EPA/AA/CTAB/87-05
                        Technical Report
            Evaluation of Emissions From Low Mileage
        Catalysts On A Light-Duty Methanol-Fueled Vehicle
                               by
                      Gregory K.  Piotrowski
                           April 1987
                             NOTICE

Technical  Reports  do  not   necessarily   represent  final  EPA
decisions or positions..  They are intended to present technical
analysis  of  issues using data  which  are  currently  available.
The purpose  in  the  release of such reports is to facilitate the
exchange  of  technical  information and  to inform the  public of
technical developments which  may form  the basis for a final EPA
decision, position or regulatory action.

             U.  S.  Environmental Protection Agency
                  Office  of Air  and Radiation
                    Office of Mobile Sources
              Emission Control Technology Division
           Control Technology and Applications Branch
                       2565 Plymouth Road
                   Ann Arbor,  Michigan  48105

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         UNITED STATES ENVIRONMENTAL PROTECTION AGENCY

                      ANN ARBOR. MICHIGAN 48105
                                                          OFFICE OF
                                                       AW AND RADIATION
 July 29, 1987
MEMORANDUM
SUBJECT:    Exemption  From Peer  and Administrative .Review
FROM:      Karl H.  Hellman,  Chief
           Control  Technology  and Applications Branch

TO:        Charles  L.  Gray,  Jr.,  Director
           Emission  Control  Technology Division


     The  attached  report entitled  "Evaluation  of Emissions From
Low Mileage  Catalysts On A  Light-Duty Methanol-Fueled Vehicle,"
(EPA/AA/CTAB/87-05)  presents  the  results of  testing  methanol
catalysts  in a two-phased  program.   Phase  I concerned  the use
of  base  metal  or  lightly  loaded   noble  metal  catalysts  in
three-way  and  oxidation catalyst  modes.   Phase  II  involved the
use  of heavily  loaded  noble-metal  catalysts  in  an effort  to
reduce HC and aldehyde  emissions  to very  low  levels.

     Since this  report  is concerned only with the  presentation
of data and  its  analysis and does  not  involve  matters of policy
or   regulations,   your   concurrence   is   requested  to  waive
administrative review according  to  the policy outlined  in your
directive of April  22,  1982.
Approved:      ^r^".^.-  ' i.-.,^ / /-^	  Date ; (~?' - >" -cfrj?
           ChVrles L. Gray  J/. f,-l3ir . ,  ECTD
                            / /
Attachment

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                        Table of Contents

                                                           Page
I.    Summary	  1
II.   Introduction	  l
III.  Vehicle Description 	  2
IV.   Test Facilities and Analytical Methods  	  3
V.    Phase I - Low Mileage Catalyst Screening
      A.   Program Design	3
      B.   Catalysts Tested  	 4
      C.   FTP Test Results	4
      D.   HFET Test Results	  10
VI.   Phase II - Low HC/Aldehyde Catalyst Screening
      A.   Program Design	  14
      B.   Catalysts Tested   	  14
      C.   FTP Test Results	14
      D.   HFET Test Results	   16
VII.  Conclusions
      A.   Phase I	16
      B.   Phase II	18
VIII. Acknowledgements  	 18
IX.   References  .   .	19

Appendix A -  '   Test Vehicle Specifications
Appendix B -     Phase I - FTP Emissions
Appendix C -     Phase I - HFET Emissions
Appendix D -     Phase II - FTP Emissions
Appendix E -     Phase II - HFET Emissions

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 I.   Summary

     This  methanol catalyst  test  program was  conducted  in two
 phases.   The purpose  of Phase  I  was  to  determine whether  a
 substrate  loaded  with  a  base metal  catalyst  or  noble  metal
 catalyst in amounts less than  those  usually  found on a gasoline
 vehicle converter  could provide superior reductions in methanol
 engine  exhaust  emissions.    The  goal  of  Phase   II  was  the
 reduction  of  aldehyde  and  unburned  fuel emissions  to  very low
 levels  by  the  use  of  heavily loaded  noble  metal catalysts.
 Catalysts   tested   in   Phase  I  were  evaluated  as  three-way
 converters  as  well   as  under  simulated  oxidation  catalyst
 conditions.   Phase   II  catalysts  were  tested  as  three-way
 converters only.

     For  Phase  I,  the  most  consistently  efficient  catalysts
 over  the  range of  pollutants  measured were  platinum/rhodium
 configurations.  None  of the  catalysts  tested in Phase  I were
 able to  meet a NOx  level of  1  gram per mile  when operated in
 the oxidation mode.   Testing of the heavily  loaded  noble metal
 configurations   in  Phase   II  demonstrated   that   additional
 catalyst loading beyond  60 grams per cubic  foot did not improve
 catalyst  efficiency  for most categories  of  pollutants.   The
 heavily  loaded  platinum/rhodium configurations were much more
 efficient  converting  the range of pollutants measured  than the
 heavily loaded silver or silver/rhodium catalysts.

 II.   Introduction

     Section  211   of  the  Clean Air  Act[l]  requires the U.S.
 Environmental Protection Agency  (EPA)  to play a key role  in the
 introduction of  new motor vehicle fuels.   EPA  studies[2] have
 suggested  that  methanol  stands  out  from  other  alternative
 transportation  fuels   from  an  environmental  perspective.   The
 use of  alcohol fuels  can also play  a significant  role  in the
 reduction  of  the  foreign  trade deficit  and  aid the  security
 interests  of  the  United States  by reducing  U.S.  dependence on
 imported petroleum.[3]

     The  use  of  methanol  fuel rather   than  gasoline  may  be
 expected to benefit the performance  of a catalytic converter in
 two  ways.   First,  pure   methanol   contains   low   levels  of
 substances  such  as  sulfur  and  lead which  act   as  catalyst
poisons.    Second,   reduced  exhaust  gas  temperatures  at  the
 catalyst   inlet  should   reduce  thermal   degradation  over  an
 extended period of  vehicle operation.

     The Emission  Control  Technology Division  (ECTD)  of  the
Office of  Mobile Sources,  EPA,  assesses technology that  could
be used to reduce  mobile  source  emissions.   One part of this
 assessment  has  been  a  program   to  evaluate  various  exhaust
catalysts   at  low  mileage  on  a   neat  methanol  (M100)  fueled
Volkswagen Rabbit vehicle.

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                               -2-

     The goal  of  this program at its inception was to determine
if  a  lower cost  catalyst might  provide superior—or  at  least
comparable—reductions of  methanol  engine exhaust emissions.   A
number  of  catalysts  were  procured  for testing,  some  having
conventional  noble  metal catalyst  loading,  while others either
were  more  lightly  loaded or  involved  the  use  of base  metal
catalysts.   The catalysts  tested,  with one exception,  had the
same geometric  construction  and all were evaluated in  the same
underfloor  location in the vehicle exhaust.

     Two  different  catalyst  operating modes  were chosen  for
Phase   I.   The  catalysts  were  first  tested   as   three-way
converters, to  oxidize  unburned fuel, aldehydes,  and CO as well
as  to  reduce  NOx  emissions.   An air  pump which supplied air  to
the exhaust ahead  of  the catalyst but downstream of the exhaust
oxygen  sensor  was then  enabled and  the  catalyst tested  in  an
oxidation  mode.   It  was  hoped  that this  mode  would  further
reduce  unburned   fuel   and  CO  emissions   without   seriously
impairing the  catalysts'  NOx reduction capability.   The driving
cycles  tested  included  the Federal  test  procedure  (FTP)[4]  and
the  highway  fuel  economy  test  (HFET)[5]  cycles.   Details  of
this testing  are  provided in the section labeled Phase  I  - Low
Mileage Catalyst  Screening.   This  portion  of  the program has
been reported on elsewhere.[6,7,8]

     The second phase (Phase II) of  this program  began with a
recognition  of  the  need  to  reduce  aldehyde   emissions  from
methanol-fueled vehicles  to very  low  levels.   Aldehydes  may
promote the process of atmospheric formation of ozone.[9]

     Several  substrates   very heavily  loaded  with noble  metal
catalyst were procured  and tested  over  FTP  and  HFET  cycles  to
determine the  benefits  of the  heavier loading on  aldehyde and
unburned fuel  reduction.   This  testing was  conducted  with the
catalysts operated  in the three-way  mode  only.    Results from
this  testing  are  discussed  in Phase  II  -  Low  HC/Aldehyde
Catalyst Screening.

Ill. Vehicle Description

     The test vehicle is  a 1981 Volkswagen Rabbit 4-door sedan,
eguipped  with  automatic  transmission,   air  conditioning,  and
radial  tires.   The 1.6-liter engine  is rated at maximum power
output of 88  horsepower  at  5,600  rpm.   The vehicle was tested
at  2,500   Ibs   inertia  weight  and  7.3   actual   dynamometer
horsepower.

     The emission control system was  modified by  EPA  to include
an  air  injection  pump which can inject  air  into  the  exhaust  at
a  location  approximately  1  foot   downstream  from  the  oxygen
sensor.  A  manually adjustable valve was installed in  the line
between the diverter  valve  and the  exhaust  inlet.  The  valve
permits the oxygen  concentration over the catalyst  to  be varied
while operating the engine in the closed-loop mode.

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                               -3-

     A detailed description of  the  vehicle and special methanol
modifications is provided in Appendix A.

IV.  Test Facilities and Analytical Methods

     Emissions  testing is  conducted  on a Clayton  Model  ECE-50
double-roll chassis  dynamometer,  using a  direct  drive variable
inertia  flywheel  unit  and  road  load power control  unit.   The
Philco  Ford  CVS   used has  a  nominal  capacity  of  350  CFM.
Exhaust  HC emissions  were measured  with  a  Beckman  Model  400
flame ionization detector.  No corrections to the  results  were
made  for  FID  response  to methanol   or  the  difference  in  HC
composition  because  of  the   use  of  methanol  fuel.   CO  was
measured  using  a  Bendix  Model  8501-5CA  infrared  CO analyzer.
NOx  emissions  were  determined  by  chemiluminescent  technique
utilizing a Beckman Model 951A NOx  analyzer.

     Exhaust formaldehyde is measured using a dinitrophenyl-
hydrazine  (DNPH)   technique.[10]    Exhaust  carbonyls  including
formaldehyde  are  reacted with DNPH  solution  forming hydrazone
derivatives.   These derivatives  are  separated   from the  DNPH
solution  by  means  of  high  performance   liquid • chromatography
(HPLC).    Quantization  is  accomplished  by  spectrophotometric
analysis of the LC effluent stream.

V.   Phase I - Low Mileage Catalyst Screening

     A.     Program Design - Phase I

     The  evaluation  of  a  catalyst  during  this  phase  was  a
three-step process.   First,  the  car  was  emission  tested on  a
chassis  dynamometer  without the  catalytic  converter present in
the exhaust stream and with  the air pump  rendered  inoperable.
The driving cycles  tested,  the FTP  and  HFET,  were repeated
three times.

     Following  these  baseline   tests,   the  catalyst   to   be
evaluated  was  attached  under   the   vehicle  in  the  exhaust
stream.    The  second  step  of   the  process was   to   repeat  the
series  of  tests   described  above  with  the  air  pump  still
disabled.   The catalyst is evaluated  in the  "three-way"  mode in
this test.

     In  the  third step,  the  air pump  was enabled  and air  was
added at a predetermined  rate  to the exhaust directly in front
of  the  catalyst  but  downstream of  the  oxygen  sensor.   This
action simulated the operation  of the catalyst as  an oxidation
catalyst.    The  3   percent   02  level  mentioned  in  the  test
results  refers to  the  amount  of necessary makeup air  to  obtain
3  percent oxygen in  the vehicle exhaust (at the catalyst  inlet)
at 30  MPH steady-state conditions as measured with  a Sun  oxygen
analyzer.   The car was  then tested  over the FTP and HFET  cycles
three  times more in this configuration.

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                               -4-

     Following   this  oxidation   catalyst   mode   testing  the
converter was  removed  from the exhaust stream, the air pump was
disabled, and  the car then  baseline tested,  beginning another
evaluation  cycle.   This  evaluation  sequence  is  summarized in
Table 1.

     B.    Catalysts Tested - Phase I

     with one  exception  all  of  the catalysts reported on here
used monolithic  substrates which contained  400 cells per square
inch and had  a wall  thickness of  6  mils.   The exception  was  a
platinum/rhodium  configuration  with  a  cell  wall  thickness of
10.5 mils and a cell density of  300  cells per  square inch.  All
substrates but  one were shaped  as  porous cylinders,  4.0 inches
in diameter and 6.0 inches in  length.   The  one substrate shaped
differently  was  an  oval-faced  ("racetrack")  monolith,  having
face dimensions  of 3.18  inches x 6.68  inches  and  a length of  6
inches.  Details  are provided in Table 2.

     With  the  dimensional  parameters   and  converter  location
fixed,  the test  results  should have been primarily affected by
the  washcoat  and  the  catalytically active materials.   Most of
the catalysts were noble  metals  though some use of base metals
was  made.   The  base  metal  catalysts  were  proprietary  to the
catalyst suppliers.

     The  catalysts  descriptions  indicate  the  ratio  of  the
constituents by weight,   and the  number  in parentheses  at the
end of the description gives the catalyst loading  in  grams per
cubic  foot.    Constituents  are   identified  by  their  chemical
abbreviations;  BM signifies base metal.

     C.    FTP Test Results

     FTP test  results  are presented  in two formats.   Tables  3
and  4  detail   emission   levels  obtained   over  two  catalyst
operating modes,  three-way and  oxidation catalyst performance,
respectively.   Baseline (no  catalyst)  results  with the air pump
disabled  are  also  presented   for   each   pollutant  category.
Tables   5  through  8  rank  catalysts  for  each  pollutant  and
operating mode  by their  efficiency  at  reducing emissions from
baseline  levels.   Emission   statistics  for  each   catalyst  are
presented in Appendix B.

     Baseline  emission  levels  have  been  averaged  over  all
baseline tests  from  the beginning of Phase I through the end of
Phase II testing.  Trends  in baseline  emissions were  commented
on  in  an  internal  EPA  memo r andum [ 11 ]  and  an  ASME  technical
paper. [8]   The analysis done in these two reports  shows a rough
parallel between  catalyst   ranking  by  lowest emission  levels
allowed and a  ranking  involving  catalyst efficiency using only
baseline  tests   run   immediately  prior  to  and  following  a
catalyst's  evaluation.   For  this  reason,  baseline results  by
pollutant  category over  the  life  of  the  entire  program were
averaged and are presented as "baseline test  results."

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                               -5-

                             Table 1

            Phase I - Low Mileage Catalyst Screening
             Sequence of Individual Catalyst Tests
    Conditions
Baseline

Catalytic Converter
Attached

Catalytic Converter
Attached
       Test Cycles

       FTP, HFET

       FTP, HFET


       FTP, HFET
Air Pump

  Off

  Off


  On
No. of Tests
of Each Cycle

     3

     3
                             Table 2

                   Catalysts  Tested in Phase  I
 Abbreviated
Catalyst Code

5Pt:Rh(40)
12Pt:Rh(40)
12Pt:Rh(40)*
3Pt:2Pd(20)
Pd(40)
Pd+BM(35)**
Pd(20)
Ag(150)
Pd+BM(5)**
CuO
9Pd:Rh(10)
10Ag:Rh(150)
Pd(10)
               Wall                     Substrate
 Cells Per  Thickness  Substrate Diameter  Volume
Square Inch  (mils)       and Length	  (in3)
    300.        10.5         4."X6."        75
    400.         6.           4."X6."        75
    400.         6.      3.18"X6.68"X6.0"   110
    400.         6.           4."X6."        75
    400.         6.           4."X6."        75
    400.         6.           4."X6."        75
    400.         6.           4."X6."        75
    400.         6.           4."X6."        75
    400.         6.           4."X6."        75
    400.         6.           4."X6."        75
    400.         6.           4."x6."        75
    400.         6.           4."x6."        75
    400.         6.           4."X6."        75
     Racetrack configuration.
     BM signifies base metal.

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                                 -6-

                                Table  3

                    Summary of FTP Cycle Emissions
                             HC (q/mi)
       Catalyst
None (Baseline)
5Pt:Rh(40)
12Pt:Rh(40)
12Pt:Rh(40)*
3Pt:2 Pd(20)
Pd(40)
Pd+BM(35)**
Pd(20)
Ag(150)
Pd+BM(5)**
CuO
Pd(10)
9Pd:Rh(10)
10Ag:Rh(150)
Operat
Three-Way
.96
. 15
. 11
.13
. 15
. 17
.28
. 18
.54
. 19
. 19
.17
. 14
.36
ing Mode
Oxidation
N/A
. 14
. 12
.13
.16
. 14
.28
. 16
.43
. 18
.25
. 17
. 15
.36
Aldehydes (mg/mi)
Operating Mode
Three-Way
252.1
30.3
11.6
11.5
33.0
41.5
118.9
41.0
59.3
38.3
27.8
29.8
18.9
83.7
Oxidation
N/A
15.4
15.6
14 .4
72.9
68.0
129.4
94.2
52.0
80 . 6
37.6
95.2
35.0
95. 1
                                Table 4

                    Summary of FTP Cycle Emissions
                             CO (q/mi)
       Catalyst
None (Baseline)
5Pt:Rh(40)
12Pt:Rh(40)
12Pt:Rh(40)*
3Pt:2 Pd(20)
Pd(40)
Pd+BM(35)**
Pd(20)
Ag(150)
Pd+BM(5)**
CuO
Pd(10)
9Pd:Rh(10)
10Ag:Rh(150)
Operating Mode
Three-Way
6



1
1
2
1
6
1
1


2
. 54
.78
.69
.77
.47
.99
.85
.84
.53
.21
.08
. 74
.60
.95
Oxidation
N/A
.60
.39
.40
.35
.38
2.05
.40
5.93
.55
1.64
.65
.59
2.61
   NOx (q/mi)
Operating Mode
Three-Way
1





1

2

1


1
.79
.84
.62
. 77
.85
.74
.97
.67
.03
.83
.73
.87
.81
.05
Oxidation
N/A
1
2
2
2
1
1
1
1
1
1
1
1
1
.95
.01
.05
.07
.98
.95
.90
.99
.80
.95
.86
.84
.42
     Racetrack configuration.
     BM signifies base metal.

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                             -7-

                           Table 5

              Catalyst Comparison With Baseline
              HC Emissions - FTP Driving Cycle
Three-Way Operating Mode
Oxidation Mode
Catalyst
12Pt:Rh(40)
12Pt:Rh(40)*
9Pd:Rh(10)
5Pt:Rh(40)
3Pt:2Pd(20)
Pd(40)
Pd(10)
Pd(20)
Pd+BM(5)
CuO
Pd+Bm(35)
10Ag:Rh(150)
Ag(150)
Efficiency %
88.5
86.5
85.4
84.4
84.4
82.3
82.3
81.3
80.2
80.2
70.8
62.5
43.8
                                  Catalyst
                               12Pt:Rh(40)
                               12Pt:Rh(40)*
                               5Pt:Rh(40)
                               Pd:40
                               9Pd:Rh(10)
                               3Pt:2Pd(20)
                               Pd(20)
                               Pd(10)
                               Pd+BM(5)
                               CuO
                               Pd+BM(35)
                               10Ag:Rh(150)
                               Ag(150)
           Efficiency %
              87
              86
              85.4
              85.4
              84
              83
              83
              82
              81.3
              74.0
              70.8
              62.5
              55.2
 5
 5
,4
,3
 3
 3
  Racetrack configuration.
                          Table  6

             Catalyst Comparison With Baseline
           Aldehyde Emissions -  FTP Driving Cycle
Three-Way Operating Mode
Catalyst
12Pt:Rh(40)
12Pt:Rh(40)*
9Pd:Rh(10)
5Pt:Rh(40)
CuO
Pd(10)
3Pt:2Pd(20)
Pd+BM(5)
Pd(20)
Pd(40)
Ag(150)
10Ag:Rh(150)
Pd+BM(35)
Efficiency %
95.4
95.4
92.5
91.9
89.0
88.2
86.9
84.8
83. 7
83.5
76.5
66.8
52.8
Oxidation Mode
Catalyst
12Pt :Rh(40)*
5Pt :Rh(40)
12Pt :Rh(40)
9Pd:Rh(10)
CuO
Ag(150)
Pd(40)
3Pt:2 Pd(20)
Pd+BM(5)
Pd(20)
10Ag:Rh(150)
Pd(10)
Pd+BM(35)
Efficiency
94.3
93.9
93.8
86.1
85.1
79.4
73.0
71. 1
68.0
62.6
62.3
62.2
48. 7
  Racetrack  configuration.

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                            -8-

                          Table 7

             Catalyst  Comparison With Baseline
             CO Emissions - FTP Driving Cycle
Three-Way Operating Mode
Oxidation Mode
Catalyst
9Pd:Rh(lO)
12Pt:Rh
Pd(10)
12Pt:Rh(
(40)

40)*
5Pt:Rh(40)
CuO
Pd+BM(5)
3Pt:2Pd(
Pd(20)
Pd(40)
Pd+BM(35
10Ag:Rh(
Ag(150)


20)


)
150)

Efficiency %
90
89
88
88
88
83
81
77
71
69
56
54

.8
.4
. 7
.2
. 1
. 5
.5
.5
.9
. 6
. 4
.9
-0-
Catalyst
3Pt:2Pd(20)
Pd(40)
12Pt:Rh(40)
12Pt:Rh(40)*
Pd(20)
Pd+BM(5)
9Pd:Rh(10)
5Pt:Rh(40)
Pd(10)
GuO
Pd+BM(35)
10Ag:Rh(150)
Ag(150)
Efficiency %
94.6
94.2
94.0
93.9
93.9
91.6
91.0
90.8
90. 1
74 .9
68.7
60. 1
9.3
  Racetrack configuration.
                          Table  8

             Catalyst Comparison With  Baseline
         NOx Emissions  -  FTP  Driving  Cycle  Cycle
Three-Way Operating Mode
Catalyst
12Pt:Rh(40)
Pd(20)
Pd(40)
12Pt:Rh(40)*
9Pd:Rh(10)
Pd+BM(5)
5Pt:Rh(40)
3Pt:2 Pd(20)
Pd(10)
10Ag:Rh(150)
CuO
Pd+BM(35)
Ag(150)
Efficiency %
65.4
62.6
58.7
57.0
54.7
53.6
53. 1
52.5
51 .4
41.3
3.4
(10.1)
(13.4)
Oxidation Mode
Catalyst
10Ag:Rh(150)
Pd+BM(5)
9Pd:Rh(10)
Pd(10)
Pd(20)
CuO
Pd+BM(35)
5Pt:Rh(40)
Pd(40)
Ag(150)
12Pt:Rh(40)
12Pt :Rh(40)*
3Pt:2Pd(20)
Efficiency %
20.6
(0.6)
(2.8)
(3.9)
(6.1)
(8.9)
(8.9)
(8.9)
(10.6)
(11.2)
(12.3)
(14.5)
(15.6)
  Racetrack configuration.

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                               _Q	

     Hydrocarbon  emission reductions  are very  significant  for
most catalysts  with ten  catalysts  having 80 percent  or better
efficiency  in  the three-way  operating mode and  nine  catalysts
with similar  efficiencies in  the oxidation mode.  Combinations
containing  rhodium,  with  the exception  of the  silver/rhodium
catalyst,   were   exceptionally   effective.   Aldehyde   levels
followed trends' similar to HCs,  with most  noble metal/rhodium
catalysts having  efficiencies  in excess of 90 percent.  Many of
the  other  catalysts   showed  significant  aldehyde  reduction
activity,  though  none provided efficiencies greater  than  90
percent.

     CO  emissions  were significantly  reduced  by  virtually  all
catalysts,   particularly  when  operated  in the  oxidation  mode.
Again with  a  few  notable  exceptions,  the conventionally loaded
noble  metal/rhodium   configurations  allowed   the   lowest   CO
levels.  With  the  exception  of  Ag(150), all catalysts tested
met  the   levels  of  the  current  CO  standards   for  light-duty
gasoline vehicles when operated  in  either the three-way  or
oxidation modes.

     Most catalysts  provided  a  substantial  (40-60 percrent)  NOx
reduction efficiency when tested  in  the three-way mode.   Nearly
all, however,  allowed  greater than  baseline levels  when tested
in  the oxidation  mode.   In  addition,  no  catalyst was  able  to
meet the current  1  gram  per  mile  gasoline light-duty  vehicle
standard when operated as an oxidation catalyst.

     The  platinum/rhodium   combinations  tested  allowed   the
lowest  emission levels of  most  pollutants  when  tested in  the
three-way and oxidation modes.   The most  notable exception  was
the  comparatively   poor   efficiency   of  these  catalysts   at
reducing NOx levels in the oxidation mode.   Pollutant  levels  in
most  categories  were  similar  for  the  12Pt:Rh(40)    and  the
12Pt:Rh(40)  racetrack  configurations.   The additional  volume  of
the  racetrack  configuration   did not  appear  to significantly
reduce  pollutant   levels  below  those   allowed  by the  smaller
catalyst.

     The  substrates coated only  with palladium catalyst did not
exhibit a good correlation between heavier loading and  catalyst
effectiveness.     Indeed,   the   most   lightly    loaded   Pd(10)
configuration provided the  greatest  efficiency  of  the  three
all-palladium catalysts  for  several  pollutants.  The  overall
performance  of  these  catalysts,   however,  as well as  the  Pt/Pd
and  CuO  configurations  was  mixed.   Though sometimes   allowing
only very low pollutant levels in a particular  category (e.g.,
the  94.6 percent  efficiency of 3Pt:2Pd(20)   in  reducing  CO
emissions in  the  oxidation  mode),  none  of  these  catalysts
consistently  placed   as   one   of   the   three   most  effective
Catalysts in every pollutant  category.

-------
                              -10-

     Though the use of a base metal  catalyst  is attractive from
a   cost   standpoint,   neither  base   metal   configuration  was
consistently  as  effective  as  the platinum/rhodium  catalysts.
The   lightly   loaded   Pd+BM(5)   combination   proved   fairly
effective,  however,  at  reducing  most  pollutants  over  both
operating  modes.    The  silver(150)   catalyst   was   not  very
effective  in  either  operating  mode.   The  addition  of  rhodium
enhanced the  effectiveness  of  the silver catalyst significantly
over  both  modes  for most  pollutants.   Efficiency  for  each
pollutant  for this  catalyst,  however,  still  did  not  approach
the efficiency given by the platinum/rhodium configurations.

     D.    HFET Results

     HFET test  results  are  presented in the same  format  as FTP
results.    Tables  9  and  10 detail  emission  averages  obtained
over  the three-way  and  oxidation operating  modes.   Baseline
results  with  the  air   pump  disabled  are  presented for  each
pollutant  category.   Tables  11  through  14  rank  catalysts for
each  pollutant  and  operating  mode  by  their  efficiency  at
reducing  emissions from  baseline levels.   Emission  statistics
for each catalyst are presented in Appendix C.

     All of  the catalysts  tested  reduced HC emissions  to very
low levels over  both  operating  modes.   This was  not  unexpected
due  to  the  high  speed driving  characteristics  of  the   cycle
which caused  catalysts  to  light-off  very early.   The oxidation
reactions which produced lower  aldehyde and CO  emissions were
similarly affected.

     Though  efficiencies for  these pollutant  categories  were
uniformly high  some distinctions  are  evident.   Catalysts  which
were most  effective in  reducing  emissions  over  the FTP   cycle
generally  were  the  most   effective  performers  over the  HFET
cycle.    With  the  exception  of  Ag/Rh,  the  rhodium-containing
catalysts  proved  most   efficient  in  oxidation  reactions.   An
increase in  catalyst  volume did  not  correlate with  a  decrease
in pollutant  emissions  (12Pt:Rh(40)).   The  catalyst loaded only
with silver lagged  the  others  in efficiency and  allowed fairly
high levels of CO over both operating modes.

     NOx reduction efficiencies were higher  on the average over
the HFET cycle  than  under FTP  conditions.   Two all-palladium
configurations had  efficiencies  slightly greater  than  the very
consistent  platinum/rhodium  combinations  over  the  three-way
mode.   The most  effective configuration  was  a platinum/rhodium
catalyst   with  an  efficiency  of  96  percent.    All  catalysts
showed an increase in NOx output under  the oxidation simulation.

-------
                               -11-
                              Table 9

                     Summary of HFET Emissions
       Catalyst
None  (Baseline)
5Pt:Rh(40)
12Pt:Rh(40)
12Pt:Rh(40)*
3Pt:2Pd(20)
Pd(40)
Pd+BM(35)
Pd(20)
Ag(150)
Pd+BM(5)
CuO
Pd(10)
9Pd:Rh(10)
10Ag:Rh(150)
	HC  (q/mi)	       Aldehydes  (mq/mi)
    Operating Mode          Operating Mode
 Three-Way  Oxidation    Three-Way   Oxidation
    43
    002
    003
    008
    007
    005
    017
    009
    024
    007
    Oil
    010
    006
    014
N/A
N/A
.008
.009
.010
.008
.013
.009
.019
.012
.012
.010
.008
. 014
185.5
  0.3
  0.5
  1.2
  1.1
  0.9
  3.1
  2.0
  2.4
  6.7
  5.9
  2.7
  1. 1
 18.6
  N/A
  N/A
 1.2
 2.0
 1.7
 1.8
 3.0
 2.7
 1.9
 9.3
 6.7
 5.1
 1.8
22. 5
N/A signifies not available.
*    Racetrack configuration.
                              Table 10

                      Summary of  HFET  Emissions
                           CO (q/mi)
       Catalyst
None (Baseline)
5Pt:Rh(40)
12Pt:Rh(40)
12Pt:Rh(40)*
3Pt:2 Pd(20)
Pd(40)
Pd+BM(35)
Pd(20)
Ag(150)
Pd+BM(5)
CuO
Pd(10)
9Pd:Rh(10)
10Ag:Rh(150)
    Operating Mode
Three-Way   Oxidation
                              NOx  (q/mi)
  5.54
    . 11
    .05
    .06
    .22
    .33
  1.30
    .38
  4.25
    . 17
    .05
  0.00
  0.00
    .32
N/A
N/A






3
0

0
0

.01
.02
.01
.01
. 03
.01
.47
.00
.08
. 00
.00
. 07
              Operating Mode
           Three-Way   Oxidation
             2.50
              .09
              .61
              .55
              .64
              .51
             1.51
              .35
             2.74
              .93
             2.26
             1.26
              .95
             1. 57
                 N/A
                 N/A
                2.73
                2.84
                2.77
                2.65
                2.57
                2.54
                2.64
                2.65
                2.66
                2.72
                2.71
                2. 52
N/A signifies not available.
*    Racetrack configuration.

-------
                              -1.2-

                            Table 11

                Catalyst Comparison  With Baseline
                HC Emissions - HFET  Driving Cycle
   Three-Way Operating Mode
Oxidation Mode
Catalyst
12Pt:Rh(40)
Pd(40)
9Pd:Rh(10)
3Pt:2 Pd(20)
Pd-l-BM(5)
12Pt:Rh(40)*
Pd(20)
Pd(lO)
CuO
10Ag:Rh(150)
Pd+BM(35)
5Pt:Rh(40)
Ag(150)
Efficiency %
99.3
98.8
98.6
98.4
98.4
98. 1
97.9
97.7
97.4
96.7
96.0
95.3
94.4
N/A signifies not available.
*    Racetrack configuration.
Catalyst
12Pt :Rh(40)
Pd(40)
9Pd:Rh(10)
12Pt:Rh(40)*
Pd(20)
Pd(10)
3Pt:2 Pd(20)
CuO
Pd+BM(5)
Pd-l-BM(35)
10Ag:Rh(150)
Ag(150)
5Pt :Rh(40)
Efficiency %
98.1
98.1
98. 1
97.9
97.9
97.7
97.7
97.2
97.2
97 .0
96.7
95.6
N/A
                            Table 12

                Catalyst  Comparison  With Baseline
             Aldehyde Emissions  - HFET Driving Cycle
   Three-Way Operating Mode
Oxidation Mode
Catalyst
5Pt:Rh(40)
12Pt:Rh(40)
Pd(40)
12Pt :Rh(40)*
3Pt:2 Pd(20)
9Pd:Rh(10)
Pd(20)
Ag(150)
Pd(10)
PD+BM(35)
CuO
Pd+BM(5)
10Ag:Rh(150)
Efficiency %
99.8
97.7
99.5
99.4
99.4
99.4
98.9
98. 7
98.5
98.3
96.8
96.4
90.0
N/A signifies not available.
*    Racetrack configuration,
Catalyst
12Pt :Rh(40)
3Pt:2 Pd(20)
Pd(40)
Ag(150)
9Pd:Rh(10)
12Pt:Rh(40)*
Pd(20)
Pd+BM(35)
Pd(10)
CuO
Pd+BM(5)
10Ag:Rh(150)
5Pt :Rh(40)
Efficiency %
99.4
99. 1
99.0
99.0
99.0
98.9
98.5
98.4
97.3
96.4
95.0
87.9
N/A

-------
                              -13-

                            Table 13

                Catalyst Comparison  With Baseline
                CO Emissions - HFET  Driving Cycle
   Three-Way Operating Mode
                        Oxidation Mode
   Catalyst
Pd(10)
9Pd:Rh(10)
CuO
12Pt:Rh(40)
12Pt:Rh(40)*
5Pt:Rh(40)
Pd+BM(5)
10Ag:Rh(150)
3Pt:2 Pd(20)
Pd(40)
Pd(20)
Pd+BM(35)
Ag(150)
Efficiency %

  100.0
  100.0
   99.1
   99.1
   98.9
   98.0
   96.9
   96.9
   96.0
   94.0
   93. 1
   76.5
   23.3
   Catalyst
PD+BM(5)
Pd(10)
9Pd:Rh(10)
12Pt:Rh(40)
3Pt:2 Pd(20)
Pd(40)
Pd(20)
12Pt:Rh(40)*
PD+BM(35)
10Ag:Rh(150)
CuO
Ag(150)
5Pt:Rh(40)
Efficiency %

   100.0
   100.0
   100.0
    99.8
    99.8
    99.8
    99.8
    99.6
    99.5
    98.7
    98.6
    37.4
    N/A
N/A signifies not available.
*    Racetrack configuration
                            Table 14

                Catalyst  Comparison  With Baseline
               NOx Emissions - HFET Driving Cycle
   Three-Way Operating Mode
                        Oxidation Mode
   Catalyst
5Pt:Rh(40)
Pd(20)
Pd(40)
12Pt:Rh(40)*
12Pt:Rh(40)
3Pt:2 Pd(20)
Pd+BM(5)
9Pd:Rh(10)
Pd(10)
PD+BM(35)
10Ag:Rh(150)
CuO
Ag(150)
Efficiency %

   96. 4
   86.0
   79.6
   78.0
   75.6
   74 .4
   62.8
   62.0
   49.6
   39.6
   37.2
    9.6
   (9.6)
   Catalyst
10Ag:Rh(150)
Pd(20)
Pd+BM(35)
Ag(150)
Pd+BM(5)
Pd(40)
CuO
9Pd:Rh(10)
Pd(10)
12Pt:Rh(40)
3Pt:2 Pd(20)
12Pt:Rh(40)*
5Pt:Rh(40)
Efficiency %
    (0
    (1
    (2
    (5
    (6
    (6
    (6
    (8
    (8,
    (9,
   (10,
   (13,
    N/A
8)
6)
8)
6)
0)
0)
4)
4)
8)
2)
8)
6)
Parentheses   on   catalyst   efficiency
emissions greater than baseline levels.
N/A signifies not available.
*   Racetrack configuration.
                         statistics   indicate

-------
                              -14-

VI.  Phase II - Low HC/Aldehyde Catalyst Screening

     A.    Program Design - Phase II

     This phase  of the  catalyst  evaluation program  emphasized
reduction  of  HC  and  aldehyde  emissions  through  the use  of
heavily  loaded .catalysts.   Oxidation mode  testing was deleted
as  the  previous  Phase  I  evaluation  had  suggested  that  the
three-way operating  mode was the  more  efficient  approach  with
respect to aldehyde and NOx levels.

     The  test   sequence   for   Phase  II  is  similar  to  that
presented in Phase I, with two  exceptions.   First,  no oxidation
mode;  second,  as  baseline  results were fairly  consistent,  the
car was  baseline tested only  after the complete  evaluation  of
every  second  catalyst.   This evaluation  sequence  is summarized
in Table 15.

     B.    Catalysts Tested - Phase II

     All  of  the  catalysts  reported on here  used  monolithic
substrates which  contained  400  cells  per  square inch  in  the
substrate material.   These  substrates  were shaped  as  porous
cylinders, 4.0   inches  in diameter and  6.0  inches  in length.
The active catalytic materials were noble  metals,  with catalyst
loading  in  the   range  of  60  to  300   grams  per cubic  foot.
Details are provided in Table 16.

     C.    FTP Test Results

     Emissions   results    for   each  measured   pollutant   are
presented  in  Table  17.    Baseline   test   results  are  also
presented for  comparison.   Tables  18  and 19 rank  catalysts  by
efficiency.    Emissions   statistics  for   each   catalyst   are
presented in  Appendix D.

     The  platinum/rhodium   combinations  tested   proved   very
effective  at  reducing   both  HC  and  aldehyde  emissions.   The
5Pt:Rh(80) configuration allowed a  very  low  (average 5.5 mg/mi)
aldehyde  emission  level  over   the  FTP  cycle.    HC  level
reductions  appear   limited,  however,   by  the   size   of   the
converter and its  location in  the exhaust stream.   CO emissions
are greatly reduced, the  platinum/rhodium combinations allowing
levels  easily  meeting  current   light-duty  gasoline  vehicle
standards.  The  low  CO emissions  are not greatly  improved  over
the levels allowed by the more  lightly loaded  platinum/rhodium
catalysts tested during  Phase  I,  however.  NOx  emission levels
are roughly  equivalent  to those  allowed by the most efficient
catalysts tested  under  three-way  conditions  during  Phase  I.
The higher catalyst  loadings did  not,  therefore,  significantly
aid NOx reduction.

-------
                              -15-

                            Table 15

           Phase II - Low HC/Aldehyde Catalyst Effort
              Sequence of Two Catalyst Evaluations
 Conditions

Baseline

1st Catalyst

2nd Catalyst
Test Cycles

 FTP, HFET

 FTP, HFET

 FTP, HFET
Air Pump

  Off

  Off

  Off
No. of Tests
of Each Cycle

      3

      3

      3
Begin  baseline   testing   prior   to  evaluation  of  additional
catalysts.
Abbreviated
 Catalyst
   Code

5Pt:Rh(60)
Ag(300)
10Ag:Rh(300)
19Pt:Rh(60)
5Pt:Rh(80)
19Pt:Rh(80)
                            Table 16

                  Catalysts Tested in Phase II
Cells
Per Square
Inch
400
400
400
400
400
400
Wall
Thickness
(mils)
6
6
6
6
6
6
Substrate
Diameter
And Length
4. "x6. "
4. "x6. "
4. "x6. "
4. "X6. "
4."x6."
4."x6. "
                                      Substrate
                                       Volume
                                        (in3)

                                          75
                                          75
                                          75
                                          75
                                          75
                                          75

-------
                              -16-

                            Table 17

                 Summary of FTP Cycle Emissions
                     Three-Way Configuration
   Catalyst
None (Baseline)
5Pt:Rh(60)
Ag(300)
10Ag:Rh(300)
19Pt:Rh(60)
5Pt:Rh(80)
19Pt:Rh(80)
      HC
    (g/mi)

      .96
      . 12
      .42
      .35
      . 10
      . 11
      .09
Aldehyde
(mg/mi)

 252.1
  10.6
  29. 1
  19.3
  15.0
   5.5
   9.6
 54
 43
 53
 92
 68
 69
,58
          NOX
         (g/mi)
.79
.69
.60
.20
.84
.82
.74
                            Table 18

                Catalyst Comparison  With Baseline
          FTP Driving Cycle - Three Way Operating Mode
         HC Emissions
                       Aldehyde Emissions
   Catalyst
19Pt:Rh(80)
19Pt:Rh(60)
5Pt:Rh(80)
5Pt:Rh(60)
10Ag:Rh(300)
Ag(300)
Efficiency %

   90.6
   89.6
   88.5
   87. 5
   63.5
   56.3
    Catalyst
 5Pt:Rh(80)
 19Pt:Rh(80)
 5Pt:Rh(60)
 19Pt:Rh(60)
 10Ag:Rh(300)
 Ag(300)
 Efficiency  %

     97.8
     96.2
     95.8
     94.0
     92.3
     88.5
                            Table 19

                Catalyst  Comparison  With Baseline
          FTP Driving Cycle - Three Way Operating Mode
         CO Emissions
                         NOx Emissions
   Catalyst
5Pt:Rh(60)
19Pt:Rh(80)
19Pt:Rh(60)
5Pt:Rh(80)
10Ag:Rh(300)
Ag(300)
Efficiency %

   93.4
   91.1
   89.6
   89.4
   55.4
   15.4
    Catalyst
 5Pt:Rh(60)
 19Pt:Rh(80)
 5Pt:Rh(80)
 19Pt:Rh(60)
 10Ag:Rh(300)
 Ag(300)
 Efficiency %
    61.4
    58.7
    54.2
    53.1
    33.0
    10. 6

-------
                              -17-

     The  heavily  loaded Ag(300)  outperformed  the  more lightly
 loaded  Ag(150)  catalyst  tested in  Phase  I in  every pollutant
 category.   Despite its  heavier loading,  however,   the Ag(300)
 catalyst  allowed  pollutant levels greatly  exceeding those from
 the  platinum/rhodium  group.    The   additional  loading  of  the
 silver/rhodium  catalyst helped  it  attain a greater efficiency
 in  most pollutant  categories  than  the  lightly  loaded version
 tested  in Phase  I.   However,   as  in  the  case of  Ag(300),  the
 levels  attained were  not  low  enough  to be  comparable  to  the
 platinum/rhodium combinations.

     D.    HFET Test Results

     HFET  test  results are presented  in the same format as FTP
 results.   Table   20   details   emissions   obtained   over   the
 three-way  operating mode while Tables 21 and  22 rank catalysts
 by  efficiency  at  reducing  pollutants  from  baseline  amounts.
 Emission statistics for  each catalyst  are presented in Appendix
 E.

     HC  and  aldehyde  emissions are  reduced  to extremely  low
 levels  by  all of the  catalysts  tested.   All  catalysts attained
 efficiencies  of  greater than 90  percent for  these pollutants.
 These  levels,  however,  are approximately the  same  as emissions
 levels   allowed   by  similar,    though  less  heavily  loaded,
 catalysts  tested   in  Phase  I.   CO  emissions were  reduced  to
 insignificant levels by all of the rhodium-containing
 catalysts.   While  the  lower  CO  levels  allowed  by the Ag(300)
 catalyst represented a  near  doubling in effectiveness  over the
Ag(150)  configuration,  the  54  percent  efficiency  does  not
 compare   favorably   to   the   platinum/rhodium    tests.    NOx
 efficiency of  the  rhodium-containing  heavily loaded catalysts
did not  compare favorably with the results  obtained  with the
 lightly loaded Phase I configurations.

     The  difference in  loading  between 60  and  80  grams  per
 cubic foot did not influence catalyst  performance over the HFET
cycle.    Generally,  efficiencies  at  lower  loadings  were  high
enough  to  make  contributions   to  catalyst  efficiency of  the
heavier loading of limited significance.

VII.  Conclusions

     A.     Phase I

     1.     The  most  consistently  effective  catalysts  tested
owere the Pt/Rh configurations.

     2.     With the exception of the Ag(150)  configuration,  all
catalysts  tested  were  able  to meet  the  levels of  current
gasoline   light-duty   vehicle   CO   emission  standards,   when
operated as three-way  or oxidation catalysts.

-------
                              -18-

                            Table 20

                 Summary of HFET Cycle Emissions
                    Three-Way Configuration	
   Catalyst
None  (Baseline)
5Pt:Rh(60)
Ag(300)
10Ag:Rh(300)
19Pt:Rh(60)
5Pt:Rh(80)
19Pt:Rh(80)
      HC
    (g/mi)

      .43
      .007
      .033
      .002
      .007
      .006
      ,004
             Aldehyde
             (mg/mi)

              185.5
                1.1
                1.1
                0.6
                5.1
                1.5
                4.6
              5.54
              0.00
              2.52
              0. 12
              0.00
              0.00
              0.00
         NOx
       (g/mi)

        2.50
        0.83
        2.34
        1.76
        1.05
        0.98
        0.85
                            Table 21

                Catalyst Comparison  With Baseline
          HFET Driving Cycle - Three Way Operating Mode
         HC Emissions
   Catalyst
10Ag:Rh(300)
19Pt:Rh(80)
5Pt:Rh(80)
19Pt:Rh(60)
5Pt:Rh(60)
Ag(300)
Efficiency %
                       Aldehyde Emissions
                 Catalyst
      5
      1
99
99
98.6
98.4
98.4
92.3
10Ag:Rh(300)
Ag(300)
5Pt:Rh(60)
5Pt:Rh(80)
19Pt:Rh(80)
19Pt:Rh(60)
Efficiency %

   99. 7
   99.4
   99.4
   99.2
   97.5
   97.3
                            Table 22

                Catalyst  Comparison  With Baseline
          HFET  Driving Cycle - Three Way Operating Mode
         CO Emissions
                         NOx Emissions
   Catalyst
5Pt:Rh(60)
19Pt:Rh(60)
5Pt:Rh(80)
19Pt:Rh(80)
10Ag:Rh(300)
Ag(300)
Efficiency

  100.0
  100.0
  100.0
  100.0
   97.8
   54. 5
                 Catalyst
              5Pt:Rh(60)
              19Pt:Rh(80)
              5Pt:Rh(80)
              19Pt:Rh(60)
              10Ag:Rh(300)
              Ag(300)
                 Efficiency

                    66.8
                    66.0
                    60.8
                    58.0
                    29.6
                     6. 4

-------
                              -19-

     3.    Nine  of the  thirteen  catalysts tested were  able to
meet the  levels of  the  gasoline  light-duty vehicle NOx standard
when operated as three-way catalysts.

     4.    Substantial  aldehyde  reduction  efficiency  was shown
by    all    catalysts   tested.     The    platinum/rhodium   and
palladium/rhodium  configurations  had FTP  efficiencies  of about
90 percent under three-way or oxidation conditions.

     5.    HFET   performance   exhibited    relative   catalyst
efficiency  trends   similar  to  the  FTP  results.   HFET  emission
levels,  except  for  NOx,  were  substantially  lower  than  FTP
emission  levels.

     6.    A  catalyst  slightly larger  than  the average  size
tested  in  this  program  may  not   generally  increase  catalyst
efficiency  significantly.    Location of  the  converter   in  the
exhaust   stream  (time  to  light  off)  and  choice  of  active
catalyst  material  may  be  marginally  more  important  than  an
increase  in catalyst volume.

     7.    HC and CO  emission  levels with  some exceptions  were
generally  lower  in oxidation  mode rather  than three-way mode.
Aldehyde  and NOx levels generally  increased as  the oxygen level
at the catalyst inlet increased.

     B.    Phase II

     1.    Performance of a heavily loaded noble metal catalyst
generally  is  not   improved  by  additional  loading  beyond  60
g/ftj.

     2.    Heavily  loaded  platinum/rhodium catalysts  were  much
more efficient  at  converting the  range  of pollutants  measured
here than the heavily loaded silver or silver/rhodium catalysts.

     3.    The  platinum/rhodium catalysts tested  demonstrated
very high HC and aldehyde  efficiencies.   These  catalysts  were
able to meet the levels  of  the light-duty gasoline NOx and CO
standards.

VIII.  Acknowledgements

     The author greatly appreciates the efforts of  the  Test and
Evaluation Branch,  Emission  Control Technology Division, which
made  possible  the  successful  testing   detailed  here.   The
efforts of James Garvey  and  Ernestine Bulifant, EPA technicians
who conducted many  of  the  dynamometer tests   in  this  program,
are particularly appreciated.

-------
                              -20-

     The  author  gratefully acknowledges the efforts of Jennifer
Criss and Cheryl Hogan, both  of  ECTD,  whose attention to detail
during  the  typing of the  manuscript  and  the tables was greatly
appreciated.   Carmen  Garrett,   of   the  Programs  Management
Office,  is  extended a special thank you  for  typing many of the
tables  that appear in this report.

IX.  References

     1.    The  Clean Air  Act  as  amended  through July  1981,
Section 2ll(c)(l).

     2.    Speech  by Charles  L.  Gray,  Jr.,  EPA,  QMS,  OAR,  to
1983 Midyear Refining Meeting of the API, May 11, 1983.

     3.    Policy  Statement  by  Vice  President  of   the  U.S.A.,
George  Bush, March 6, 1987.

     4.    1975  Federal   Test   Procedure,   Code   of  Federal
Regulations,   Title  40,   Part   86,   Appendix   I(a),   Urban
Dynamometer Driving Schedule.

     5.    Highway   Fuel   Economy  Jriving   Schedule,  Federal
Register, Vol. 41, No. 100, May 21, 1976, Appendix  I.

     6.    "Low    Mileage     Catalyst     Evaluation   With     a
Methanol-Fueled  Rabbit  -  Interim  Report,"  Wagner,  R.  and  L.
Landman, EPA-AA-CTAB-83/05, May 1983.

     7.    "Low    Mileage     Catalyst     Evaluation   With     a
Methanol-Fueled Rabbit - Second  Interim Report," Wagner, R. and
L. Landman,  EPA-AA-CTAB-84/03, June 1984.

     8.    "Evaluation   of   Catalysts    for   Methanol-Fueled
Vehicles Using  a Volkswagen  Rabbit Test  Vehicle,"  presented at
the  Joint  Conference On   the  Introduction  and  Development  of
Methanol As An Alternate  Fuel, Columbus,  OH,  June  26-27,  1986,
ASME.

     9.    Moving America  to  Methanol,  Gray,  C. L.   Jr.,  and  J.
Alson,  U of M Press, Ann Arbor, MI, 1985, p. 29.

     10.   Formaldehyde Measurement In  Vehicle  Exhaust At MVEL,
Memorandum,  Gilkey, R. L.., OAR,  QMS,  EOD, Ann Arbor, MI, 1981.

     11.   Results  of Methanol  Catalyst  Testing  Analyzed  For
Trends   in  Baseline  Variance,  Memorandum,  Piotrowski,  G.  K. ,
OAR, QMS,  ECTD, Ann Arbor,  MI, 1985.

-------
                             A-l

                           APPENDIX A

            Methanol-Powered Volkswagen Test Vehicle
     Specifications  and Changes To Accommodate Methanol Fuel
     Vehicle Item
Engine:

  Displacement
  Bore
  Stroke
  Compression Ratio
  Valvetrain
  Basic  Engine
Fuel System:

  General



  Pump Life
  Accumulator-Maximum Holding
  Pressure

  Fuel Filter
  Fuel  Distributor
  Air  Sensor


  Fuel Injectors



  Cold Start  Injectors



  Fuel Injection  Wiring



  Idle Setting
      Spec i f icat ion/Change
1.6 liter
7.95 cm
8.00 cm
12.5:1
Overhead camshaft
GTI  basic   engine  -  European
high   performance   engine   to
withstand  higher  loads  -  U.S.
cylinder head.
Bosch  CIS  fuel   injection  with
Lambda  feedback  control,  cali-
brated for methanol operation..

1 year  due to  corrosiveness  of
methanol.   Improved  insulation
on wiring exposed to fuel.

3.0 Bar
One-way check valve deleted
because   of   fuel   incompati-
bility.

5.0-5.3  bar   system  pressure,
calibration     optimized    for
methanol,  material  changes  for
fuel compatibility.
Modified
teristics
airflow
 charac-
Material   changes    for   fuel
compatibility,   plastic  screen
replaced by metal screen.

2  injectors,  valves  pulse for 8
seconds beyond  start  mode below
zero degrees centrigrade.

Modified  for  cold start  pulse
function   and   to   accommodate
relays and thermo switch.
Specific
calibration.
  to
methanol

-------
                           A-2

                       APPENDIX A (cont'd)

            Methanol-Powered Volkswagen Test Vehicle
     Specifications and Changes To Accommodate  Methanol  Fuel
     Vehicle Item
PCV:


Ignition:

  Distributor
  Spark Plugs

Transmission:

  General


  Torgue Converter Ratio

  Stall Speed

  Gear Ratios:

    1

    2

    3

    Axle

Fuel Tank:

  Material

  Coating

  Seams and Fittings

  Cap

  Fuel
      Specification/Change
PCV    valve   with
plunger-no  orifice.
calibrated
Slightly     reduced     maximum
centrifugal      advance     and
slightly     modified     vacuum
advance/retard characteristics.

Bosch W260T2
1981     production    automatic
3-speed.

2.44

2000-2200 RPM
2.55

1.45

1.00

3.57



Steel

Phosphated Steel

Brazed

European neck and locking cap,

Neat methanol (M100)

-------
               APPENDIX  B



 Phase  I  -  Low  Mileage  Catalyst  Screening



Emission Statistics For FTP Driving Cycle

-------
                 B-l
Emission Statistics For FTP Driving Cycle
        For Catalyst:  5Pt:Rh(40)
Variable
Aldehyde (mg/tni)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Variable
A 1 dehyde ( mg/m i )
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Emiss
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx ( g/mi )
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
C02 (g/mi)
NOx (g/mi)
Exhaust Oxygen
N Minimum
4 17.2
6 .14
6 .70
6 278.
4 .53
Exhaust Oxygen
N Minimum
Level 0%
Maximum
26.3
. 19
.90
295.
1.68
Level 3%
Maximum
Mean
20.3
.15
.78
289.
.84
Mean
1 15.4 15.4 15.4
1 .14 .14 .14
1 .60 .60 .60
1 298. 298. 298.
1 1.95 1.95 1.95
ion Statistics For FTP Driving Cycle
For Catalyst: 12Pt:Rh(40)
Exhaust Oxygen
N Minimum
3 8.5
3 .10
3 .42
3 292.
3 .50
Exhaust Oxygen
N Minimum
3 12.9
3 . 11
3 .31
3 282.
3 1.88
Level 0%
Maximum
13.2
. 12
.93
295.
.70
Level 3%
Maximum
17.5
. 13
.50
301.
2. 10
Mean
11.6
. 11
.69
294.
.62
Mean
15.4
. 12
.39
293.
2.01
                                           Std Dev

                                             4.2
                                               .02
                                               .08
                                             5.4
                                               .56
                                           Std Dev
                                           Std Dev

                                             2.7
                                               .01
                                               .26
                                             1.5
                                               .11
                                           Std Dev

                                             2.4
                                               .01
                                               .10
                                             9.5
                                               . 11

-------
                  B-2
Emission Statistics For FTP Driving Cycle
  For Catalyst: 12Pt:Rh(40) - Racetrack
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Variable
Aldehyde ( mg/mi )
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Emission
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO2 (g/mi)
NOx (g/mi)
Exhaust Oxygen
N Minimum
2 9.9
2 . 11
2 .70
2 291 .
2 .76
Exhaust Oxyqen
N Minimum
Level 0%
Maximum
13.0
. 15
.84
296.
.77
Level 3%
Maximum
Mean
11.5
. 13
.77
294.
.77
Mean
3 13.4 15.1 14.4
3 .12 .13 .13
3 .24 .51 .40
3 297. 300. 298.
3 2.02 2.07 2.05
Statistics For FTP Driving Cycle
For Catalyst: 3Pt:2Pd(20)
Exhaust Oxyqen
N Minimum
2 29. 5
3 . 15
3 1.36
3 294.
3 .84
Exhaust Oxygen
N Minimum
1 72.9
2 . 16
2 .35
2 304.
2 2.05
Level 0%
Maximum
36.4
. 16
1.65
299.
.87
Level 3%
Maximum
72.9
. 16
.35
307.
2.09
Mean
33.0
. 15
1.47
296.
.85
Mean
72.9
. 16
.35
306.
2.07
                                           Std Dev

                                             2.2
                                               .03
                                               . 10
                                             3.5
                                               .01
                                           Std Dev

                                             1.0
                                               .01
                                               . 15
                                             1.3
                                               .02
                                           Std Dev

                                             4.9
                                               .01
                                               .16
                                             3.0
                                               .02
                                           Std Dev
                                             2.0
                                               .02

-------
                 B-3
Emission Statistics For FTP Driving Cycle
          For Catalyst: Pd(40)
Variable
Aldehyde (mg/mi)
HC (g/rai)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Emission
For
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Variable
A 1 dehyde ( mg/m i )
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Exhaust Oxygen Level 0%
N Minimum Maximum
3 38.6 46.9
3 .15 .19
3 1.59 2.29
3 300. 304.
3 .73 .75
Exhaust Oxygen Level 3%
N Minimum Maximum
Mean
41. 5
. 17
1.99
302.
.74
Mean
2 59.3 76.7 68.0
2 .14 .15 .14
2 .37 .39 .38
2 304. 307. 306.
2 1 .96 2.01 1.98
Statistics For FTP Driving Cycle
Catalyst: Pd+Base Metal(35)
Exhaust Oxygen Level 0%
N Minimum Maximum
2 118.5 119.2
2 .28 .28
2 2.72 2.98
1 286. 286.
2 1.95 1.99
Exhaust Oxygen Level 3%
N Minimum Maximum
2 117.5 141.2
2 .27 .28
2 1.94 2.17
1 292. 292.
2 1.90 2.00
Mean
118.9
.28
2.85
286.
1.97
Mean
129.4
.28
2.05
292.
1.95
                                           Std Dev

                                             4.6
                                              .02
                                              .36
                                             2.0
                                              .01
                                           Std Dev

                                            12.2
                                               .01
                                               .02
                                             2.0
                                               .04
                                           Std Dev

                                             0.6

                                               .18

                                               .03
                                           Std Dev

                                            16.8

                                               . 16

                                               .07

-------
                             B-4
            Emission Statistics For  FTP Driving  Cycle
               Driving Cycle For Catalyst: Pd(2Q)
Exhaust Oxygen
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
N
3
3
3
3
3
Minimum
35.4
.17
.49
293.
.63
Exhaust Oxygen
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
N
2
2
2
2
2
Minimum
88.7
. 15
.39
295.
1.85
Level 0%
Maximum
48.6
.20
2.09
297.
.70
Level 3%
Maximum
99.7
.16
.40
298.
1.94

Mean
41.0
.18
1.84
295.
.67

Mean
94.2
.16
.40
297.
1.90
                                                       Std Dev

                                                         6.8
                                                          .02
                                                          .31
                                                         2.0
                                                          .04
                                                       Std Dev

                                                         7.8
                                                          .01
                                                          .01
                                                         2.3
                                                          .06
            Emission
    Variable
Aldehyde (mg/mi)
   HC (g/mi)
   CO (g/mi)
   CO2 (g/mi)
   NOx (g/mi)
 Statistics  For
  For  Catalyst:
           FTP  Driving
           Ag(150)
            Cycle
                     Exhaust  Oxygen Level  0%
N

4
4
4
4
4
Minimum

  41.8
    .45
   6.29
 282.
   2.01
Maximum
 Mean
71

6
287
2
.0
.61
.69
,
.05
59

6
285
2
.3
.54
.53
,
.03
Std Dev

 12.8
   .07
   . 17
  2.6
   .02
    Variable
Aldehyde (mg/mi)
   HC (g/mi)
   CO (g/mi)
   CO2 (g/mi)
   NOx (g/mi)
 Exhaust  Oxygen  Level  3%

N    Minimum    Maximum
3
3
3
3
3
  34.7
    .35
   5.47
 285.
   1.98
  71.0
    .48
   6.48
 293.
   2.01
 Mean

 52.0
   .43
  5.93
290.
  1.99
Std Dev

 18.3
   .07
   . 51
  4. 1
   .01

-------
                  B-5
Emission Statistics For FTP Driving Cycle
     For Catalyst:  Pd+Base Metal (5)
Exhaust Oxygen
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Emission
N
Minimum
3 36.0
3 .19
3 1.08
3 265.
3 .82
Exhaust Oxygen
N
Minimum
3 67.6
3 .18
3 .49
3 281.
3 1.76
Statistics For
For Catalyst
Exhaust Oxygen
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
N
Minimum
3 26.0
3 .19
3 1.07
3 281.
3 1.73
Exhaust Oxygen
N
3
3
3
3
3
Minimum
33.0
.24
1.63
295.
1.94
Level 0%
Maximum
41.7
.20
1.37
267.
.85
Level 3%
Maximum
Mean
38.3
.19
1.21
266.
.83
Mean
98.3 80.6
.20 .18
.65 .55
287. 283.
1.89 1.80
FTP Driving Cycle
: CuO
Level 0%
Maximum
29.0
.20
1.11
286.
1.73
Level 3%
Maximum
41. 5
.27
1.66
296.
1.96
Mean
27.8
. 19
1.08
283.
1.73
Mean
37.6
.25
1.64
295.
1.95
                                           Std Dev

                                             3.0

                                               . 15
                                             1.3
                                               .01
                                           Std Dev

                                             15.9
                                               .01
                                               .09
                                             3.5
                                               .07
                                           Std Dev

                                              1.6

                                               .03
                                              2.5
                                           Std Dev

                                              4.3
                                               . 01
                                               . 01

                                               .01

-------
                  B-6
Emission Statistics For FTP Driving Cycle
          For  Catalyst: Pd(10)

Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)

Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)

N
3
3
3
3
3

N
3
3
3
3
3
Emission
Exhaust Oxygen
Minimum
25.9
.16
.64
288.
.83
Exhaust Oxygen
Minimum
72.2
. 16
.58
300.
1.85
Statistics For
Level 0%
Maximum
34.3
.18
.81
297.
.90
Level 3%
Maximum
133.9
. 17
.74
304.
1.88

Mean
29.8
.17
.74
293.
.87

Mean
95.2
. 17
.65
302.
1.86

Std Dev
4.2
.01
. 10
4.7
.03

Std Dev
33.7
-
.08
2. 1
.02
FTP Driving Cycle
For Catalyst: 9Pd:Rh(10)

Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)

Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
C02 (g/mi)
NOx (g/mi)

N
3
3
3
3
3

N
3
3
3
3
3
Exhaust Oxygen
Minimum
18.1
. 13
.52
264.
.79
Exhaust Oxygen
Minimum
32. 1
. 14
.54
286.
1.82
Level 0%
Maximum
20.4
. 14
.69
272.
.84
Level 3%
Maximum
37.5
. 16
.64
286.
1.85

Mean
18.9
. 14
.60
268.
.81

Mean
35.0
. 15
.59
286.
1.84

Std Dev
1.3
-
.09
4 . 1
.03

Std Dev
2.7
.01
.05
-
.02

-------
                 B-7

Emission Statistics For FTP Driving Cycle
        For  Catalyst:  10Aq:Rh(15Q)

Variable
A 1 dehyde ( mg/m i )
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)

Variable
Aldehyde (mi/mg)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)

N
3
3
3
3
3

N
3
3
3
3
3
Exhaust Oxygen
Minimum
57.5
.32
2.42
255.
.97
Exhaust Oxygen
Minimum
60.9
.35
2.43
280.
1.40
Level 0%
Maximum
105.2
.38
3.52
269.
1.21
Level 3%
Maximum
120 . 5
.39
2.73
291.
1 .46

Mean
83.7
.36
2.95
264.
1.05

Mean
95. 1
.36
2.61
286.
1.42

Std Dev
24.2
.03
.55
7.6
.14

Std Dev
30.8
.02
.16
5.5
.03

-------
                APPENDIX C



 Phase I - Low Mileage Catalyst Screening



Emission Statistics For HFET Driving Cycle

-------
                              C-l

           Emission Statistics For HFET Driving Cycle
                    For Catalyst:  5Pt:Rh(40)

                    Exhaust Oxygen Level  0%

    Variable       N    Minimum    Maximum    Mean    Std Dev

Aldehyde (mg/mi)   3        .10        .70      .30      .35
   HC (g/mi)       4        .001       .004     .002     .002
   CO (g/mi)       4        .08        .15      .11      .04
   C02 (g/mi)      4     226.        229.      228.        1.4
   NOx (g/mi)      4        .05        .13      .09      .04

-------
                    02
Emission Statistics For HFET Driving Cycle
         For  Catalyst:  12Pt:Rh(40)
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Variable
Exhaust Oxygen
N Minimum
3 0.30
3 .003
3 .03
3 236.
3 .58
Exhaust Oxyqen
N Minimum
Level 0%
Maximum
1.0
.004
.06
239.
.63
Level 3%
Maximum
Mean
0.5
.003
.05
238.
.61
Mean
Aldehyde (mg/mi) 3 1.0 1.6 1.2
HC (g/mi) 3 .008 .009 .008
CO (g/mi) 3 0.00 0.01 0.01
COz (g/mi) 3 220. 241. 232.
NOx (g/mij 3 2.43 2.89 2.73
Emission Statistics For HFET Driving Cycle
For Catalyst: 12Pt :Rh(40) (Racetrack)
Variable
A 1 dehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx ( g/mi )
Exhaust Oxygen
N Minimum
3 0.8
3 .005
3 .06
3 228.
3 .48
Exhaust Oxygen
N Minimum
3 1.6
3 .008
3 . 02
3 236.
3 2.80
Level 0%
Maximum
1.6
.013
.07
240.
.70
Level 3%
Maximum
2.3
.009
.03
238.
2.86
Mean
1.2
.008
.06
232.
.55
Mean
2.0
.009
.02
237.
2.84
Std Dev
0.4
.01
1.6
.03
Std Dev
0.3
11.0
.27
Std Dev
0.4
.004
6.7
.13
Std Dev
0.4
1.0
.03

-------
                   C-3
Emission Statistics For HFET Driving Cycle
        For Catalyst:  3Pt:2Pd(20)
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Emission
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx ( g/mi )
Exhaust Oxygen Level 0%
N Minimum Maximum
2 0.9 1.2
3 .006 .009
3 .20 .23
3 237. 243.
3 .63 .65
Exhaust Oxygen Level 3%
N Minimum Maximum
Mean
1.1
.007
.22
240.
.64
Mean
1 1.7 1.7 1.7
3 .010 .010 .010
3 0.00 .02 .01
3 241. 245. 243.
3 2.74 2.81 2.77
Statistics For HFET Driving Cycle
For Catalyst: Pd(40)
Exhaust Oxygen Level 0%
N Minimum Maximum
2 0.7 1.1
3 .004 .006
3 .30 .35
3 241. 243.
3 .43 .57
Exhaust Oxygen Level 3%
N Minimum Maximum
2 1.7 1.9
2 .007 .009
2 .01 .01
2 241. 242.
2 2.65 2. 65
Mean
0.9
.005
.33
242.
.51
Mean
1.8
.008
.01
242.
2.65
Std Dev
0.2
.001
.02
3. 1
.01
Std Dev
.01
2.0
.04
Std Dev
0.2
.001
.02
1.0
.07
Std Dev
0. 1
. 001

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                   C-4

Emission Statistics For HFET Driving Cycle
     For Catalyst:  Pd+Base Metal (35)
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Variable
Exhaust Oxygen Level 0%
N Minimum Maximum
2 2.6 3.6
4 .015 .018
4 1.09 1.66
1 232. 232.
4 1.24 1.72
Exhaust Oxygen Level 3%
N Minimum Maximum
Mean
3.1
.017
1.30
232.
1.51
Mean
Aldehyde (mg/mi) 2 2.8 3.2 3.0
HC (g/mi) 3 .012 .013 .013
CO (g/mi) 3 .01 .06 .03
C02 (g/mi) 2 235. 243. 239.
NOx (g/mi) 3 2.53 2.64 2.57
Emission Statistics For HFET Driving Cycle
For Catalyst: Pd(20)
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Exhaust Oxygen Level 0%
N Minimum Maximum
2 1.9 2.0
3 .008 .011
3 .32 .41
3 236. 240.
3 .30 .42
Exhaust Oxygen Level 3%
N Minimum Maximum
2 2.4 2.9
2 .008 .009
1 .01 .01
2 241. 242.
2 2.51 2.57
Mean
2.0
.009
.38
238.
.35
Mean
2. 7
.009
.01
242.
2.54
Std Dev
0.5
.001
0.26
0.20
Std Dev
0.2
.02
4.0
.06
Std Dev
.001
.05
2.0
.06
Std Dev
0.2
.03

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                              C-5
           Emission Statistics For HFET Driving Cycle
                      For Catalyst:  Ag(150)
    Variable
Aldehyde (mg/mi)
   HC (g/mi)
   CO (g/mi)
   CO2 (g/mi)
   NOx (g/mi)
  Exhaust  Oxygen  Level  0%

N    Minimum    Maximum    Mean
3
3
3
3
3
  1.9
   .021
  4.09
233.
  2.72
  3.2      2.4
   .027     .024
  4.36     4.25
235.      234.
  2.77     2.74
Std Dev

  0.7
   .003
  0. 14
  1.0
  0.02
    Variable
Aldehyde (mg/mi)
   HC (g/mi)
   CO (g/mi)
   CO2 (g/mi)
   NOx (g/mi)
  Exhaust Oxygen  Level  3%

N    Minimum    Maximum    Mean
4
4
4
4
4
  1 . 5
   . 016
  3.29
229.
  2. 57
  2.4      1.9
   .023     .019
  3.68     3.47
237.      233.
  2.72     2.64
Std Dev

  0.4
   .003
  0. 19
  3.7
  0.07
           Emission Statistics For HFET Driving Cycle
                 For Catalyst: Pd+Base Metal(5)
    Variable
A1dehyde (mg/mi)
   HC (g/mi)
   CO (g/mi)
   C02 (g/mi)
   NOx (g/mi)
    Variable

A1dehyde (mg/m i)
   HC (g/mi)
   CO (g/mi)
   CO2  (g/mi)
   NOx (g/mi)

N
3
3
3
3
3

N
3
3
3
3
3
Exhaust
Oxygen
Minimum
5


210

Exhaust
.6
.006
. 12
,
.85
Oxygen
Minimum
8

0
230
2
.3
. Oil
.00
,
.61
Level 0%
Maximum
7


214
1
.3
.008
.24

.05
Mean
6


212

.7
.007
. 17

.93
Std Dev
0.9
.001
.06
2. 1
. 10
Level 3%
Maximum
10

0
235
2
.2
.013
.01
,
.72
Mean
9

0
232
2
.3
. 012
.00
,
.65
Std Dev
0.9
.001
-
2.6
.06

-------
                   C-6
Emission Statistics For HFET Driving Cycle
            For Catalyst: CuO
Variable
A 1 dehyde ( mg/m i )
HC (g/mi)
CO (g/mi)
C02 (g/mi)
NOx (g/mi)
Variable
Exhaust Oxygen Level 0%
N Minimum Maximum
3 5.3 6.3
3 .010 .011
3 .05 .05
3 213. 215.
3 2.24 2.27
Exhaust Oxygen Level 3%
N Minimum Maximum
Mean
5.9
.011
.05
214.
2.26
Mean
Aldehyde (mg/mi) 3 6.6 6.9 6.7
HC (g/mi) 3 .011 .012 .012
CO (g/mi) 3 .08 .08 .08
C02 (g/mi) 3 230. 232. 231.
NOx (g/mi) 3 2.62 2.70 2.66
Emission Statistics For HFET Driving Cycle
For Catalyst: Pd(10)
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Variable
A 1 dehyde (mg/mi)
HC (g/mi)
CO (g/mi)
C02 (g/mi)
NOx (g/mi)
Exhaust Oxygen Level 0%
N Minimum Maximum
3 2.6 2.8
3 .010 .010
3 0.00 0.00
3 224. 228.
3 1.20 1.35
Exhaust Oxygen Level 3%
N Minimum Maximum
3 3.6 7.0
3 .010 .011
3 0.00 0.01
3 239. 240.
3 2.68 2.74
Mean
2.7
.010
0.00
226.
1.26
Mean
5. 1
.010
0.00
239.
2.72
                                           Std Dev
                                             0.6
                                             1.0
                                              .01
                                           Std Dev

                                             0.1
                                              .001

                                             1.0
                                              .04
                                           Std Dev
                                             0.1
                                             2.0
                                              .08
                                           Std Dev
                                             1.7
                                             0.5
                                              .03

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                   C-7

Emission Statistics For HFET Driving Cycle
         For Catalyst:  9Pd:Rh(10)

Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
COz (g/mi)
NOx (g/mi)

Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
C02 (g/mi)
NOx (g/mi)

Exhaust Oxygen
N Minimum
3
3
3
3
3

N
3
3
2
3
3
Emission
0.9
.005
0.00
212.
.93
Exhaust Oxygen
Minimum
1.5
.006
0.00
234.
2.67.
Statistics For
Level 0%
Maximum
1.3
.007
0.00
214 .
.96
Level 3%
Maximum
2.3
.009
0.00
237.
2.75

Mean
1.1
.006
0.00
213.
.95

Mean
1.8
.008
0.00
235.
2. 71

Std Dev
0.2
.001
-
1.0
.01

Std Dev
0.5
.001
-
1.3
.04
HFET Driving Cycle
For Catalyst: 10Ag:Rh(150)

Variable
A 1 dehyde ( mg/m i )
HC (g/mi)
CO (g/mi)
C02 (g/mi)
NOx (g/mi)

Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
COz (g/mi)
NOx (g/mi)

N
3
3
3
4
3

N
2
3
3
3
3
Exhaust Oxygen
Minimum
8.7
.011
. 15
216.
1.37
Exhaust Oxygen
Minimum
21.6
.013
.04
232.
2.46
Level 0%
Maximum
24.8
.016
.48
220 .
1 . 72
Level 3%
Maximum
23.4
.015
. 11
239.
2. 58

Mean
18.6
.014
.32
217.
1 .57

Mean
22.5
.014
.07
236.
2.52

Std Dev
8.6
.002
. 17
1.4
. 12

Std Dev
1.3
.001
. 04
3.9
.06

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               APPENDIX D



   Phase II - Low HC/Aldehyde Catalyst



Emission Statistics For FTP Driving Cycle

-------
                              D-l

            Emission Statistics  For  FTP Driving  Cycle
                    For Catalyst: 5Pt:Rh(60)

                     Exhaust  Oxygen  Level  0%

    Variable        N    Minimum    Maximum    Mean    Std Dev
Aldehyde (mg/mi)    3       9.6       11.9     10.6      1.2
   HC (g/mi)        3        .11        .13      .12      .01
   CO (g/mi)        3        .42        .45      .43      .01
   C02 (g/mi)       3     271.        275.      273.        2.2
   NOx (g/mi)       3        .67        .70      .69      .01
            Emission Statistics  For  FTP Driving Cycle
                      For  Catalyst:  Ag(30Q)

                     Exhaust  Oxygen  Level  0%

    Variable        N    Minimum    Maximum    Mean    Std Dev
Aldehyde (mg/mi)    2      25.6       32.5     29.1      4.9
   HC (g/mi)        2         .39         .45       .42       .04
   CO (g/mi)        2       5.43       5.63     5.53       .14
   C02 (g/mi)       2     288.       293.     291.       3.6
   NOX (g/mi)       2       1.58       1.62     1.60       .03
            Emission Statistics  For  FTP  Driving Cycle
                   For Catalyst: 10Ag:Rh(3QO)

                     Exhaust  Oxygen  Level  0%

    Variable        N    Minimum    Maximum    Mean    Std Dev
Aldehyde (mg/mi)    3      14.0       27.8     19.3      7.4
   HC (g/mi)        3        .30        .37       .35      .04
   CO (g/mi)        3       2.22       3.56     2.92      .67
   C02 (g/mi)       3     286.        290.      287.       2.2
   NOx (g/mi)       3       1.02       1.32     1.20      .16

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                   D-2
Emission Statistics For FTP Driving Cycle
        For Catalyst:  19Pt:Rh(60)
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Emission
Variable
Exhaust Oxygen
N Minimum
Level 0%
Maximum
Mean
2 7.4 22.6 15.0
3 .09 .10 .10
3 .62 .77 .68
3 285. 290. 287.
3 .83 .86 .84
Statistics For FTP Driving Cycle
For Catalyst: 5Pt:Rh(80)
Exhaust Oxyqen
N Minimum
Level 0%
Maximum
Mean
Aldehyde (mg/mi) 3 4.0 7.0 5.5
HC (g/mi) 3 .10 .13 .11
CO (g/mi) 3 .64 .72 .69
C02 (g/mi) 3 285. 288. 287.
NOx (g/mi) 3 .80 .84 .82
Emission Statistics For FTP Driving Cycle
For Catalyst: 19Pt:Rh(80)
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Exhaust Oxygen
N Minimum
3 7.8
3 .08
3 .53
3 297.
3 .71
Level 0%
Maximum
10.8
.10
.63
302.
.77
Mean
9.6
.09
.58
299.
.74
                                           Std Dev

                                             10.7
                                               .01
                                               .08
                                             2.6
                                               .02
                                           Std Dev

                                              1.5
                                               .02
                                               .04
                                              1.5
                                               .02
                                           Std Dev

                                              1.5
                                               . 01
                                               .05
                                              2.5
                                               .03

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                 APPENDIX E



Phase II - Low HC/Aldehyde Catalyst Screening



 Emission  Statistics For HFET Driving Cycle

-------
                   E-l

Emission Statistics For HFET Driving Cycle
         For Catalyst: 5Pt:Rh(60)
Variable
Exhaust Oxygen
N Minimum
Aldehyde (mg/mi) 3 0.6
HC (g/mi) 3 .006
CO (g/mi) 3 0.00
C02 (g/mi) 3 218.
NOx (g/mi) 3 .80
Emission Statistics For
For Catalyst:
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
C02 (g/mi)
NOx (g/mi)
Emiss
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Exhaust Oxygen
N Minimum
Level 0%
Maximum Mean
1.8 1.1
.008 .007
0.00 0.00
224. 220.
.88 .83
HFET Driving Cycle
Ag(300)
Level 0%
Maximum Mean
2 0.8 1.3 1.1
2 .031 .034 .033
2 2.47 2.57 2.52
2 223. 223. 223.
2 2.31 2.36 2.34
ion Statistics For HFET Driving Cycle
For Catalyst: 10Ag:Rh(300)
Exhaust Oxygen
N Minimum
3 0.4
4 .015
4 0.00
4 220.
4 1 .66
Level 0%
Maximum Mean
1.0 0.6
.019 .017
.28 .12
226. 222.
1.82 1.76
                                           Std Dev

                                             0.6
                                              .001

                                             3.5
                                              .04
                                           Std Dev

                                              .36
                                              .002
                                              .07

                                              .03
                                           Std Dev

                                             0.3
                                              .002
                                              . 12
                                             2.9
                                              .09

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                   E-2
Emission Statistics For HFET Driving Cycle
        For Catalyst:  19Pt:Rh(60)
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Emiss
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Emiss
Variable
Aldehyde (mg/mi)
HC (g/mi)
CO (g/mi)
CO 2 (g/mi)
NOx (g/mi)
Exhaust Oxygen
N Minimum
Level 0%
Maximum
Mean
3 0.2 12.2 5.1
3 .006 .008 .007
3 0. 00 0 . 00 0. 00
3 221. 221. 221.
3 1.01 1.05 1.03
ion Statistics For HFET Driving Cycle
For Catalyst: 5Pt:Rh(80)
Exhaust Oxygen
N Minimum
Level 0%
Maximum
Mean
3 0.4 3.8 1.5
3 .005 .006 .006
3 0.00 0.00 0.00
3 218. 221. 220.
3 .96 1.01 .98
ion Statistics For HFET Driving Cycle
For Catalyst: 19Pt:Rh(80)
Exhaust Oxygen
N Minimum
3 3.4
3 .004
3 0.00
3 223.
3 .84
Level 0%
Maximum
6.4
.005
0.00
229.
.87
Mean
4.6
.004
0.00
226.
.85
Std Dev
6.3
.001
.02
Std Dev
•2.0
1.4
.03
Std Dev
1.6
3.1
.02

-------