/
CO/H2
CO
CH4
NH3
Catalyst at 350° ,150 ppm NO,
3#H2, 6I/min.
1500 ppm NO, 700 ppm hydro-
carbons, 1.5$ CO, l?oH2,0.5£
02, 12$C02, 3$H20,
20,000 hr-1.
2#CO, 104 CO2, 12$H2O,
20,000 ppm NO, 30,000 hr'1.
1^O2, 10#H2O,12#CO2,350
ppm NO, 20 ppmSO2,450° C.
100 ppm SO2, 225 ppm NO,
2$O2, 450 ppm NHg.
V2°5 - A12°3
Khar'k Politekh Inst.
im Lenina, Kharkov
USSR.
NH
.11 vol^NO, .11
10,000 hr-1, 250 -290°C.
Ni-Ce oxide
Pt compounds
Cu, Rh or Ru and
alkali + alk. earth
or transition metals
Pt on al.
Cu, La, Zr
oxides
Ru-Pd
Hitachi Maxell Ltd.
Maruenu Seisakusho
Co. Ltd.
Hitachi Shipbuilding
and Engineering
Co. Ltd.
Markvart, Pour,
Koci.
Hitachi Ltd.
Hitachi Ltd
CO 0.1$ NO, 2$CO, 800°,
20 4/hr.
decom- 94 ppm NOV in N0, 180°C.
X £,
position
CO [CO]/(2[02HNO}) = l.O -
1.5, 450°C.
NH 30$stoich excess of NH.,,
220 °C, 30,000 hr"1-
NH 735 ppm NO, 800 ppm SO2,
570 ppm NH3, 12$H2O,12£
CO2, rest Ng, 350°C.
CO/hydro- 3000 ppm NO, 500 ppm hydro-
carbons carbons, 3#CO, 30,000
hr'1', 400 C.
FenOn - CuO-
Hitachi Ltd.
SO2, 20 ppm s6o, 250ppm ,
12.5^CO2,10^H20,104/hr, 300OC.
196
-------
Conversion . Ref.
or Outlet Cone. Selectlve SO2 Resistant Duration NQ Remarks
100$ no NR NR 175
40 ppm no NR NR 176 Gas also contained 180
100$ no
95$ no
90 $ yes
NR NR 177
yes NR 178 OH / HO added to ex-
haust gas.
NR NR 184
~100$ yes NR NR 187
90-100$ no
94$ no
NR
NR
1000 hr
NR
192
193
~100$ no yes NR 194
90$ yes NR 6 months 196
99$ yes yes NR 197
> 98$ no NR NR 198
> 90 $ yes yes NR 200 (cont>
197
-------
(cont.) Catalyst
Conipany/^stutution Reductant Operating Conditions
Hitachi Ltd.
300 ppm NO, 20 ppm NO , 500
ppm SO2, 20 ppm SOg, 250
ppm NHa, 2#D 12 . 5£CO , 15%
H20, lOVhr, 300°C.
CuO-Cr203
MnO2 and Ni
oxide
NiO, Ru
Cu, La, Zr
oxides
Pt group and Ru
or Ru oxide
NiO-CuO
Hitachi Ltd.
Toray Industries
Inc.
Mitsubishi Mining
Co, Ltd.
Hitachi Ltd.
Hitachi Ltd.
Japan Gasoline Co.
Ltd.
NH3
Oxida-
tion
CO
NH3
CO
.hydro-
carbons
C3H8
300 ppm NO, 20 ppm NO , 500
ppm SO_, 250 ppm NH , 2$O2,
12.555 C02, 15$ H2O, 300° C,
104/hr.
7500 m3/m3/hr, l50°C.
1850 ppm NO, 256CO, 8$O ,
10£H2O, 10,000 hr'1,
735 ppm NO, 800 ppm SO ,
570 ppm NH3, 156 O2, 1255 H2O,
1256 co0.
z
2500-3000 ppm NO, 500-900
ppm hydrocarbons, 0.8$O ,
2. 5-3. 0$ CO, 20, 000 hr-lf
800 ppm NO, 500 ppm CgH ,
l^CO, 1055 H20, 12, 000 hr-1.
NIO-CuO
Hitachi Ltd.
NH
300 ppm NO, 500 ppm SO2,20
ppm NO2, 20 ppm SO3, 250
ppm NH3, 2% O2,
, 2£/min.
V2O- (10^6), OsO2 Mitsubishi Heavy
(O.lj^), CoO (0.8$), Industries, Ltd.
S°
300 ppm NOX, 500 ppm SO2,
2%O2t CO_ and H2O present
(Baler exhaust),80,000 hr~l,
40QQC.
Mn0
Toray Industries Inc.
Oxida-
tion
0.43^ NO, 20^60 (vol),
2480C, 7500 hr~r.
V2O5-Cr2O3-CuO Hitachi Ltd.
NH3 300 ppm NO, 20 ppm NO2, 500
ppm SOg^O ppm SO3,250 ppm
NH3,25603,12.5^0,
H2O, 104 hr-1,
198
-------
Conversion _ . t. Ref.
or Outlet Cone. Selectlve SO2 Resistant Duration N80$ yes yes NR 201
yes yes NR 202
84-86$ __ NH NR 204 80<£ conversion with
, only
99$ yes NR NR 205
yes NR NR 212
no NR NR 214
100$ no NR NR 216
93 $ yes yes NR 217
30 ppm yes yes NR 221 SCL oxidized to SOg, 10
ppm residual SO2-
91$ — JNR NR 222
90$ yes yes NR 223
(cont.)
199
-------
V2°5' Cr2°3
Hitachi Ltd.
NH
(cont ) Catalyst Company/Institution Reductant Operating Conditions
300 ppm NO, 20 ppmNO2,500
ppm SO2, 20 ppm SO3, 250
ppmNH3,12.5$CO2, 15$
H20,2#O2,s.v. 104/hr,
30QOC,
3 vol.$ CO, 7xlOappm NO.
\ onnO/-i /o\ y«Ar>O/-i /o\
(M=Cu, Ni, Kanegafuchi Chem. Ind.
Mg, Zn) and/or Co. Ltd.
CO
M, M'=Cu, Ni, Co, Zn)
U V\JL. p \j\J, IAJ.U Pl-ILLl M\J
(1) 300°C. (2) 400°C, (3)
500°C, S.6xlO-3,hr-l.
and CuO
Hitachi Ltd.
NHr
300 ppm NO, 20 ppm NO2,
500 ppm S02, 20 ppm SO3>
250 ppm NH3, 12.5$ CO2,
"H20, 2.5xl04/hr, 300°
C.
CuO (>5 wt f-) and Hitachi Ltd.
MnO2. MnO2/CuO
M.R. = .12-5.8.
Same as above. (1) 250°C,
(2) 300°C.
Fe2O3 and metal TDK Electronics Co.,
oxides—A12O3- Ltd.
CO
C3H8
Ho,
1.0$ CO2, 0.
NO, 0.64$Q , lO^H^Qj
2 x 104/hr.
LaCoOs and doped U.C. L.A.
3
CO NO, CO variable concentra-
tion, variable temperature.
Pt, Pd, Ru and
Rh catalysts
U,C.L.A.
NH
^ C02, 5-% H20,3#0o,250-
1000 ppm NO, NH3/N(J0.5-
2.4, 10,000 hr'1, 250°C.
Ru, Pd on cor-
dierite
Toyota Central Research CO/HC
and Development Labs, Inc.
Exhaust gas at 400°C.
0.10 - O.lS^Pd
and 0.10-0.15^Ru
on Y-A12O
64 O
Tr. Mosk. Khim.- oxidation
tekhnol. Inst. (USSR)
0.42-0.4^ NO, 4.8-4.9^
O, 50-300°C.
Al-Fe alloy layers
on Fe and Ru, Ru
+ Rh or Ru + Pt
Hitachi Maxell, Ltd. CO/H0/
HC2
Automobile exhaust gases,
5 x 104/hr.
Noble metals in
A12°3 lavers on
metals.
Hitachi Maxell, Ltd.
CO 0.1$ NO, 2% CO, 20,000
200
-------
Conversion , nef
or Outlet Cone. Selective SO2 Resistant Duration Remarks
~ 90$ yes yes
(1) 95$ no NR
(2) 99$
(3) 99^
>80$ yes yes
(1) 80< yes yes
(2)87$
90$ NR NR
<80$ NR NR
NR 224 High catalytic activity at
high temperatures.
v2°5/Cr2°3 = °-5-2-0
NR 225
NR 226 CuO/V2O5 = 0 . 04 - 1. 0
V0OC > 10 wt $
2 5
NR 227
1 0 & "nrt" f\"F 9 TYi i Tri*
X1"D OOQ -LV^CWt. Ul 0. LLLiAi.
1 N X\ w « O —
and'CuO a2^ V
NR 229
yes
yes
NR 230 Conversion of NO is a
function of NHs/NO in-
let ratio from0.5-2.3.
86$ no
NR
NR 231
NR
NR
NR 232
no
NR
NR 233
95 ppm no
NR
NR 234
(cont.)
201
-------
(cont.)
Catalyst Company/Institution Reductant Operating Conditions
Pt, Ru and Mg
and/or Sr
Toyota Central Re-
search and Develop-
ment.
CO/HC Automobile exhaust gases
500°C, 3 x 104/hr.
BaRuOg and
MgRuO0
Johnson, Ma they and
Co., Ltd.
CO 4.04CO, 2.5$ H O, 0.4#O2,
0.2$ NO, 0.05$CHA.
Y zeolite [M-Y] Fac. Eng., Kyushu
type Univ. Fukoka, Japan.
NH
Not specified in abstract.
Ru on A1O
Bell Lab., Murray Hill CO/H NO, CO, H in the presence
N.J. ofH2OandC02.
CeO2,a-Al2O Mitsui Toatso Chemicals, NH..
Inc.
500 ppm NOX> 500 ppm NHg
" " ~ , 12,000/hr, 350°C.
V°5 - A12°,
wt. V2O_
Mitsubishi Chemicals, NH,
Ind., Co., Ltd.
1700 ppm NO, 300 pom NO2,
3000 ppm NH3,10$O2,2xl04
hr. (1) 3 00°(2) 420, (3)50QOC.
Oxides of Mn, Cu Mitsui Toatsu Chemicals, NHQ
. o
and/or Ag. Inc.
500 ppm NOX, 500 ppm NH3,
4$O0, 2 x 104/hr, 250°C-
Oxides of Mn, Cu
and/or Ag and >
I % Fe, Co or Ni
on carriers.
Mitsui Toatsu Chemicals, NH,
_ .<•.-. J
Inc. ~~~
500 ppm NOX, 500 ppm NH3,
4 vol. $ 02, 104/hr, 300°C.
500 ppm NO , 500 ppm NH
4 vol. %O2,Xl.2X 104/hr,
310°C. /'
Oxides of Mn and >^
1^6 of Cr, Mo or W
on carriers.
Mitsui Toatsu Chemicals, NH,
Inc.
Oxides of Mn, Cu
and/or Ag, and ^
1«6 Cr, Mo or W if
needed on carrier.
Mitsui Toatsu Chemicals,
Inc.
500 ppm NOX, 500 ppm NHg,
4 voK $ O0, 2 x 104/hr,
&
4 vol. $ 02,
290°C.
202
-------
Conversion
or Outlet Cone.
Selective SO0 Resistant Duration
No.
Remarks
87,92,97,9856 no
for air/fuel ratio
13,13.5,14 and
14.5
NR
NR 235
NR
no
NR
NR 236
NR
NR
NR
JNri
Catalytic activity was
.
enhanced considerably
when a second cation
esp., Co(H) or Fe(HI)
was coexchanged to-
gether with Cu(EI) in
Y-Z co lite.
NR
5 ppm
no
yes
NR
NR
NR 238 Ru is active in the
formation of CH from
CO and H.
40 ppm yes NR
(1) 76% yes NR
(2) 90<
(3) 87#
5 ppm yes NR
NR 239
NR 240
NR 241
NR 242
10 ppm
yes
NR
NR 243
5 ppm
yes
NR
NR 244
(cont.)
203
-------
(cont.) Catalyst
Company/Institution Reductant
Operating Conditions
Oxides of Mn and
Fe, Co and/or Ni
on carriers.
Mitsui Toatsu Chemicals, NH,
Inc.
500 ppm NO^ , 500 ppm
4vol. #O_,X8000/hr, 300°C.
a
Fe(> 5 wt % Fe2O )
and Cu
Hitachi, Ltd.
NH,
300 ppm NO, 20 ppm NO2,
500 ppm SO , 20 ppm SO3,
250 ppmNHg, 2$ O2, 12. 5$
CO2, 15$H2O, 2000 ml/min
Rare earth oxides Yamaguchi Univ.
oxidation
NO
Sulfides of Cu, Mn, Kuroshiki Boseki K. K.
Ni, Fe and Co
NH,
200 ppm NOX,1200 ppm
1% CO2, 5% O2> 10$ H2O,'
260 ppm NH_, 500 ml/min
400°C-
Oxides of rare earth Hitachi Ltd
metals (La.Pr.Nd,
Sm, Gd) Cu oxide
and Zr oxide into
ALO hydrate.
550 ppm NO, 940 ppm SO +
SOo, 1.2;£>9, 12.1$ H2O,
12.3% CO2, 0.435 Kg
NH^/hr, 5 x 104/hr, 360°C
O
Sintered Ferrite Kanebo, Ltd
1% CO, 10* CO , 12^H20,
1000 ppm NO, 30, 000 /hr.
(1) 500, (2) 600, (3) 70u
(4) 800°C. _
Sn02,
Asahi Glass Co., Ltd
NH
, H20, 800 ppm
SO2, 750 ppm NOjj, (650
ppm NO) with NHg in a
mole ratio
10, 800/hr.
Fe oxide supported Univ. Calif. Berkeley ' CO/Hr
on aluminum
Flue Gas
SnO_ and
Cr263
Garzuakciokinet Tansz, CO, H2 Not specified in Abstract
Magy. Tud. Akad., Szeged, C2H.
Hung.
204
-------
Conversion „ , . Ref.
or Outlet Cone. Selective SO2 Resistant Duration NQ> Remarks
10 ppm
yes
NR
NR 245
> 90 %
yes
yes
NR 246
FeO /CuO mole ratio
1.5 - 20.
NR
NR
NR 248
Catalytic activity of
nonsesqui oxides >.
sesqui oxides.
93$
yes
yes
NR 249
23 ppm
yes
yes
NR 250
(1) 23 % (2) 85% no
(3) 100$ (4)10($
NR
NR 251 Equal moles of a-
Fe O and CoO.
ft O
NOx cone. 90, 4, yes
2,5,3.5, 130 ppm
at 275, 344, 373
383, 407,430°C.
resp.
yes
NR 252
"NO and CL are
reduced"
no
no
NR 253
NR
NR
NR
NR 254
(cont.)
205
-------
TABLE A-2 (cont.)
Catalyst Company/Institution Reductant
Operating Conditions
Oxides of Mn and at
least one of Fe, CO
and Ni and at Least
one of Cr, Mo and
W on carrier.
Hirokawa, Takahashi,
Nagayama
MITS TOA
NH_
NOV, 500 ppm NH?
o e AO /-i "
500 ppm NOX, 500 ppn
4$O2, 104/hr, 350°C.
MnO , V2O3,
LagOg, CeO2,
Nb2O5 and/or
Fe203
Toyota Central Research CO/HC
and Development Lab-
oratories.
NO 1000 ppm (exhaust gas)
NiO, Ru (0.1 -
.5 wt.
Mitsubishi Metal Corp.
CO 1800 ppm NO, 1.8$ CO,
0.7#O2, 10$ H2O,10,000/h£
(1) 400, (2) 500 (3) 600°C.
Pt
Fe203- Y-A1203
Stanford University
Tokyo List. Technol.
Decompo-
tion of NO
by Pt
H2
NO, 02
Not specified
in abstract
Ru (0.02 - 0.85$)
Pt, Pd and/or Rh
(0.001 - .7 < )
Nissan Motor Co. Ltd.
CO/H
1000 ppm NO, 500 ppm pro-
pane, 2.0,; co, 12.056 co2,
5< O2, 1.0$ H2, 5.0
290°C.
Cu and > 1$ of al-
kali, alk. earth,
transition or noble
metals on y- alu-
mina support.
M20 ' Fe20
(M= Li, Na, K,
Ba, Cu)
Fe oxide and
V oxide
Hitachi Shipbuilding.
Kanegafuchi Chem.
Industry
Asahi Glass Co., Ltd
NH 4.2$ O2, 12$ CO2,10
-------
Conversion Selective SO Resistant Duration Ref. Remarks.
or Outlet Cone. No.
5 ppm
yes
NR
NR
255
150 ppm
no
NR
NR 256
(1) 85 % no
(2) 98$
(3) 100$
NR NR 257
NR
yea.
NR
NR
259
NR
NR
NR
NR
260
90
no
NR
NR
261
(1) 83$
(2) 100
(3) 98$
(4) 99$
yes
yes
NR 262 Catalyst tested: Rh
(0.03$ Cu (5 ^ and
Mg ( 3$)
(1) 65$
(2) 98$
(3) 100$
no
NR
NR
2B3
NOX: 200, 10, yes
35,13,7,20,100,
200ppmat260,285,
302,335-, 370,400,
420,450°C,resp.
NR
NR
265
: 10,50,18,1, yes
5 ppm at 305, 320,343
395,42 7°C'rasp.
NR
NR 265.
(cont.)
207
-------
(cont.) Catalyst Company/Institution Reductant
Operating Conditions
Cu (0.1-10$), La Hitachi, Ltd.
(0.1- 20£), Zr (0.01-
12$) oxides or double
oxides
CO/HC Exhaust gas pipe of a 4-cy-
linder gas engine.
0-contg. S compel.
and Fe, Cu, Cr,
Mn, V, Ni and/or
Ti
Hitachi, Ltd.
NH,
300 ppm NO, 20 ppm NO2,
500 ppm SO2, 20 ppm SOg
250 ppm NH3, 12. 5 $O2,
CO2, 195? H2O (vapor), 5 x
lOVhr, 300°C.
SnO_, MoO3
Ni-Cu-Cr
Asahi Glass Co.
Ltd.
NHr
750 ppm NO , (650 ppm
NO) with NHg at mole raf 10, 000 hr-1, 20Q-
5000 C.
427 ppm NO, 613 ppm NHg
2.8 % O2, 89.4^ N2,7.8&
H2O, 15,600 hr-1.
2.6*5 O2, 11.7^H2O. 307
ppm NO, 629 ppm NHg, 1.36
x 10~4/hr, 200° - 250o.
300 ppm NO, 20 ppm NO2>
500 ppm SO2, 20 ppm SOg,
250 ppm NHg, 2 % O2J.2.5#
CO2, 15$ H2O, lO^ hr-1,
250-45QOC,
1000 ppm NOX, 2. 5 i/min.
(1) 300, (2) 450 (3) 600
(4) 75QOC. "Mk
Pt group Sumitomo Chemical Co. H* CH4, 0.5 m3/hr H2O, 0.'2^NOX,
-C2H6,etc. 2.1-2.8% O2, 17-18 m3for,
430-440°C.
Kobe Steel Ltd.
CO 2.7$ NO, 1.1% CO,
2000/hr, 650°C.
-------
Conversion _ , ,.
Outlet Cone Selectlve SO2 Resistant Duration Remarks
~99$ no NR NR 266 Porous ceramic
carriers.
yes NR NR 267
45 ppm yes NR NR 268 NO2=Oppm.
> 954 yes NR NR 270
9 ppm yes NR NR 271 NHg 3 ppm.
91$ yes NR NR 272 A = Ni, CO, Zn, Mo,
W, Sn, P, TL
~85$ yes yes "improved 273 x,y=0.5-12$
durability" z = 1 - 54$.
(1) 82*, (2) 92$ NR NR NR 274
50 - 70 ppm no NR > 70 hr 278
100$ no NR NR 280
(cont.)
209
-------
TABLE A-2 (cont}
Catalyst Company/Institution Reducfcant Operating Conditions
CeO-—Fe oxide
Mitsubishi Chemical
Ind. Co., Ltd.
2000 ppm NO (300 ppm
(NO),3000 ppm NH3, 1$
vol O2r 2 x lQ4/hrs (1)350S
(2)410, (3)4400C.
Fe oxide
Mitsubishi Chemical
Ind-. Co. 'Ltd.
NH 10$ Og-, 1700 ppsn NO, 300
d ppm NO2> 3000 ppm NH3,
2xl04/hr"1, (1)350
(2) 400 (3) 480° C.
Ce oxide
Mitsubishi Chemical
Ind. Co. Ltd.
NH,
1700 ppm NO, SOOPpmNCh
3000 ppm NH3, 10% O , 2~
x 104 hr'1, (1) 36fr, (2) 390
(3.) 420 (4) 460° C.
Rh, Ru
Asani Chemical Industry
Co. Ltd.
CO
2.2 -2.5 % CO, 2,
ppm NOx, 3.2 x 104 hr~l.
(1) 350,X(2) 5000C.
620 ppm NO, NH3/NC=l-53
1.2 x 104 hr-1, 305°C.
Cu
Research Foundation for
the Development of Indus-
tries.
NHr
Zeolite with Cu
Toray Industries Inc.
NH 0.3$ NO, 3;;NH3, 5$ O2,
1.6f, HO, 10,000 hr'1
400°C.
720 ppm NO, 910 ppm NH
44 O2, 21,000 hr-1 (l)30ff
(2) 350, (3) 400 (4) 450
(5) 500°C.
Ce, W
Hitachi, Ltd.
NH,
SiO_, Si acid or
silicates
Kobe Steel, Ltd.
oxidation 200 ppm NO, 3rfO2, 400
witk ppm HNOg, 100 # rel. h\x-
HNO midity at 27°C.
Pt
Mitsubishi Heavy Ind.
Ltd.
NH,
ll?b CO?, 15 <* HgO, 2.SJ?
O2> 175 ppm NO^ 3200
ppm SO2> 176 ppm NHg.
Fe compound
Hitachi Ltd.
200 ppm NOx,500ppmSO2,
20 ppm 803, 40 nig/m3
dust_ 10,000 hr-1
210
-------
Conversion or Selective SO Resistant Duration Ref. Remarks
Outlet Cone. No.
(1)60.9$ yes NR NR 281
(2) 98.2$
(3) 64. 9"
(1) 77.5^ yes NR NR 282
(2) 87.3$
(3) 90.555
(4) 92.3$
(1) 69.5% yes NR NR 283
(2) 73.75^8
(3) 76.25$
(4) 73.0$
NOX: (1) 85•£• no NR NR 288
(2) 38«S.Ha; (1) 82$
(2)95$(Ru).
97$ yes NR NR 289
99^ yes NR NR 291
(1) 98$ (2) 100$ yes NR NR 290
(3) 106$
(4) 100$
(5) SI"?
50 - 98
-------
(cont.) Catalyst
Company/Institution Reductant Operating Conditions
Ir-Al2O3 plus
Ru-ALO0
Toa Nenryo Kogyo K.K. C3H6
CO, H0
1500 ppm NO, 400 ppm
C3H .l.O^CO.lO^COg,
0. 5$ H2,10$H2O, (O2
G£ needed to oxidize all CO,
C3H6andH2>= (1)0.45, (2)
0.8 (3)1.0 (4)1.2 (5)1.6;
300 m3/hr, 50QOC.
2400 ppm NO, 10 ppm NO_,
300 ppm NH3, 600 ppm
SOg.6000 hr-1.250°C.
Sulfate of Mn,
Cr, Cu,Fe,V
or Ce
Mitsubishi Gas Chemical NH
Co., Inc.
Na,K,Mg,Al,
Sn, Mn, Cr,Ni,
Cd, Cu,Fe,Li
and/or Be Sulfates
plus oxides of V,
Mn, Cr, Cu and/or
Fe on conventional
carriers
Mitsubishi Gas Chemical NH3 240 ppm NO, 10 ppm NO2,
r*s\ Tr»*-» o nn i-mw* XTTT cnn mrim*
Co., Inc.
^j-fcu pfLLi INVJ, iu yyLii nv
300 ppm NH3, 600 ppm
SO , 3#0 , 12#C02,
-1, 250<>C.
Sn, W and Mo
oxides
Hitachi, Ltd
NH
290-310 ppm NO, 240-260
ppm NH3, 450-550 ppm
HO, ll.OOOhr-1, (1)250
(2) 300 (3) 350 (4) 400
(5) 450, (6) 50QQC.
Rh-Al2O3
V-oxide
W-oxide
Fe203 (94.5$
Cr0O«, (5.5^5)
£i O
Fe,Ag or their
oxides with Cu,
Pb,In-, Ce.Be or
their oxides on
Monsanto Co. H2, CO
Sumitomo Chemical Co. , NH»
Ltd.
Hitachi Ltd. Oxidation
Asahi Chem. , Co. ^4^10
*&$ H20, 10,000 hr"1 , 26%°C
2.6^O2, 12.1^H2O,555
ppm NO, 617 ppm NHg,
13,700 hr'1, 250-400 oc.
Not specified in abstract.
450 ppm NOX,2.5#O2,(15
nvVhr) mixed with C^^Q
(0.1 m3/hr).
212
-------
Conversion
or Outlet Cone.
Selective SO0 Resistant Duration
2 No.
Remarks
(1) 92$
(2) 100%
(3) 96$
(4) 85$
(5) 60$
no
NR
NR 301 Two stage reactor
(Ir section first).
96$
yes
yes
NR
306
18 ppm
yes
yes
NR
307
(1) 64$ yes
(2) 84$
(3) 91$
(4) 93$
(5) 94$
(6) 93$
50<* no
>97# yes
NR
yes NR 310 Pressed Catalyst
NR NR 311
NR NR 315 V/W= (7-11.7):
(0.3-5) molar
no oW.eri- 0,0
yes ... 312
J oration in
100 hrsi.
91$
no
NR
NR
316
(cont.)
213
-------
(cont.) Catalyst
Company/Institution Reductant Operating Conditions
Ru, Pd on
A12°3
Cu2O on stainless
steel wire
CuO, CoO on
A12°3
CuS04, FeS04
on A12O3
CuSO4 on Al2Og
NiO
Hitachi, Ltd.
Fujikura Cable Works
Ltd.
Mitsui Petrochemical
Industries, Ltd.
Okayama University,
Okayama, Japan
Mitsui Petrochemical
Industries, Ltd.
Dep. Catalisis, Cons.
Super. Invest. Cient.
Spain
NH 300 ppm NO, 10-15 ppm NO
450-500 ppm SO2, 250-300
ppmNHg, 3-5$O2, 10-13$
H0O, 3 x 104 hr-1, 350<>c.
Li
CO 1565 ppm NO, 2. 1$ CO, 12.04
H2O, 0.5$ O2, 3 x 104 hr-1
4800C.
NH 300 ppm NO, 3^O2, 15<* CO2>
12$H2O, 400 ppmNHg, 1.5
x 104 hr-1, 350°C.
NH 500 ppm NO, 1000 ppm SO,,
667 ppm NH3, 15#O2, 10 f
H2O, 1000 N Cm3/min,
<~400°C.
NH3 300 ppm NO, 400 ppm NHg
3% O2, 15$ CO2, 12*H2O,
1.5xl04hr-!, 350°C.
tin U.O x' ?' 2'
372-1969 ml/min, 210-449°C
Mo
Osaka Munic. Tech. Res.
Inst., Osaka, Japan.
NH 850-950 ppm SO2, 1100 ppm
NO, 1380 NH3> 5.22-5.314
0,
, 10,700 -900
hr-1, (i) 200 (2) 350°C.
Cu-Cr oxide
Mitsui Toatsu Chemicals NH-
Inc.
300 ppm NOX, 50 ppm SOX,
38 ppm CO,
CO2,
O, 6.
2,
O, 30 £/
hr NH
Ir-Au on
Toa Nenryo Kogyo K.K. CO,H2
propy-
lene
1500 ppm NO , 400 ppm
propylene, 1.
^~2, O.Sfo H2, 10^H36,
0.42-15 %O0, SxlO^hr-l.
ft
Mn-Cr oxides on
A12°3
Mitsubishi Chemical
Industries, Co., Ltd.
NH 2000 ppm NOX (300 ppm NO)
3000 ppm NH3, 10^ O2, 2 x
104 hr'1, 32(Toc.
214
-------
Conversion
or Outlet Hone
Selective
Ref.
SO9 Resistance Duration " Remarks
—£ Ma,
*1VI
80$ yes
90$ no
98$ yes
"Excellent yes
conversion"
12 ppm yes
99$ no
NO2 yes
(1) 25.8 ppm
(2) 0 ppm
30- ppm yes
73$ no
yes continuous 321 Not readily inactivated
over 100 by SOV, O0, CO0
A & £
hr
NR NR 323 Catalyst with only Cu
required 820ocfor 90$
removal.
yes NR 324
yes NR 328 For CuSO4, presence
^f SOX made rate higher
yes NR 336
NR NR 338 Catalyst lost activity
but regenerated by
heating in O2 flow.
yes no de-: 339
crease
after 30hr.
NR NR- 343-
NR NR 344
72$
yes
NR
NR 345
(cont.)
215
-------
(cont.) Catalyst Company/Institution Reductant Operating Conditions
FeCr oxides
Ube industries, Ltd.
NH 3£O , 1000 ppm NO, 1100
ppm NH , 700 ppm SO2>
15,000 hr-1, 400°C.
on
Toa Nenryo Kogyo K. K.
CO,H2 1500 ppm NOX, 400 ppm pro
propy- pylene, 10$ CO, 10#CO2>
lene (?. 5$ H2, 10$ H2Oi, 0.42 * -
Compounds of Ti, Takeda Chemical
Cr.Mn, Fe, Co>,Ni, Industries, Ltd.
Cu, V.Mo.or W with
H3Bo3 or H3PO4 or
their salts on C
NH3 0.2£ NO, 0.3^ NH3, 1
5$ O2, 93. 5^ He. (1)
(2) 150°, (3) 25QOC.
V O on Y--«-lunaina Mitsubishi Heavy Indus
tries, Ltd.
NH 8.5# CO2, 16. 8'HO, 2.6^
O2, 169 ppm NOX, KO ppm
NO, 217 ppm NH3, 104 hr-1,
300-400°C.
Rh on Al O Mitsubishi Heavy Indus- CO 1500 ppm NOX, 30 ppm SO2,
tries, Ltd. 2$ CO, 14£ CO2,
1* O0, 300°C-
MoO_, CoO
tJ
Toyo Engineering Corp. NH., 600 ppm NO, 50 ppm
O2, 6< H2O, 15*g CO2,
1500 ppm SO2, plus NH3
(NH3/NOX= 1.35) 15,000
hr-1, 500°C.
Fe-W Mitsubishi Petrochemical NH 700-900 ppm NO, 850-1100
Co., Ltd ppm NH3, 4$O2, 1.07xl04
hr-1, 200°C.
V2°5 °n A12°3
Agency of Industrial
Sciences and Technology
•NH,
300 ppm NO, 500 ppm NH
3.0$ O , 9.2# H20, 16, OIK
hr-1- (I) 250°, (2) 300°,
(3)350°, (4)450°C.
Fe-Al Co-Mn
oxides, Pt group
Hitachi Maxell, Ltd.
CO,H 1.2-5 CO,
H2, 14#CO2,
.2, 20, 0.05^
C3H8, 0.1% NO, 2 x 104 hr-1
5000C.
216
-------
Conversion „ ,
or Outlet Cone. Selective SO2 Resistant Duration
93$
yes
Remarks
yes
more 346
than
80 hrs
90$
no
NR
NR 347
(1) 91$
(2) 99f.
(3) 100«?
yes
NR
NR 348 Example Catalyst:
on C.
903
yes
NR
NR 349
~100$
no
yes
NR 350 Produced ~400 ppm NH0
110 ppm yes
NR
NR 351
yes I
NR
NR 352 Fe/W ratio 9/2
(1)
(2) 99$
(3) 100$
(4)
yes
NR
NR 353
no
NR
NR 356
(cont.)
217
-------
(cont.)
Catalyst Company/Institution Reductant Operating Conditions
Ru-Rh
Hitachi Maxell, Ltd. CO, CgHg/
1.2% CO, 14#CO , 0.05$
C3H6> 0.3 - 1.0$TO2, 0.6
H2, 10* HO, O.KNO
Refractory inorg.
oxides coated with
CuO and NiO
Ube Indus triesv Ltd..
NH
1660 ppm NO, 2.5% O2,
1570 ppm NH3,
1.5xl04/hr, 3000C.
Pt on surface of a Inoue Japan Research
conveyor belt. Institute
NR
Flue gas containing NO .
1st layer: NiO-CuO, Toyota Central Research Oxida-
NbgOg-YgO^-CuO, and Development Lab- tion
Nb2O3-CoO, Y2O3- oratories, Inc.
CoO, CeO2, L^OS
Fe2O~, NbgOg - or
NiO-Mn,,O0. See remarks.
£ 3
Automobile Exhaust Gases
Pt, Ru, Pd on
A12°3
VOX, A12O3 and
BN, Al hydro-
xychloride
Al, Cu, Mn
Fe-Cr-Oxides.
Nippon Shokubai Kagaku Oxida-
Kogyo Co. , Ltd. tion
Kanegafuchi Chemical NH
Industry Co. , Ltd.
Hitachi Shipbuilding NH3
and Engineering Co. , Ltd
Ube Industries, Ltd. NH,,
Waste gas 500°C.
400 ppm NO2, 40 ppm NH ,
1500 ppm SO , 2£O2, 10
-------
NR
NR 357 NH» 0-100
o
ppm
yes
NR
NR
358
NR
NR
NR
359
80-100$ NR
NR
NR 360 2nd layer: Pt,Pt-Rh,.
Pt-Pd on NiO-Cr2O -
CuO- Fe20~ - BaO.
Also a layer of Cu,
CuO.
92$
90-95$
NR NR NR 361
yes yes NR 366
~60-70<* yes yes NR 367
0.
(1)
(2)
(3)
83.7$
0054 vol.,1
99.8$
61.5$
80. 3#
84. 5<
93$
yes yes NR 368
see NR 30 min. 370 O0 is in slight excess.
remarks ^
yes yes NR 371
yes NR NR 372 VgOg/MnO < 1
NO NR NR 373
219
-------
(cent.) Catalyst
Company/Institution Reductant
Operating Conditions
Fe2O3, MnO2, CuO, TDK Electronics Co.,
RuonAL2O Ltd.
NH
4$ O2, 400 ppm NOX, 1000
ppm SO2, 10< H2O, 400 ppm
NH3, 5 x 103/hr, 400°C.
Ti, V
Mitsubishi Petrochemical
Co., Ltd
700- 800 ppm NO, 600-700
ppm NH3, 482 ppm SO?. 4$
O2> 7.14% H2O, 5 x lOVhr,
250°C.
Ti, V oxides and/
or Mo, W, P and/
or B oxides
Takeda Chemical Indus- NH,
tries, Ltd.
0.03$ NO, 0.06$SO2, 6.0$
O2, 10$H2O, 0.03 vol$
NH3, 5x 103/hr, 200°C.
CuO MnO2
Mitsui Toatsu Chemicals NH,
Inc.
(1) 500 ppm NOX, 500 ppm
NHg, 4$O2, 15$H2O, 2 x
lO'Vhr, 250°C. (2) same
as 1 except O2 = 8<* .
MnO2, Fe2O ,
CuO, Ru
TDK Electronics
Ltd.
CO 1$CO, 0.1$ hydrocarbons,
0.1$ NOX, 10$H2O, 1$O2,
lOVhr, 40QOC.
MCo204
Mitsui Toatsu Chemical, NH3
Inc.
150 ppm NO, 15 ppm N2O,
4$ O2. 23$ H2O, 50 ppm
SO2, 10^ CO2, 165 ppm
NH3> 104/hr, 300°C.
SnO2, Cr2Og
Cu with alkali metals
or transition metals
and with Rh or Ru on
Asahi Glass Co. , Ltd NHQ
O
Hitachi Shipbuilding and H2
Engineering Co. , Ltd.
750 ppm NOX, 800 ppm SO2,
8 $ 02, 8$ H20 (NH3/NO
mole ratio = 1.3) 10,000/nr.
600 ppm SO2, 500 ppm NO,
0.4<*O2> 1.1$ H2, 15£CO2,
10$ H2O, 104/hr, 4500C.
Sulfates of Co, Mn,
Ce and/or Ni,
coated with Ru on ;<,V
A1203
Hitachi Makuseru Co. ,
Ltd.
H2 • Exhaust gases, 2 x 104/hr,
1500 ppm NO. f~
Al alloy, Fe, Ni
and Ce oxides
Hitachi Makuseru Co. ,
Ltd.
CO/H2 Automobile exhaust gases,
HC 5 x 104/hr.
220
-------
^ i.i i. /-, Selective SO. Resistant Duration „ * Remarks
or Outlet. Crnin. ?• No.
> 804 yes yes NR 374
97 80$ no
NR NR 378
83.2$ yes yes NR 379 M = Ni, Zn, Mg, Ca,
Mn, Cu or Fe.
100$ yes yea NR 381
100^6 nt> yes NR 385
100 ppm NR yes NR 386
NR NR 1150 hr 387 ((jont
221
-------
(cont.) Catalyst Company/Institution Reductant Operating Conditions
Carboxylates of Fe
metals or Cu on
A12°3
Mitsui Mining and
Smelting Co., Ltd.
NHC
Exhaust gas, 1000 ppm NO,
Ru and Cu, Zn,
Ni, Co, Cr and/
or Ag.
Hitachi, Ltd.
CO 3$CO, 3000 ppm NO, 3 x
104/hr, 300°C.
Cu or CuO on
Y - A10
Japan Gasoline Co., Ltd.
1100 ppm SO2> 500 ppm NO
550 ppm NH3, 3$O2> 10^
H20, 94.1 4/hr, 40T>OC.
Si02 -A1203
coated with Cr,
Mn, Fe.Co, Ni
and/or Cu oxide
Mitsubishi Chemical In
dustries Co., Ltd.
NH,
O , 2000 ppm NOX
3000 ppm NH3, 2 x 104/hr,
360°C.
Cr, Mn, Fe.Co, Ni
and/or Cu oxides
on acid-treated
carriers.
Mitsubishi Chemical In-
dustries Co., Ltd.
O2, 2000 ppm NOX,3000
ppm NH , 2 x 104/hr,
Fe and Cr oxides
•y- A12O3 carriers
Mitsubishi Chemican In-
dustries Co., Ltd.
Waste gas, 380°C.
Ni, Cu, Cr oxides
Toyota Central Research
and Development Lab.
CO/H9/ Exhaust gas. 600°C,
HC
6 x 104/hr.
Alloy of metals
from groups IB,
HI, VH B and VIII
International Harvester
Co.
CO/H- Exhaust (automobile)
HC 800-1400 °F.
Si,Si oxide
Kobe Steel, Ltd.
370 ppm HNOo, 0.12$ SO2
210 ppm NO [10 ppm NO2
200 ppm NO J, 4>O2,
co2.
Ti and > \* of Mo,
W,Fe,V,Ni,Co,Cu,
Cr, U and Sn as
oxides.
Mitsubishi Petrochemical
Co., Ltd., Hitachi Ltd.,
Babcock-Hitachi K.K.
NR
200-500°C.
Cu alloy containing
Zn, Fe,Mg, etc.
Inone Japan Research CO/H-
last. HC
Waste gas, 3600 ppm NO
100 ml/min.
222
-------
Conversion Ref.
or Outlet Cone". Selective SO2 Resistant Duration No. Remarks
78£
40$
90$
75.3$
76. 5#
74$
76$
>90£
<5ppm
~95£
yes
NR
yes
yes
yes
yes
NR
NE
yes
NR
yes
NR
yes
NR
NR
NR
NR
NR
yes
NR
NR 388
NR 389
NR 394
NR 395
NR 396 Example: y- A12O
carrier.
NR 397
NR 398 Catalyst contains 2-12<*
O0, honeycomb shape.
&
NR 400 Ni, Cu,Fe,Mn,Y
NR 402
NR 404 Example: Ti + Mo
(Ti/Mo= 9:1)
13 ppm NO2 NR NR NR 407 (cont.)
223
-------
(cont^Catalygt
Company/Institution Reductant
Operating Conditions
Cu, Al, Fe and
StOo
Japan Gasoline Co.,
Ltd.
NH,,
500 ppm NO, 550 ppm NH3
1500 ppm SO2> 3# O2,
H20.
CuO on A12O3
Fujikura Cable Works Oxidation
Ltd.
1200 ppm NO, 10$O2,
5je/mLn.
Ni-Cu-Co
(30:10:10)
Nissan Motor Co., Ltd. NR
(1) 400°, (2) 900°
(3) 120QQC.
Ti,Mo,Ni and Fe
(Pelletized with C
and fired)
Hitachi, Ltd.
^ N2O, 20$ H2, 3<* O2,
5000/hr, 375-500°c>
SKX
Kobe Steel, Ltd.
Oxidation 200 ppm NO, 34 O , 400
ppmHNO3-
CeO,, TiO2 on
Mitsubishi Chemical
Industries Co., Ltd.
NHr
10<*O2, 300 ppm 2,
1700 ppm NO,3000 ppm
NH3, 2xl04/hr. (1)260C
(2)310°, (3) 410°, (4)
450°, (5) 505°C.
CeO2 on T -
Mitsubishi Chemical
Industries Co., Ltd.
NH,,
O , 300 ppm NO2,
1700 ppm NO, 3000 ppm
NH3,4xl04/hr. {1)250°,
(2) 310°, (3) 370 ,
i^J-AX > -fcrf>.J. vr / AA^. • \*, y
(2) 310°, (3) 370 ,
(4)430°, (5)460°C.
CeO2 °n a-
Mitsubishi Chemical
Industries Co., Ltd.
NH
*.» -'*->•&, 300 ppm NO2>
1700 ppm NO, 3000 ppm,
NH3,4xlQ4/hr. (1) 300<>
(2) 380° (3) 420°C.
Pt on a - A12O3
Mitsubishi Chemical
Industries Co., Ltd.
NH
--,—z, 300 ppm NO2,
1700 ppm NO, 3000 ppm
NHL, 4xl04/nr. (1)225°^
(2)230°, (3)235°>(4)240°C
V-oxide on a -Al2Og
Mitsubishi Chemical
Industries Co., Ltd.
NH,
O2, 300 ppm NO2,
1700 ppm NO, SOOO.ppm
NH«, 40,000/hr. (1)210°
(2) "270°, (a) 330° (4)360°C
224
-------
Conversion
or Outlet Cone. Selective SO2 Resistant Duration *ef. Remarks
NR
No.
yes
yes
NR 413 Catalyst prepared from
sulfates, roasted at
5500C.
69$
NR
NR
414
(1) 98fS
(2) 97$
(3) 97%
NR
NR
NR
415
100$
yes
NR
NR 417 > 5$ Ti. Example:
Ti:Fe= 9:1. Nitrous
oxide reduction.
86$ converted
to NOn
NR
yes
NR 419 N2° sut)sequently aK-
sorbed in 2$ Mg(OH)2
slurry.
(1) 54.8#
(2) 71.5$
(3) 86.34
(4) 87.04
(5) 84. 0$
yes
NR
NR
421
(1) 24.0^
(2) 49.0$
(3) 73.8<
(4) 80. 5-*
(5) 78.0$
yes
NR
NR
422
(1) 47. 5<
(2) 72.8$
(3) 75. 5$
yes
NR
NR
423
(1) 82.0$
(2) 84.0$
(3) 84. 0$
(4) 79.0$
yes
NR
NR
424
(1) 40. 84
(2) 67.04
(3) 81. 0<*
(4) 77. 0£
yes
NR
NR
425
(cont.)
225
-------
(cont.) Catalyst Company/Institution Reductant
Operating Conditions
V2°5
Duengemittel-Prod.,
BASF, Ludwigshafen Ger.
NH,
Effluent gases from a HNO3
plant. 500-1000 ppm NO
X
Cu oxide and alkali
metal oxide
C-carrier.
T6ray Industries, Inc. NR 0.47$ NO, 6000/hr.
FeSO4 on
Hitachi Shipbuilding and Decompo-
Engineering Co., Ltd. sition or
Oxidation
500 ppm NO, 500 ppm
4$O2, 12$ C02, 10$ h
2 x lOVhr, 390-500°C
CuSO4, FeSO4 on
Y-A12©3
Mitsui Petrochemical
Industries, Ltd.
NHL
3$02, 154 C02, 12$H20
300 ppm NO, 1500 ppm S
200 ppm NH3, 15vOeO/kr
350°C.
Fe-containing ores
cinders, scales,
etc.
Nippon Kokan K.K.
NH
7$ CO2, 13$ O2, 79.7$ N2,
0.3$ CO, 15 ppm NO2, 13£-
155 ppm NX), 200 ppm NHg.
300 i/hr, 300 - 370°C.
Sn, Sn/Fe
at. ratio: 0.01-20
Graphite carrier.
Hitachi, Ltd.
NH,
290-310 ppm NO, 240-260
ppm NH3, 450-550 ppm SO2,
2-4$ O2, 12.53 CO2, 15$
HO, 59,000/hr. (1)300°
(2) 350°, (3) 4000 (4) 45QOC.
Corp. Res. Lab. ,
Exxon Res. and Eng.
Co. , Linden, N. J.
CO CO-NO + 75 $ excess ox-
idants .
Ni and Thorla,
Mullite carrier
Ube Industries, Ltd.
CO Helium contg;: 0.3$ NO,
1.3?,H2, 0.7$ O , 0.05$
C2H4, 2. 5$ CO, V C02,
1 5$ H2O, 1800 ppm SOg,
700°C 5xl04/hr. (1) (Thr,
(2) 1 hr, (3)2 hr, (4)5 hr.
2000 ppm NO, J.O, 000 ppm
CO, (1) 385° (2) 450°,
(3) 540°C, 40,000/hr ,
ABOr
A12O carrier
duPont de Nemours, E.
I., and Co.
CO
226
-------
or
Sonversion Selective SO0 Resistant Duration Bef. Remarks
utlet Cone. & No.
50-150 ppm yes NR NR 426
NR NR NR 428 0.1-2.0#Cu. Probable
reaction with C.
95% — yes NR 429
93$ yes yes NR 430 Example: CuSO4 60$
SO4 1. 5$
87$ yes NR NR 431
(1) 82. 8$ yes
(2) 91.'5jS
(3) 97. 056
(4) 92. 3<
yes NR 432 Fe> 2$ (as Fe2O )
Sn/Fe = 0.01-2(f.
90$ yes NR NR 435
(1)9658 no yes NR 436 Example: Ni:Th= 1:0.1
(2) 934?
(3) 93<*
(4) 924
(1) 25% no NR NR 438 A = metal with atomic #
/2) 5($ 11-51, 56-71, 89-103.
(3) 904 BE part Pt-group, part
non-Pt ionic radius
0.4-1. 4A, valence 3.
227
-------
(cont.) Catalyst
Company/Institution Reductant
Operating Conditions
AB0
carrier
E.I. du Pont de Nemours CO
2000 ppm NO, 10, 000 ppm
CO, 40, 000/hr (1)
(2) 380°C, (3) 550°C.
Oxides of Cu, Cr
and Fe on Al-Og
V12.x MOXW Alz
x=0-8, y=0-5,
x+y= 0.3-8,
z= 40-430
CuO on Y-A12O3
Agency of Industrial NH~
Sciences and Technolo-
gies.
Sumitomo Chemical Co. , NH_
Ltd. 3
Asahi Chemical Industry NH«
Co. , Ltd.
L300 ppm NO, 300 ppmSOg
300 ppm NH3, 2.5^ O2,
15, 000/hr, 350°C.(l)Okr»
(2) 4 hrs, (3) 12 hrs.
E. 300 ppm NO, 300 ppm
NH3 2.5$O2, 10.2<«H2O
15, 000/hr, 320-480 C.
130-180 ppm NOx, 800-1200
ppm SO2, 50-100 ppm SO3,
1.3/1 NH3/NOX, 5000-
14000/hr, (1)250°, (2)350 C
230 ppm NO, 2.5%O2, 10%
CO2, 1056 HoO, 210 ppm
NHg. 12,506Vhr, 200-500 C
CuO on mordenite Toray Industries, Inc. NHC
300 ppm NO 300 ppm
300 ppm NH3, 2% O2,
H2 O, 1000 ml/rnin. (1)275
(2)300°C, (3)350°C.
MnO,
Nippon Steel Corp.
I. 873 ppm NOX,
ratio=2,l,2000C, 4536/hr
H. 830 ppm NO , g
-2.05, 180°C,X4536Ar.
CuO and Idemitsu Kosan Co., Ltd NHL
1-10«6 oxides of Zn,
Mn and Fe on
498 ppm NO ,1005 ppmSOg
» SOOppna
NH3, I04/hr, 3500-4000C.
m NOx, 580 ppm §px
2 , 21 Oppm NHs , 1 nW Hr
200
NH 2 . 62
6 3506C(1) 1 (2)10 (3) 30 days.
Cu oxide on
A1203
Asahi Chemical Industry
Co., Ltd.
228
-------
Conversion Selective
or Outlet C^onc.
(1) 25^ no
(2) 50$
(3) 90$
I. (1)69.0$ yes
(2) 97.1$
(3) 99-100$
n. -100$
SO2 resistant Duration R^ef. Remarks
NR NR 439 A=metal with atomic no.
11-51, or 89-103. B=
part Pt group metal,
part mon-Pt metal, ionic
radius 0.. 4 -1.4 A,. 25^
multivalent. metal in 1
oxide state, > 5$ same
metal in different oxide
state.
yes NR 441 Example: 10
-------
(cont.) Catalyst Company /Institution > Reductant Operating Conditions
V, Cr,Mo and/or
W on 9-or JF-A12O3
Toray Industries,
Die.
NH
300 ppm NO, 300 ppm SO2, 200
ppm NH.,, 9# H0O, 2$ O0, 104/
jj & £i
hr. 250°f:.
hr,
Hitachi, Ltd;
Babcock, Hitachi
K.K.
NH,
300 ppm NOx, 500 ppm SO2>30
ppm SO , 50 mg/m3 dust,
H20, 1.500 , 11<*C02, 1.1 NH /
NO, 10,000/hr, (100, 000 m3/hr
flow, 370-420°C.
300 ppm NO, 300 ppm SO , 300
ppmNHs. 9#H2O, 2% O^, 5000/
V and/or Fe on
9-or K-A1203
carrier
Toray Industries,
Inc.
NHr
Cu and/or Ni
porous C fiber
Toray Industries,
Inc.
CO 0.5$ O , 0.2^ NO, 1.5<£CO,
104/hr, 400°C.
Vanadium sulfate
on AUO
Mitsui Petrochem- NHr
ical Industries,
Ltd.
300 ppm NO, 3<* O2> 15<8 CO, 12
12$ H2O, 300 ppm SOo, 300 ppm
NH0, 15,000/hr, 350°C.
MnO2 on Ti grid
carrier
Nippon Steel Corp. NH3
200 ppm NO, 200 ppm NHg,
O0, 2 x 104/hr, 150-3000
U
V205 on A1203
Nippon Steel Corp. NH3
300 ppm NO, 1000 ppm SO2>400
ppmNH3> lo%O2, 2fi/min,200°C.
Zeolite-type
Aluminum silicate
Chiyoda Chemical
Engineering and Con-
struction Co., Ltd
300 ppm NO, 2$ H2O, 15$ O
120 je/hr, 300°C.
CuO-Al203
Niigata Engr. Co.. NHg
Ltd.
5#O2, 10^H2O,400 ppm NO, 200
ppm SO2, 400 ppm NHg, 2000/hr
340-48 0°C.
Ni, Cu, Th and/
or La on mullite
Ube Industries Ltd. CO/Hg 0.25^NO, 1.0^ H2, 1.7^5 CO, 0.4?
O, 0.03CH, 8<£CO, 3.5HO,
O2,
40 ppm SO2 , balance He; 65, OOO/
hr. (1) Ihr, (2) 2 hrs, (3) 5 hrs.
500 ppm NO, 500 ppm NHg, 1500
ppmSO2, 33 O2, 10^H2O, 30-500
i/hr, 550°C.
on -
C, SMX or diatomar-
ceous earth
Japan Gasoline Co. NH
Ltd.
230
-------
Conversion Selective SO* Resistant Duration Ref. Remarks
or Outlet Cone. f No.
99.5£ yes yes NR 458
>90$ yes yes 4000 hr 459 Treatment was upstream
of economizer. Treat
gas after economizer at
360°C, conversion was
only 60$ after 1000 hrs.
93.7$ yes yes NR 460
90$ no"i NR NR 461 C fibers sensitized in
SnCl2 and HC1, activate
in PdCl2 + HC1 , then
_ dipped in
99< yes yes NR 462 3.9-? V, SO4/V = 1
yes NR NR 464
> 99<£ yes yes 140 hrs 465 Catalyst pretreated with
~ 2000 ppm SO^at 2000°C
25 ppm yes NR NR 466 NH was provided by
pretreatment of
"catalyst" with NH4NO3
92.2% yes yes NR 467
(1) 96<* no yes NR 468 Example: Ni:Cu:Th =
(2) 94$ 0.7:0.3:0.8; 8^Ni + Cu.
(3) 88%
984 yes yes NR 469
231
-------
TECHNICAL RliPORT DATA
(Picasc rcaJ Inatrucnons on flic reverse before completing)
1. REPORT NO.
EPA-600/7-76-026
2.
4. T,TLE AND SUBTITLE Parametric studies of Catalysts for
NOx Control from Stationary Power Plants
3. RECIPIENT'S ACCESSION NO.
5. REPORT DATE
October 1976
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
KenNobe, George L. Bauerle, andS.C. Wu
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
University of California, Los Angeles
405 Hilgard Avenue
Los Angeles, CA 90024
10. PROGRAM ELEMENT NO.
EHE624
11. CONTRACT/GRANT NO.
Grant R803653-01
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final; 3/75-9/76
14. SPONSORING AGENCY CODE
EPA-ORD
15.SUPPLEMENTARY NOTES JERL-RTP project officer for this report is R.D.Stern, 919/549-
8411 Ext 2915, Mail Drop 61.
is. ABSTRACT Tne report gives results of 2i study of vanadia-alumina and iron oxide-
chromium oxide-alumina catalysts for the reduction of NO with NH3 in simulated flue
gas. Optimum catalyst compositions were 15% V2O5 on A12Q3 and 10% Fe-Cr oxides
on A12O3 with an Fe/Cr ratio of 1/9, respectively. Both catalysts were selective
for the reduction of NO to N2 in the presence of O2. Both were shown to be sulfur-
resistant during total periods of operation of 648 hours for V2O5 and 1052 hours for
Fe-Cr in the presence of SOx. Typical conversion levels for V2O5 and Fe-Cr
catalysts operating at 400 C in simulated flue gas containing 1000 ppm NO, 1000 ppm
NH3, in the presence of SOx, were about 90 and 80%, respectively, at 20,000 per
hour space velocity. Rate expressions for both catalysts have been developed for
design use. A tabulation of recent publications in the field of NOx catalysis (parti-
cularly selective reduction with NH3) is presented.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Air Pollution
Electric Power Plants
Nitrogen Oxides
Flue Gases
Catalysts
Vanadium Oxides
Aluminum Oxide
Iron Oxides
Chromium Oxides
Reduction (Chem-
istry)
Nitrogen Oxide
Ammonia
b.lDENTIFIERS/OPEN ENDED TERMS
Air Pollution Control
Stationary Sources
C. COGATI Held/Ofoup
13B
10B
07B
21B
07D
18. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
243
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
232
------- |