EPA/AA/CTAB/87-01
                        Technical Report
                Durability of Low Cost Catalysts
                  For Methanol-Fueled Vehicles
                               By
                      Robert M.  Heavenrich
                       Robert I. Bruetsch
                     Gregory K. Piotrowski
                          October 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
                                                     AIR AND RADIATION
 December 14,  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   "Durability   of   Low  Cost
Catalysts  for  Methanol-Fueled  Vehicles,"   (EPA-AA-CTAB-87-01)
describes catalysts  tested  at MVEL for efficiency  at  zero miles
and then  aged  12,000-14,000 miles in  Los Angeles,  California  as
part  of  a  California  Energy  Commission sponsored  program  in
cooperation with  Ford,  Toyota,  and  EPA.   This report  compares
FTP and  HWY test  results  at the  12,000-14,000 mile  point  with
the zero-mileage results.

     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:  	:	  Date
           Charles L. Gray, Jr.", Dir.,  ECTD
Attachment

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Background

     The  objective   of   the  project   was   to  evaluate   the
efficiency  durability   of   low  cost   catalysts   operated  on-
methanol-fueled vehicles  in  fleet  service.   The catalysts  were
first  tested   at  EPA  for efficiency  at zero  miles. [1]*   The
catalysts   were   then   operated   on  cars   in  Los   Angeles,
California.   After  12,000-14,000  miles were  accumulated  on the
catalysts,  they were  removed  from  the cars  and shipped back  to
EPA for  further testing.  This  report compares  the  tests  at the
12,000-14,000  mile  point with  the  zero-mileage  results.   The
California  Energy  Commission,  Engelhard   Specialty  Chemical
Division, Johnson Matthey Catalytic  Systems  Division,  Ford and
Toyota cooperated with EPA in this  effort.

Description of Catalysts

     Two  catalyst  types were  tested  in this program.    Both
catalyst types were monoliths with  substrates of 400 cells per
inch  and a 6-mil  wall  thickness.   Both were  composed  of two
separate biscuits  in  a  single  container.   Each biscuit  has  an
oval  cross  section measuring  3.15  by  4.75  inches.  The front
biscuit  is  2.98  inches  long and  the rear  biscuit  4.3  inches
long for a total substrate volume of 92.8 cubic  inches.

     Both catalyst  types  had  loadings  of  20   grams  of  noble
metal  per  cubic   foot.   One  catalyst  type   contained  only
palladium (Pd); the other contained  platinum (Pt)  and palladium
in  a  ratio of  3:2.   Using  standard CTA3  notation, these are
denoted Pd(20)  and 3Pt:2Pd(20),  respectively.

     A  total   of   eight  catalysts   (four  of   each  type)  were
prepared  for  this project.   Three  of  the   four  units  of  each
type  were  shipped  to California  in January  1984   without any
testing  at  EPA.   One  catalyst  of  each type  was  zero-mileage
tested  at  EPA before   being  shipped  to  California  in  April
1984.**

     Table  1   gives  a  listing  of  the  catalysts  that  were
installed on the  fleet  vehicles for  mileage accumulation:   the
catalyst  type,   formula,  catalyst   serial   number,   vehicle
identification number (VIN), fleet vehicles,  license plate, and
odometer reading when the catalyst  was removed from  the  car.


*    Numbers in brackets  denote  references  listed  at the end of
     the report.

**   The  two  catalysts  zero-mileage  tested  at  EPA  had  serial
     numbers   NPN   7-16  (PD(20»   and  9K-8579,   EPA   2648
     (3Pt:2Pd(20)).   The catalysts were  installed  on the aging
     vehicles   in  January 1984  by  Bill  Stroppe   & Son,  Long
     Beach,  CA,  but  the initial  odometer  readings  were  not
     recorded.

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                            -2-





                           Table  1



     Sample Numbers of Catalysts Aged on Fleet Vehicles
Sample Catalyst
Number Type Formula
1 OX Pd(20)
2 TWC* Pd(20)
3 TWC* 3Pt:2Pd
(20)
4 OX 3Pt : 2Pd
(20)
5 OX 3Pt : 2Pd
(20)
6 OX Pd(20)

Serial No.
NPN 6-15
NPN 8-17
9K-8583
EPA2650
9K-8580
EPA2649
9K-8584
EPA2651
NPN 3-12
Vehicle License
Ident . No. Plate No.
1FABP137 0868571
XDW237350
1FABP137 0868573
XDW237378
1FABP137 0868572
6DW237359
1FABP137 0868570
3DW237349
1FABP137 0868575
9DW237405
1FABP137 0868574
9DW237386
Odometer
Reading
13306 .3
12732.0
14249 . 2
12493.8
11809.4
13247.9
No thermactor belt.

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                               -3-

     For  each  catalyst  used  as  an  oxidizing catalysts,  the
downstream air  tube  was flush  mounted with the exhaust  pipe  to
put  air  (from  the  air  pump)  into  the  exhaust  at  least  six
inches upstream of  the catalyst.   For  each catalyst used  as  a
three-way catalyst,  the belt  to  the air pump  was  removed,  and
the downstream air tube was capped.

EPA Test Vehicle

     The catalysts were tested at EPA on  a  1982 Toyota Cressida
described in  Table  2.  This vehicle was modified  by Toyota  to
operate on methanol  fuel.   Additional  modifications were  made
to the  Cressida's exhaust system to facilitate installation  of
the   catalysts    and   to   allow   for    the    installation   of
thermocouples before  and  after the catalyst.   Fuel  injectors
were  changed  by  Toyota in  March  1984,  April  1984, May  1984,
June 1984, July 1984, August 1986,  and August 1987.

Zero Mileage Test Procedure

     The  initial  plan called  for testing of  the  catalysts over
the following sequence:

     1975 Federal Test Procedure (FTP)
     Highway Test Procedure (HWY)
     10 mph steady state
     20 mph steady state
     30 mph steady state

     After baselining  the  test  car without   a  catalyst,  the
sequence was performed  three times  for each catalyst at each of
two  exhaust  oxygen  levels.    The higher  of   the   two  exhaust
oxygen  levels  was measured  at the  catalyst  inlet  using  a Sun
oxygen analyzer and  was obtained at  30 mph steady  state.   The
two  oxygen  levels were stoichiometry  (or  near 0  percent)  and
about 6 percent.   The  air  pump  was  installed  (March  1984)  in
order to  provide the  6  percent  oxygen  level.   By  testing  at
different  exhaust oxygen  levels we  could,  therefore,  evaluate
each catalyst as  a  three-way  catalyst  and  also as  an oxidation
catalyst.

     As the  project  proceeded,  steady-state test   points  were
deleted in  order to  speed up the testing.   HC,  CO,  NOx,  MPG,
methane, and  aldehydes were initially  measured over  each  test
in the  sequence.   Measurement for   aldehydes  was  deleted for
some of the steady-state  tests.   The apparatus  used to measure
HC, CO, NOx,  and aldehyde emissions  is described  in references
2 and 3.

     The  test  fuel  used  in  this  program was pure  methanol.
Five batches  of  methanol  were consumed  in this  phase of  the
project; one was  analyzed, and described in reference  2.   The
gasoline  used  in  the  cold-start   system  of   the  Toyota  is
Indolene clear  (unleaded)  and  meets  the  EPA  specifications for
that  fuel  (40  CFR 86.307-82).

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                             Table  2

                Emission Test Vehicle  Description

             1982 Toyota Cressida (methanol-fueled)
           Vehicle  Identification Number:  MX62-083780
Engine:

     Type

     Bore x Stroke

     Displacement

     Compression Ratio

     Fuel Metering
Drive Train:

     Transmission Type


     Axle Ratio

Chassis:

     Type

     Tires


     Curb Weight

     Test weight (ETW)

     Actual  Dynamometer
     Horsepower
4-stroke Otto cycle, in-line 6

83 . 0 x 85.0 mm

2759 cc (168 CID)

10.0: 1

Two separate fuel injection
systems.  (The main fuel
injection system uses pure
methanol;  a separate
cold-start fuel injection
system uses pure gasoline.
4-speed automatic with
overdrive

3.73
4-door sedan

Dunlop 185/70SR14 steel
belted radials

2,855 pounds

3,000 pounds

10.3

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                               -5-

Zero Mileage Test Results

     Tables 3  and  4  present average zero-mile FTP emissions and
efficiencies.   (More  detailed  data  on these tests  is presented
in  reference  2.)  Due to  the substantial shift  in engine-out
emissions following the  replacement  of the fuel  injectors,  the
data in  these  tables  is  limited to those tests after the change
in  injectors.    Tables  5  and   6  present  zero-mileage  highway
emissions and efficiencies* for the two catalysts.

     Table  7  contains zero-mile  efficiencies  for  each  bag  of
the FTP.

Mileage Accumulation Vehicles

     Mileage accumulation was  performed  on six model  year  1983
methanol-fueled  Escorts  (Tables 8 and 9).   These cars were part
of a fleet based at the Los Angeles airport and driven by State
of  California  employees.   Initial  maintenance on  the vehicles
was  performed  under   contract by  Thrifty  Rent-A-Car.    After
January  1,   1986,   the  maintenance  was  performed  by  Dollar
Rent-A-Car.

     Mileage accumulation on the  Escorts was  very  uneven.  Some
selected  cars  were signed  out almost continuously,  while  some
were utilized  only on those occasions when  a  great  number  of
cars  were  needed.    The  level  of  maintenance of  these  cars
apparently  dropped   off   appreciably  before  January  1986.
Appendix A gives a summary  of  the maintenance performed on each
of the Escorts used in this project.

     A Ford  Motor  Company  engineer  examined  17  of  the  fleet
Escorts-  in  June  1985  and  observed  a number of  maintenance
problems with these vehicles.   Commonly observed problems were:

     1.     Carburetors had  been  adjusted  to  very  rich  idle
mixtures; and

     2.     Ignition timing which  should  have  been  maintained at
14° BTDC had been retarded to approximately 8°.

     Thus,  the cars were  operated by a number  of drivers,  on  a
number  of unknown  routes, under  a  number  of different  driving
conditions,  often  under  conditions   of  maintenance  different
from those recommended by the manufacturer.
     Catalyst efficiency  is defined  as the  percent  difference
     between the emissions measured with and without a catalyst.

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-6-
Table 3
Summary of Average Zero-Mile
at Different Oxygen
Catalyst
None
3Pt:2Pd(20
Pd(20)

HC (g/mi)
Oxygen
0% 6+%
.99
) .24 .27
.29 .28

Aid. (mg/mi)
Oxygen
0% 6+%
283.6
37.3 264.6
41.0 236.5
Table 4

FTP Emissions
Levels
CO (g/mi)
Oxygen
0% 6%
8.85
2.80 0.34
1.97 0.72


NOx (g/mi)
Oxygen
0% 6%
2.08
0.51 1.35
0.32 1.32

Zero-Mile FTP Catalyst Efficiency (percent)
at Different Oxyqen Levels
Catalyst
3Pt:2Pd(20
Pd(20)

HC (g/mi)
Oxygen
0% 6+%
) 76 73
71 72

Aid. (mg/mi)
Oxygen
0% 6+%
87 7
86 17
Table 5
Summary of Average Zero-Mile
at Different Oxyqen
Catalyst
None
3Pt:2Pd(20
Pd(20)
HC (g/mi)
Oxyqen
0% 6+%
.42
) .01 .01
.01 .01
Aid. (mg/mi)
Oxygen
0% 6+%
167.2
5.4 40 . 4
7.3 31.9
CO (g/mi)
Oxygen
0% 6%
68 96
78 92

HWY Emissions
Levels
CO (g/mi)
Oxyqen
0% 6%
6.33
. 0 . 74 0 . 00
0.74 0.02
NOx (g/mi)
Oxygen
0% 6%
75 35
85 36

NOx (g/mi)
Oxygen
0% 6%
1.88
0.26 1.06
0.06 1.06

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                             -7-
                            Table 6

        Zero-Mile Catalyst Efficiency (percent)  Over HWY
                   at Different Oxygen Levels*
HC (g/mi)
Oxygen
Catalyst
3Pt:2Pd(20)
Pd(20)
0%
98
98
6+%
97
97
Aid. (mg/mi)
Oxygen
0%
97
96
6+%
76
81
CO (g/mi)
Oxygen
0%
88
88
6%
99 +
99+
NOx (
g/mi)
Oxygen
0%
86
97
6%
44
43
                            Table 7

        Zero-Mile Catalyst Efficiency (percent) Over FTP
               By Bag at Different Oxygen Levels*
HC Effic.
Run As :
TWC OX
Aid. Effic.
Run As :
TWC OX
CO Effic.
Run As :
TWC OX
NOx Effic.
Run As :
TWC OX
3Pt:2Pd(20):

   Bag 1        49    48    67      8     54     87    65     19
   Bag 2        97    94    96      5     73.    100    82     50
   Bag 3        88    78    90      8     74     98    77     31

Pd(20):
Bag
Bag
Bag
1
2
3
38
97
84
44
97
81
65
96
85
1
39
-24
54
90
78
77
99
93
72
92
87
18
53
34
     "TWC"  denotes a three-way catalyst (0 percent oxygen
     level),  and "OX" denotes an oxidizing catalyst (6+ percent
     oxygen level).

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                              -8-
                             Table  8

            Mileage Accumulation Vehicle Description

                1983 Methanol-Fueled Ford Escorts
Engine:

     Type

     Bore x Stroke

     Displacement

     Compression Ratio

     Fuel Metering

Drive Train:

     Transmission Type

Chassis:

     Type
     Vehicle Identification
     Numbers
4-stroke Otto cycle,  in-line 4

80.0 x 79.5 mm

1.6 liters  (98 CID)

11.8:1

2-barrel carburetor



3-speed automatic transaxle
4-door station wagon or
4-door sedan

1FABP1373DW237349
1FABP137XDW237350
1FABP1376DW237359
1FABP137XDW237378
1FABP1379DW237386
1FABP1379DW237405

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                               -9-
                             Table  9

            Modifications  Made  to the Model Year  1983
   Gasoline-Fueled Escorts to Convert Them to Methanol-Fueled
Fuel System

     Fuel Tank:

     Same design  as gasoline-fueled Escort,  but  it is made  of
stainless steel for corrosion protection.

     Fuel Tank Sending Unit:

     Same design  as  standard unit, but  it  is nickel  plated  to
prevent corrosion and has nickel plated brass float.

     Fuel Tank Straps:

     Same design  as standard model,  but  the straps  are  coated
with  nylon  to  prevent  dissimilar  metal   corrosion  of  the
stainless steel methanol fuel tank.

     Fuel Lines:

     Same  routing  as   standard   Escort,   but   the  lines  are
fabricated from stainless steel to prevent corrosion.

     Fuel Pump:

     Same design  as standard unit,  but  all  metallic  parts have
been made  corrosion  resistant  through  nickel plating,  and all
plastic and  rubber  parts are  made from  a  material which will
withstand methanol.

     Carburetor:

     The carburetor is  stock,  modified  and  recalibrated to meet
the higher fuel-flow  requirements  of  the methanol  engine.   All
parts have been  nickel plated  or  manufactured  from  a material
which  is  compatible  with fuel  methanol.   For  example,  idle
adjusting needles  and  throttle  shafts  are  made  of  stainless
steel.   The float unit  is  an acetal hollow design  and replaces
the standard  unit.

     Carburetor Spacer :

     A  rectangular   spacer  plate   is   installed  between  the
carburet jr base and intake manifold.  This  plate uses  a round
electrical heating  unit which replaces the  square  heating unit
used on the gasoline-fueled engine.

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                           -10-

                        Table 9 (cont'd)

            Modifications  Made to  the  Model  Year  1983
   Gasoline-Fueled Escorts to Convert Them to Methanol-Fueled


Engine

     Basic Engine:

     The engine that powers the methanol vehicle is the same
basic design as the Escort's gasoline-fueled l.6L high-output
(HO) engine.

     The compression ratio has been increased from 8.8:1 to
11.8:1.  This was accomplished by installing the piston from a
European 1.3L Ford engine in the 1.6L block.  Each piston has
been fitted with a special top compression ring which is barrel
faced and hard chromed steel.   Piston rings two and three are
standard.

     A 1984 head gasket that will withstand higher compression
pressures is used to replace the standard gasoline head
gasket.  This head gasket uses a stainless steel fire ring and
special backing material.

     The base 1.6L camshaft (pink color code) is used in place
of the HO camshaft (yellow color code).

     Engine Oil:

     A unique engine oil containing a special additive must be
used with methanol-fueled engines.  The recommended oil is
marked for methanol engines only.

Ignition

     Distributor:

     The distributor is a modified,  solid-state unit.   Its
operation is the  same as the standard unit;  the advance curves
have been modified.   The major difference is less mechanical
advance.

     Spark Plugs:

     The spark plugs used in the methanol-fueled engine are two
heat ranges colder than the spark plugs in the gasoline powered
1. 6L engine.   This is necessary to prevent engine damage due to
preignition.

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                               -11-

 Tests  on Aged Catalysts

     Baseline (i.e.,  without  a catalyst)  FTP and HWY tests were
 first  run  on the  Toyota  Cressida  to  compare  to the  zero-mile
 vehicle   baseline   emissions   measured  in  1984.   The  Toyota
 Cressida was then  used  to  test the aged catalyst efficiency of
 the  six  catalysts returned from California.  FTP  and  HWY tests
 were  performed  for  each catalyst  with HC,  CO, NOx,  MPG,  and
 aldehydes measured  over  each  test in the sequence.

     The  need   to   replace  fuel   injectors  in  the  Cressida
 continued.   Table  10  gives a listing  of the dates unscheduled,
 non-routine maintenance was  performed on  the  Toyota  Cressida
 for  the  period July  1,  1984  to  September  30,  1987.   New
 injectors were  installed twice during  this  phase of the project
 in July  1984  and again in August 1986.

     Bag-by-bag  FTP and highway baseline results for the period
 August 8, 1986 to September  23, 1987  are  presented in Appendix
 B.   The  data  for  HC  in  this appendix  show that  the average
 baseline FTP  emissions for  HC  for  the tests run  November  7 to
 14,  1986 are essentially double  what  they  were for the period
 August 8 to  October  28, 1986.  At  this point  Toyota replaced
 the  fuel  injectors.   Baseline HC  emissions  with this  set of
 injectors were  about the same  as those for  the  period August  8
 to October  28,  1986,  but CO was lower  and NOx higher.

     Test  results   for  the  aged  catalysts  are  presented  in
 Tables   11  and   12.   Table   11  gives  FTP  results  for  the
 catalysts;  Table 12 gives the HWY results.

 Comparison  of New and  Aged  Catalyst Efficiencies

     Tables  13  and  14 compare  percent  conversion efficiency for
 the  new  and  aged  catalysts  for   the  -FTP   and  HWY  tests
 respectively.   Because of  the shifting of the baseline emission
 data,  percent  conversion  gives  a better  indication . of  the
^.erformance  of  the  catalyst  than  the actual  emission levels
 achieved  by   the  catalyst.    The  zero-mileage  (i.e.,   new)
 efficiencies  in  this  table  are  the  same as presented previously.

     Emission  levels  as measured on the  Cressida are likely to
 differ from those in-the Escorts for two reasons:

     1.     Zngine-out  emissions from the Cressida for  HC and CO
 are low;   and

     2.     The  two  cars have  different engine-out emission and
 exhaust  gas temperature  characteristics.

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                              -12-

                            Table 10

         Unscheduled Maintenance on  the  Toyota  Cressida*

               July  l, 1984 to September 30, 1987
      Date
               Comments
July 3, 1984


November 27, 1984

August 4,  1986

August 18, 1986


August 19, 1986


August 29, 1986

September  10, 1986




November 13, 1986

November 14, 1986


August 8,  1987


September  24, 1987


September  28, 1987
Toyota installed new injectors and a
new pulsating damper valve

New battery installed

New battery installed

Car stalled when put into gear when
started cold for LA-4

Toyota representative observes test
and agrees car needs repair

Toyota installed new fuel injectors

Stalling problem only marginally
improved, caution must be exercised to
keep car from stalling shortly into
the FTP

Several stalls at idle

Engine seems to be running rough at
cruise

Toyota replaced fuel filter and fuel
injectors.

Car stalled 22 times during FTP
preparation.

Car returned to Toyota.
     Unscheduled maintenance on the Toyota for the period
     February 1, 1984 to June 30,  1984 was previously reported
     in Reference 2.

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                           -13-


                          Table 11

            Aged Oxidation  Catalyst  FTP Emissions
Catalyst Sample
Formula No.
3Pt:2Pd(20) 4


3Pt:2Pd(20) 5

Pd(20) 6


Pd(20) 1

Pd(20) 1


Test No.
864996*
864998
865000
870165
870167
870177
870451
875295*
879453*
870506*
871339
871340
871341
Date
08/19/86
09/10/86
09/12/86
10/09/86
10/10/86
10/29/86
10/30/86
09/24/87
10/31/86
11/04/86
09/15/87
09/16/87
09/17/87

0
0
0
0
0
0
0
0
0
0
0
0
0
HC
.35
.54
.55
.53
.54
.39
.36
.24
.51
. 47
.40
.36
.41
CO
(g/mi;
3.9
4.8
4.7
5.5
5.5
5.5
5.4
0.49
5.7
7.0
.50
.64
.73
CO 2
)
387
370
369
376
377
377
379
3d7
387
397
383
381
380

0
0
0
0
0
0
0
2
0
0
1
2
2
NOx
.83
.89
.88
.97
.90
.73
.71
.31
.89
.80
.92
.03
. 10
MPG
10.
10.
10.
10.
10.
10.
10.
10.
10.
10.
10.
10.
10.

4
9
9
7
6
6
6
6
4
1
6
7
7
HCHO
(jng/mi)
152.8
124.6
83.8
94.5
140.8
366.7
164.4
400.7
187.8
125.4
521.0
611. 5
632.7
Aged Three-Way Catalyst FTP Emissions
Catalyst Sample
Formula No.
3Pt:2Pd(20) 3

Pd(20) 2

Pd(20) 2


Test No.
870169
870171
870535
870527
871334
871335
871336
Date
10/16/86
10/21/86
11/05/86
11/06/86
08/25/87
09/04/87
09/09/87

0
0
0
0
0
0
0
HC
.32
.32
.31
.36
.33
.23
.31
CO
(g/mi;
4.6
4 . 7
5.9
6.9
2.9
2.8
2.9
C02
380
385
391
421
388
391
381

0
0
0
0
1
1
1
NOx
.57
.57
.59
, 54
.36
.59
.29
MPG
10.
10.
10.
9.
10.
10.
10.

6
5
3
5
4
4
6
HCHO
(mg/mi)
68.9
53.6
51 . 5
53.6
156.7
105.8
103 .3
Essentially a void test,  not used in data analysis (injectors
changed).

-------
                           -14-

                          Table 12

            Aged Oxidation Catalyst  HWY Emissions
Catalyst Sample
Formula No.
3Pt:2Pd(20) 4


3Pt:2Pd(20) 5

Pd(20) 6

Pd(20) 1


Test No.
864997*
864999
865001
870166
870168
870438
870452
870454*
870507*

Date
08/10/86
09/10/86
09/12/86
10/09/86
10/10/86
10/29/86
10/30/86
10/31/86
11/04/86

HC
CO
C02
NOx
(g/mi)
0
0
0
0
0
0
0
0
0
.02
. 04
.04
.05
.05
.02
.02
.04
.03
2
5
5
5
5
5
5
6
6
Aged Three-Way Catalyst HWY
Catalyst Sample
Formula No.
3Pt:2Pd(20) 3

Pd(20) 2


Test No.
870170
870172
870536
870528

Date
10/16/86
10/21/86
11/05/86
11/06/86

HC
.9
. r
.1
.8
.4
.2
.4
. 1
.2
334
322
321
334
331
329
333
341
322
0.51
0 .38
0.37
0.42
0.40
0.34
0 .36
0.43
0.34

MPG
12.2
12.5
12.5
12.0
12. 1
12.2
12.1
11.7
12.4
HCHO

(mg/mi)
4.3
4 .9
2.3
3.4
0 .0
4 .7






VOID
3.5
2.3


Emissions
CO
CO z
NOx
(g/mi)
0
0
0
0
.02
.01
. 02
.02
3
2
5
5
. 1
. 6
.2
.6 .
332
333
348
359
0.27
0.27
0.26
0.26

MPG
12.
12.
11.
11.
HCHO

(mg/mi)
2 0 .
2 0.
6 1 .
2 2.
2
0
0
4
Essentially a void test, but used in data analysis (injectors
changed).

-------
-15-
Table 13
Comparison of Percent
New and Aqed Catalyst
Catalyst Formula
Aging and
Testing Mode
Sample Number
3Pt
TWC
3
:2Pd(20
OX
4
Conversion for
s on FTP Test
)
OX
5

TWC
2
Pd(20)
OX
1

OX
6
Efficiency for:
HC

CO

NOx

Aid.

Aged
New
Difference*
Aged
New
Difference
Aged
New
Difference
Aged
New
Difference
78
76
+2
63
68
-5
70
75
-5
82
87
-5
57
73
-16
66
96
-30
51
35
+ 16
67
7
+ 60
63
73
-10
57
96
-39
50
35
+ 15
65
7
+ 58
77
71
-6
62
78
-16
45
85
-40
71
86
-15
70
72
+4
92
92
0
17
36
-19
N/A
17
N/A
82
72
+ 10
73
92
-19
58
36
+22
30
17
+ 13
                            Table 14

              Comparison of Percent Conversion for
               New and Aged Catalysts on HWY Test
Catalyst Formula
Efficiency for:

   HC
   CO
Aged
New
Difference*

Aged
New
Difference
   NOx  Aged
        New
        Difference

   Aid.  Aged
        New
        Difference
                  3Pt:2Pd(20)
Aging and Testing Mode  TWC
Sample Number	   3
                        OX
97
98
-1
76
88
-12
83
86
-3
100
97
3
90
97
	 -7
60
99
-39
73
44
29
98
76
22
 OX
 91
 97
 -6

 52
 99
-47

 74
 44
 30

 99
 76
 23
TWC
 97
 98
 -1

 69
 88
-19

 82
 97
-15

 99
 96
  3
               Pd(20)
OX
OX
95
97
-2
65
99
-34
74
43
+31
99
81
18
97
97
0
70
99
-29
76
43
+23
98
81
17
     Difference is aged minus new.

-------
                              -16-

     The  percent  conversion   for   the  aged   catalysts   were
determined  by  calculating  the   average   emissions  for   each
catalyst  on  the  FTP  and HWY  tests,   and  then  comparing  these
values with the average  of  the baselines immediately before and
immediately  following   the  tests   for  that   catalyst.    For
example,  the  HWY  tests  for sample  4  run  on September 10  and
September  12,  1986  and  compared to  the  "before"  tests  run
August 8  and  August 12,  1986  and also  to  the  "after"  runs  on
October 3 and October 8,  1986.

     Appendix C shows the effect  of  the shifts  in  the  baseline
data on the percent  conversion date  of the aged catalysts.  For
some  cases,  this  effect is   relatively small.   For  example,
sample 3  on the FTP  test had a percent  conversion  range for  HC
of 76 to  80.   For many  cases,  the effect is  much larger (e.g.,
58 to 71 for CO on sample 3  on  the FTP test).

     The  highest   tailpipe  formaldehyde emission   levels  (and
lowest percent  conversions) occurred on the FTP  zero-mileage
runs  in  the oxidation mode (17  and  7 percent  compared to  TWC
mode  results  of  86  and   87  percent  for  the   Pd(20)   and
3Pt:2Pd(20) catalysts,  respectively).

     When  operated  as   oxidation catalysts,  the   aged  Pd(20)
catalysts perform  somewhat  better than  their  counterparts with
the   3Pt:2Pd(20)   formula,   particularly   on   the   FTP.    The
differences  between  the  results  for  the  two  formulas  are
smaller when the catalysts are  operated in the TWC mode.

Deterioration Factors

     To  further  compare  the  catalysts,  deterioration  factors
were calculated for each of them.  Table 15  gives  DF*  for each
of the  six catalysts for  HC,  CO, NOx,  and  HCHO,  and  compares
these  values  with the  actual  DF  for  HC,   CO,   and  NOx  for
gasoline-powered   light-duty   vehicles.    In   calculating  DF*
several assumptuions  were made:

     1.     Differences   between   the   mileage  accumulation  in
California and the AMA  mileage  accumulation route were ignored;

     2.     Maintenance  differences were not accounted for;

     3.     Engine-out emissions  were  assumed  to   be  constant
over 50,000 miles; and

     4.     An expodential extrapolation of the form:

     Efficiencyt  = Efficiency0  EXP (k miles/1000)

     was  used  to  calculate  emissions  at  4,000  and  50,000
miles.  This  is   the  same  extrapolation  method as  was  used  in
reference 4.

-------
                              -17-

     5.    Because the exact  number  of  miles each  catalyst  was
aged was  unavailable,  the odometer  readings  when the catalysts
were removed  for  shipment  to  Ann Arbor were used  as  an  assumed
number of miles aged.  This represents a "best case" scenario.

     Under these assumptions,  the formula for DF* becomes:

           (1 - EFF5o)
     DF* =
           (1 - EFF4)

     Where,  EFFSO  and  EFF4   are   the   extrapolated  catalyst
efficiencies at 4,000 and 50,000 miles, respectively.

     A value of  "1"  was  used in Table 15  for  those cases where
no deterioration  in  catalyst  efficiency  occurred.  The  data in
this  table  shows relatively  good  agreement  between  catalyst
types  and  modes.   For  example  the  3Pt:2Pd  catalyst,  when
operated in Oxcat mode  (samples 4 and 5), had DF* values of 2.2
and 2.0 for HC, and 5.3 and 4.6 for CO.

     The agreement between DF*  and DF for a gasoline car is of
order   of   magnitude  quality.    Analysis  of   this   data  is
complicated by three factors:

     1.    The number of samples is small;

     2.    Little is known about how,  when,  and  where the fleet
vehicles were driven; and

     3.    The condition of  the EPA test vehicle varied greatly
despite  the  relatively  small  number of • miles  it was  driven
during the test period.

Conclusions

     After  12,000 to  14,000  miles  of  fleet use  on  the   road
aging:

     1.    Both   catalyst  types  tested  showed  evidence  of
deterioration  in  their  ability to  convert CO  in both three-way
and oxidation modes;

     2.    There  is  little   evidence  of  any  change   in  the
ability of either catalyst type to convert HC;  and

     3.    When  tested  in  the  three-way mode,  both  catalyst
types show degradation in their ability to convert NOx.

-------
                              -18-









                            Table 15



              FTP  Deterioration  Factors  By Catalyst
Sample
Number Formula
3 3Pt:2PD(20)
4
5
2 Pd(20)
1
6

Mode
TWC
OX
ox
TWC
OX
ox

HC
1
2.
2.
1
1 .
1.



2
0

2
3

CO
1 .
5.
4 .
2.
1 .
4 .



NOx
4
3
6
5
0
3
1
1
1
3
1
1
.6


. 1
.4
. 1


HCHO
2
1
1
3

1
.0


. 1
NA

Gasoline car:  DF                  1.3      1.2      1.1      NA

-------
                              -19-

                           References
     1.    "Low    Mileage    Catalyst   Evaluation    With    a
Methanol-Fueled Rabbit - Second  Interim  Report,"  Wagner,  R.  and
L. Landman, EPA/OAR/OMS/ECTD/CTAB/84-3,  May 1984.

     2.    "Interim  Report on  Durability  Testing  of Low  Cost
Catalysts  for  Methanol-Fueled   Vehicles,"  Wagner,  R.  and  L.
Landman, EPA/OAR/OMS/ECTD/CTAB-84-4,  August 1984.

     3.    "Evaluation   of   Catalysts    for   Methanol-Fueled
Vehicles Using  a Volkswagen  Rabbit  Test Vehicle,"  Piotrowski,
G., J.  D.  Murrell,  and  K.  Hellman,   Proceedings  from Methanol:
An Alternate  Fuel,  ASME  Joint   Conference  on  the  Introduction
and Development  of  Methanol  as  an  Alternate  Fuel,  pp.  90-95,
Columbus, OH,  June 1986.

     4.    "Aftermarket    Catalyst   Durability    Evaluation,"
Bruetsch, R.,  J. P. Cheng, and K. Hellman,  SAE Paper 861555.

-------
                             A-l
                           APPENDIX A

       Maintenance of Escort/License Plate  Number  0868570
Date
06/24/84**
08/09/84
08/22/84
01/14/85
04/05/85
05/22/85
09/11/85
03/12/86
VIN
Odometer
Reading
3144
3493
3632
6222
9233
10058
12087
12493 .8
1FABP137XDW237349*
Comments
Lube, oil, filter
Tow in (mechanical)
Air conditioning water leak




Lube, oil, filter, add antifreeze
Lube, oil, filter, add antifreeze
Tow in (no reason given)
12,000-mile service
Catalyst removed for shipment
Ann Arbor


to
*    This vehicle was  used to age sample 4,  a 3Pt:Pd(20)
     catalyst,  in oxidation mode.

**   First entry in maintenance records.

-------
                            A-2
                      APPENDIX A  (cont'd)

       Maintenance of Escort/License Plate Number 0868571
Date
06/27/83
02/21/84
05/03/84**
12/26/84

03/11/85
04/30/85
07/11/85
08/19/85
10/15/85
11/08/85
11/26/85
03/12/86
VIN
Odometer
Reading
N/A
N/A
3126
6579

9242
9801
9811
10798
12345
12937 ~
N/A
13306.3
1FABP137XDW237350*
Comments
Accepted for delivery
Tow in (no reason given)
Lube and oil change
Lube, oil, filter, checked brakes,
wipers
Add antifreeze
Replace fuel filter
Replace fuel pump
Fix flat tire
12,000-mile service
Detail and check body fenders,
glass wipers, decals, upholstery
Detail exterior.
Catalyst removed for shipment to
Ann Arbor
*    This  vehicle was used to age sample 1,  a Pd(20)  catalyst,
     in oxidation mode.

**   First entry in maintenance records with mileage  recorded.

-------
                       A-3
                  APPENDIX  A  (cont'd)

  Maintenance of Escort/License Plate Number 0868572
Date
06/20/83
06/27/83
02/16/84
05/24/84
06/12/84
09/24/84
12/17/84
04/11/85
07/27/85
08/06/85
10/11/85
03/12/86 .
VIN
Odometer
Reading
N/A
03
439
2899
3365
4431
6018
9061
11833
11833
13088
14249 . 2
1FABP137XDW237359*
Comments
Predelivery inspection
Accepted for delivery
Inspected
Lube, oil, filter
Inspected
Fix driver ' s door
Lube, oil, filter
Lube, oil, filter, clean air filter
12,000-mile service
Change locks ( key lost)
Replace ash tray
Catalyst removed for shipment to
Ann Arbor
This vehicle was used to age sample 3,  a 3Pt:2Pd(20)
catalyst, in three-way mode.

-------
                            A-4
                      APPENDIX A (cont'd)

       Maintenance of Escort/License  Plate  Number  0868573
Date
12/14/84**
02/02/85
05/09/85
05/24/85
10/01/85
03/12/86
VIN
Odometer
Reading
6762
7956
9645
10089
N/A '
12732.0
1FABP137XDW237378*
Comments
Add antifreeze
Tow in — out of gas
Lube, oil, filter, change oil filter
Tow in — mechanical
12,000-mile service
Catalyst removed for shipment to
Ann Arbor
*    This vehicle was used to age sample 2,  a Pd(20)  catalyst,
     in three-way mode.

**   First entry in maintenance records  with mileage  recorded.

-------
                       A-5
                  APPENDIX A  (cont'd)

  Maintenance of Escort/License Plate Number 0868574
VIN 1FABP137XDW237386*
Date
06/27/83
01/31/84
05/15/84
05/16/84
05/30/84
06/06/84
12/10/84
05/04/85
09/20/85
03/12/86
Odometer
Reading
4
73
3073
3079
9344(?)
N/A
6143
9221
12009
13247.9
Comments
Accepted for delivery
Inspected
Inspected
Lube, oil, filter
4,000-mile service, lube, oil,
filter remove front wheels
Vehicle in accident, but not damaged
Lube, oil, filter, add transmission
fluid, antifreeze
Lube, oil, filter, add antifreeze,
clean air filter
12,000-mile service
Catalyst removed for shipment to
Ann Arbor
This vehicle was used to age sample 6,  a Pd(20) catalyst,
in oxidation mode.

-------
                       A-6
                  APPENDIX A (cont'd)

  Maintenance of Escort/License Plate Number 0868575
Date
06/27/83
04/03/84
04/18/84
05/22/84
06/07/84

07/03/84
02/15/85

07/18/85
08/26/85
08/26/85
09/20/85
03/12/86
VIN
Odometer
Reading
3
N/A
1330
1968
N/A

2545
5823

9331
10171
10171
10172
11809 . 4
1FABP1370DW237405*
Comments
Accepted for delivery
Vehicle misfueled with gasoline;
clean, drain, and flush gasoline
from tank
Fix arm rest
Inspect
Accident — fender, hood, frame
damaged
Lube, oil, filter
Lube, oil, filter, clean air filter,
adjust brakes
Lube, oil, filter
Needs fuel pump
Replace fuel filter
Replace electric fuel pump
Catalyst removed for shipment to
Ann Arbor
This vehicle was used to age sample 5, a 3Pt:2Pd(20)
catalyst, in oxidation mode.

-------
                                      B-l

                                  APPENDIX  B

                    Toyota Cressida  Baseline  (No  Catalyst)
  Date
(ODO KM)

8/8/86
(5314.7)

8/12/86



(5376.3)

10/3/86



(5832.7)

10/8/86



(5905.6)

10/23/86



(6273.4)

10/28/86



(6368.5)

11/7/86



(6800.3)

11/13/86



(6862.9)
 Test

864992
 Bag 1
 Bag 2
 Bag 3
Average

864994
 Bag 1
 Bag 2
 Bag 3
Average

865003
 Bag 1
 Bag 2
 Bag 3
Average

865005
 Bag 1
 Bag 2
 Bag 3
Average

870173
 Bag 1
 Bag 2
 Bag 3
Average

870175
 Bag 1
 Bag 2
 Bag 3
Average

870529
 Bag 1
 Bag 2
 Bag 3
Average

870531
 Bag 1
 Bag 2
 Bag 3
Average
FTP Results
Odometer
(km)
5314.7




5376.3




5832.7




5905.6




6273.4




6368.5




6800.3




6862 .9




HC
(g/mi)

2.00
1.01
0.85
1.17

2.33
1.09
.96
1.31

2.42
1.06
.97
1.31

. 2.38
1.08
.99
1.32

2.56
1.33
1.20
1.54

2.84
1.42
1.23
1.66

3.31
2.49
1.82
2.46

3.49
2.69
1.81
2.61
CO
(g/mi)

17.7
15.4
13.0
15.2

20.0
17.2
14.8
17.2

14.0
' 10.4
10.1
11.0

14.5
11.3
10.2
11.7

17.2
13.2
12.2
13.7

18.3
13.6
12.3
14.2

24.8
28.2
22. 1
25.8

26.7
28.8
22.6
26.7
C02
(g/mi)

419
351
345
363

432
351
343
366

415
. 340
341
356

418
344
342
358

426
349
346 .
364

421
346
342
360

419
347
342
360

416
342
336
355
NOx
(g/mi)

2.59
1.23
1.98
1.72

2.66
1.27
1.94
1.74

2.74
1.41
2.16
1.89

2.84
1.37
2.11
1.88

2.73
1.44
2.11
1.89

2.71
1.43
2.09
1.87

2.42
1.20
1.86
1.63

2.38
1.09
1.84
1.56
HCHO
(g/mi)

395.7
321.2
261.4
312.4

392.8
374.0
200.9
324.5

435.9
288.1
241.3
305.7

467.5
273.0
246.8
303.9

437.4
315.2
500.6
391. 5

344.0
362.1
235.3
323.0

338.6
436.7
431.9
415.3

504.9
360.1
338.8
393.6
MPG




10.5




10.4




10.9




10.8




10.5




10.6




10.1




10.2

-------
 Date


11/14/86



(6924.5)

08/18/87



(7137.0)

08/19/87



(7200.7)

08/20/87



(7211.7)

09/10/87



(7415.9)

09/11/87
09/22/87



(7569.7)

09/23/87



(7592.0)
           Test
870533
 Bag 1
 Bag 2
 Bag 3
Average

871328
 Bag 1
 Bag 2
 Bag 3
Average

871330
 Bag 1
 Bag 2
 Bag 3
Average

871332
 Bag 1
 Bag 2
 Bag 3
Average

871337
 Bag 1
 Bag 2
 Bag 3
Average

871338
 Bag 1
 Bag 2
 Bag 3
Average

871342
 Bag 1
 Bag 2
 Bag 3
Average

871343
 Bag 1
 Bag 2
 Bag 3
-.verage
                                    B-2

                              APPENDIX B (cont'd)

                    Toyota Cressida Baseline  (No Catalyst)
FTP
Odometer
(km) (g
6924.5
3
2
1
2
2
0
1
1
2
1
0
1
2
1
0
1
2
1
0
1
2
0
0
1
2
1
0
1
2
1
0
1
Test
HC
/mi)

.45
.59
.77
.52
.31
.66
.08
.12
.34
.15
.97
.35
.25
.08
.94
.28
.37
.11
.93
. 31
.24
.1
.92
.29
. 17
.13
.94
.29
.24
.15
.95
.32
Results
CO
(g/mi) (

26
28
22
26
7
7
6
7
9
7
6
7
10
7
6
7
10
6
r^
7
10
7
6
7
10
7
5
7
10
7
6
8

.2
.6
.0
.3
.69
.25
.33
.69
.99
.31
.75
.71
.15
.33
.43
.66
.79
.97
.24
.56
. 6
.4
.2
.7
.6
.6
. 6
.9
.3
.9
.6
. 1
CO 2
Lg/mi )

414
341
340
356
404
375
347
373
406
379
348
376
403
373
345
372
398
360'
338
362
397
359
337
361
394
362
331
360
394
362
330
360
NOx
(q/mi)

2
1
1
1
3
3
2
3
3
1
3
2
3
1
2
2
3
1
2
2
3
1
2
2
3
1
2
2
3
1
2
2

.29
.03
.81
.51
.22
.28
.92
. 17
.16
.19
.15
.48
.34
.81
.96
.43
.45
.83
.90
.45
.35
.81
.83
.42
.39
.81
.89
.43
.46
.74
.85
.40
HCHO
(q/mi)

470
379
331
390
590
636
392
560
523
480
380
462
1798
577
399
778
219
307
271
279
235
305
4
209
604
509
445
511
445
448
382
430

.7
.7
.4
.0
.5
.1
.3
.9
.0
.4
.6
.0
.2
. 1
.4
.8
.9
.2
.4
.2
. 6
.3
.4
1
.0
.2
. 6
. 5
.5
.4
.2
.3
                                                               MPG
10.2
10.6
10.5
10.6
10.9
                                                                          10.9
10.9
10.9

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 Date

08/08/86
08/12/86

10/03/86
10/08/86

10/23/86
10/28/86

11/7/86
11/13/86
11/14/86

08/18/87
08/19/87
08/20/87
                              B-3

                        APPENDIX B  (cont'd)

               Toyota Cressida Baseline (No Catalyst)
Highway Test Results
Test No.
864993
864995
865004
870164
870174
870176
870530
870532
870534
871329
871331
871333
HC
(q/mi)
0.31
0 .37
•0 .47
0 .51
0.61
0. 60
0.88
0.80
0 .91
0 .62
0.61
0 . 59
CO
(q/mi)
14.1
15.7
10.4
11.1
12.9
12.8
22.5
22.5
21.7
5.5
5.9
5.8
CO 2
(q/mi)
318
317
315
316
321
318
322
324
317
292
305
298
NOX
(q/mi)
1.24
1.23
1.54
1.51
1.61
1.54
1.36
1.42
1.28
2.69
2.89
2.81
MPG
12. 1
12.0
12.4
12.3
12.0
12.1
11.4
11.4
11.6
13.6
13\0
13.3
HCHO
(mq/mi)
191.6
181.8
181.8
182.3
203.1
210 .0
251.0
285.2
270.8
52.7
172. 7
N/A

-------
                              C-l

                           APPENDIX C

                 Effect of Baseline Changes On
                 Percent Conversion On HWY Test
Catalyst
Formula
Pd(20)

Pd(20)

3Pt:2Pd(20

3Pt:2Pd(20

Pd(20)

3Pt:2Pd(20

Sample
Number
1

6

) 4

) 5

2

) 3

Test and
Aqinq Mode
OX

OX

OX

OX

TWC

TWC

Baseline
Comparison
Before*
After**
Before
After
Before
After
Before
After
Before
After
Before
After
Percent Conversion
HC
70
70
77
85
56
59
59
67
77
77
76
80
CO
92
92
61
79
71
58
52
61
63
62
59
67
NOx
17
17
62
54
49
53
50
50
48
42
70
70
Aid.
-141
-25
25
34
67
66
61
67
80
50
80
83
*    Compared to baseline tests  made before catalyst was tested

**   Compared to- baseline tests  made after  catalyst  was tested.

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                            C-2

                      APPENDIX C (cont'd)

                 Effect of Baseline Changes On
                 Percent  Conversion On FTP  Test
Catalyst Sample
Formula Number
Pd(20) 1

Pd(20) 6

3Pt:2Pd(20) 4

3Pt:2Pd(20) 5

Pd(20) 2

3Pt:2Pd(20) 3

Test and Baseline
Aqinq Mode Comparison
OX Before*
After**
OX Before
After
OX Before
After
OX Before
After
TWC Before
After
TWC Before
After
Percent Conversion
HC
94
96
97
98
89
92
90
92
97
98
97
98
CO
52
72
59
76
66
53
48
56
58
76
74
78
NOx
75
72
78
74
70
75
73
74
84
81
82
83
Aid.
99
99
98
98
98
98
99
99
99
99
100
100
*    Compared  to  baseline  tests  made  before  catalyst  was  tested

**   Compared  to  baseline  tests  made  after catalyst was tested.

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