EPA/AA/CTAB/88-11
                       Technical Reoort
            Resistively Heated Metal Monolith As A
           Cold Start Assist For  a Methanol Engine
                        Interim Reoort
                               by
                     Gregory K. Piotrowski
                         December 1988
                             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
"~ i 9 1989

 MEMORANDUM


 SUBJECT:    Exemption From Peer and Administrative Review
 FROM:
 TO:
Karl H. Hellnan, Chief   VW
Control Technology and Applications Branch

Charles L. Gray, Jr., Director
Emission Control Technology Division
      The   attached   report  entitled  "Resistively  Heated  Metal
 Monolith  As A Cold Start Assist  For  a  Methanol Engine - Interim
 Report,"   (EPA/AA/CTAB/88-11)  describes  the  evaluation  of this
 technology with  regard  to its ability to provide a  cold start
 assist  for a  light-duty methanol engine.  The primary focus of
 this   work  was  the  determination  of   the  ability  of  this
 technology  to   act   as  a  methanol  dissociator   capable  of
 supplying gaseous H2/CO fuels to  an engine during cold start.

      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 oolicy  outlined  in your
 directive of  April  22, 1982.
    Concurrence
                                    Date:
                Charles L.  Gtfay,/Ji/.,  Dir.,
                                ECTD
 Nonconcurrence:
                                    Date:
                Charles L.  Gray, Jr., Dir., ECTD

 cc:   E.  Burger,  ECTD

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                       Table of Contents

                                                          Page
                                                         Number
I.    Summary	   1
II.   Introduction  	   1
III.  Discussion of Technology  	   2
IV.   Program Design	2
V.    Discussion of Test Results	5
     A.  Evaluation of Dual-Stage Unit	5
     B.  Evaluation of Single-stage Unit 	   7
     C.  Evaluation of Single/Duai-Stage Configuration .  .  10
VI.   Conclusions	13
VII. Future Effort	13
VIII.Acknowledgments 	 13
 IX.  References	14
APPENDIX A - Resistively Heated Metal Monolith Dissociator A-l
             Specifications and Power Requirements
APPENDIX B - Test Engine Specifications	    B-l

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I.    Summary

     A methanol dissociation  system was constructed  to provide
a cold  start  assist  for  a  methanol-fueled  light-duty engine.
The system  consisted  of  a fuel delivery  unit,  fuel  injector,
and   a    palladium-catalyzed   dissociation    element.     The
dissociation  element   substrate  was   resistiveiy  heated  and
constructed primarily from metal foil.

     The  objective of  this  experimentation was  to  start  and
idle a 4-cylinder  engine  on the product gas  from  this methanol
dissociator.

     Three  different  configurations of the  resistiveiy heated
metal  monolith  were  evaluated.   The  first  consisted  of   a
catalyzed,  heated  bed  followed  by a  catalyzed  unheated bed.
The product stream  from this  dual-bed  configuration was liquid,
rather than gaseous,  under the conditions given  in  Section V,
Discussion,  of this  report.   We tested  a  resistiveiy heated,
but  uncatalyzed  single-bed  configuration;  though the product
was vaporized rather  than dissociated  methanol, the test engine
started  and idled without hesitation  with no other fuel source
than  the   single   injector-fed  fuel   vaporizer.    Finally,   a
two-stage  system utilizing the single-bed unit  as  a vaporizer
and the dual-bed unit as  a methanol dissociator was constructed
and evaluated.   Product gas from this  configuration was used to
start  and  idle the  test  engine   in  the  same  manner as  the
single-bed  unit.   The   product  gas   temperature  out  of  the
dissociator  was very low,  approximately   130°F.   This suggests
that  the engine started  on vaporized  methanol,  rather than H2
and CO gases.

II.   Introduction

     Light-duty M100  neat methanol-fueled engines are  difficult
to  start and  run in cold weather  because of  the high boiling
point  of methanol,  methanol's high  heat  of  vaporization  (5.5
percent  of  the  heat  of combustion  compared  to  less  than  1
percent  for gasoline),  and  the increased  fuel flow  needed for
methanol   (about   double   that  of  gasoline).   Gasoline-fueled
engines  start  with less  difficulty  under the same   conditions
partly  because of  the  easily  ignitable light ends of this  fuel
such  as  butanes,   which  are  vaporized   at  relatively  low
temperatures.

      Some   state-of-the-art   methanol   engines   require  the
 addition   of   gasoline   to   the   fuel   to    improve   their
startability.[1]   Other  methanol engines  utilize separate  cold
 start  systems  relying  on gasoline or propane for  cold  start
 assist.[2,3]    Finally,   some  researchers  have  suggested  that
 stratified-charge  combustion will  produce  reliable cold  starts
of  a  neat  methanol-fueled  engine at relatively  low ambient
 conditions.[4]

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                               -2-

     Methanol may  be cataiytically  decomposed  to  hydrogen  and
carbon monoxide gases.   Hydrogens'  higher  flame speed and lower
boiling point may make it an ideal cold start fuel.

     The  coal  of  <:he  project  was  to construct  and  test  a
methanol  dissociation  system  that  could  provide H2  and  CO
gaseous fuels in quantities  that could be used as a cold start
assist  for  a  methanol-fueled  engine.   This dissociator  would
utilize resistively heated metal  foil  technology  to provide the
energy   necessary   co   bring   the   catalyst    to   operating
temperatures quickly.

     Methanol  dissociation  systems  using  resistively  heated
ceramic  technology  have  been  evaluated  by  EPA  to  determine
"their cold  start  assist potential.[5,6]  Reference  6  refers to
a  dissociation  unit  which was  able to cold start  and  idle a
4-cylinder,  1.8-liter  light-duty engine which  had  been  soaked
to   43°F.    We   hoped   to  improve  H2/CO  yield,  dissociator
durability  and  heat transfer  to the methanol  fuel beyond what
was   experienced   in  that  effort  through  the  use  of  the
resistively  heated metal  foil.

III. Discussion of Technology

     The  subject  technology  is  a. metal   foil   which  may  be
washcoated.  catalyzed  and resistively heated.  The  rolled metal
foil is encased in a metal housing; the housing  is  electrically
insulated   from   the  electrified  foil.   Two   metal  contacts
protrude  from the  sides of the  housing.   Electrical contact to
a  direct  current  power source,  a  12-volt automobile battery, is
made to these contacts.

     Two   resistively   heated   monoliths  were  tested  in  this
effort.   The first  was a dual-bed configuration consisting of
an unheated metal monolith  catalyst and a  smaller  resistively
heated  metal   monolith  catalyst.   The  second   unit  was  an
uncatalyzed, resistively heated monolith similar   in size to the
smaller   heated   bed   in  the  dual-bed   configuration.   The
exteriors  of both housings were  insulated  with ceramic fiber
insulation to  improve  heat  retention.   Details are provided in
Appendix A.

     The  resistively heated monoliths  were provided by Camet, a
manufacturer and sales  agent  for W. R. Grace Company.  Details
relating   to catalyzing  the   foil,  packaging,   and   resistive
heating  of  the  catalysts  are considered proprietary  to Camet
and Grace.

IV.  Program Design

     Three different configurations,  a single-bed, a  dual-bed,
and a combination of these two  systems were evaluated  for their
ability to provide a cold start assist.  The dual-bed  catalyzed

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                              -3-

system  had  the  potential  to  act  as  a  methanoi  dissociator,
using resistive heating to first vaporize the  feed methanoi and
then  to  supply   the   necessary  energy  for  the  endothermic
dissociation  reaction.    The  single-bed,  uncatalyzed  monolith
was evaluated  to  determine the  ability of  the heated substrate
to transfer energy to  the feed  methanoi  in the  absence  of the
larger  catalyzed-but-unheated monolith  located downstream.  The
combination system used the single-bed  unit as a vaporizer and
the dual-bed as the dissociation element.

     Figure 1  contains a diagram  of the system  we constructed
to   support   the   various   configurations   mentioned    above.
Methanoi is pumped to  the catalyst or vaporizer  from a 2-gallon
plastic  fuel  tank by  an electric  roller-type fuel  pump.  The
fuel  passes   through   stainless  steel  tubing   fitted  with   a
flowmeter.    The   flowmeter  is  connected  to  an  electrically
actuated clock.   Given the proper  electrical  signal, the  clock
and  flowmeter  operate simultaneously  to  determine  fuel flow
over the desired time period.

     A  fuel   injector  was   installed in  the  catalyst  housing
approximately   3    inches   from  the   face   of.   the  smaller,
resistively  heated metal monolith.   When  testing the dual-bed
unit  alone,  the   methanoi  spray  impacted   on the  resistively
heated  catalyst  first before  passing through  to  the larger,
catalyzed  but  unheated  monolith.    To  prevent  metering fuel
which did not pass through the  injector, a recycle was provided
around  the  injector and the pump.

     Fuel  flow to the dissociator  was controlled  by changing
the  pulse  width  of  the  non-continuous  flow  injector.   Line
alternating   current   (AC)   operated  a   Wavetek   Model  193
wave/frequency generator.  The  equipment was used to generate
pulsed  square  wave signals of  various widths  that controlled
the  quantity  of  fuel  injected.   An AC to  direct current (dc)
device  was  then used to  change  the  pulse to a dc  signal  before
it passed to  the fuel  injector.

     Thermocouples  were  installed  to  measure  liquid  fuel
temperature as well as gas temperatures midbed  in the monolith
and  immediately  after  the dissociator.    N2  gas  was  used   to
replace the air in the dissociator just prior  to heating.   N2
was  added  for two reasons:   1)  to encourage the  dissociation  of
methanoi,  and 2)  to  provide a  safety  factor upon the initial
heating.

     The test procedure  consisted  of supplying the fuel  to the
resistively   heated    elements   at   various   flowrates  and
determining whether a vaporized fuel  was  produced.  Provision
was  made for  sampling the dissociator  gas product  stream and
analyzing   it  with  a  gas   chromatograph  to  determine  its   H2
content,  if a  gaseous  product  was  generated  from a catalyzed
unit.

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                       -4-
                     FIGURE 1
      METHANOL DISSOCIATION SYSTEM
   WAVETEK      AC TO DC                DISSOCIATOR
   	     	    INJECTOR     	
AC  ,        AC          DC  	FUEL
                         •»•        i »        -
                        FUEL
               FLOW METER
                        FUEL
                FUEL PUMP
TO ENGINE
                                  RECYCLE
                        FUEL
                FUEL TANK

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                              -5-

     The production  and analysis of  the  hot product  gas would
be  followed  by  its  introduction  into  a  light-duty  vehicle
engine for cold start testing.

V.   Discussion of Test Results

     A.    Evaluation of Dual-Stage Unit

     Methanol   may   be  dissociated   to   hydrogen  and  carbon
monoxide via the reaction:

     CH3OH(1) 	2H2(g) + C0(g)

     This  reaction  is  endothermic;  assume  that   the  reaction
occurs  at  atmospheric  pressure  and  500°F.[7]   This situation
requires the input of energy to:

     1.    Preheat the methanol at  148°F;

     2.    Vaporize   the  methanol   at   148°F,   l  atmosphere
           pressure;

     3.    Superheat the vapor  to 500°F;  and

     4.    Decompose the vapor  to H2  and  CO gases.

     The   dissociated   product   flowrate  to  start  an  engine
similar  in displacement to our test  engine  has been calculated
[8,9]  as  0.3 to 0.6 grams per  second.  Karpuk  [10]  in a  private
communication  to EPA,   calculated  a power  requirement  of  2,256
watts  necessary to dissociate  2,000 g/hr  of  methanol  at  25°C.
Our  calculations  of this  requirement   shows  it  to be  2,230
watts,  essentially  the  same.   We  hoped  that  the  resistively
heated monolith  would  generate power at  a  rate  in excess  of
these  requirements and  transfer  energy to the fuel  efficiently
to  ensure at least partial dissociation  in the brief timeframe
of  interest.

     The   dual-stage  unit  was  tested with  the  fuel  injector
mounted  in front of the  resistively  heated element.  The  spray
would  then  impact  the  heated element before passing through  to
the  catalyzed,  unheated catalyst.   Some  results and  conditions
of  testing in this  configuration are given in Table 1.

     N2  gas  at 2  psig was  admitted into  the catalyst vessel
for  1-minute  prior to operation  to  assist  the  dissociation
reaction.   The gas flow  was  shut off prior to catalyst  heating
however,  and remained  off during the test.

     The  heating scheme involved preheating the catalyst for  10
seconds  prior  to  fuel  on and  heating for 30  seconds following
fuel on.   We measured current  in  the electrical  leads  to the
catalyst  at approximately 300  amps  at the beginning of heating;
current  dropped  in straight  line  fashion over  the 30-second
heating  period to  approximately 220  amps  at the  conclusion  of
heating.   We charged the battery power source to 12  volts  prior
to. each  test.

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                             -6-

                            Table  1

                Dual-Bed Configuration Evaluation
     Variable
    Specification or Result
N2 flowrate
2 psig over catalyst prior to
test, off during test
Battery voltage
11.5-12.5 volts
Voltage across monolith
during heating
9-volts
Current to monolith
290 amps at start of heating,
210-230 amps at finish
Heating scheme
Heat on for 10 seconds prior
to fuel on; heat on for 30
seconds after fuel on
Fuel to injector
Flow rates 35-140 cc over a
period of 30-33 seconds
Gas Temperatures;
Fuel into dissociator (liquid)   70-72°F
Mid-bed gas temperatures
Approximately 300°F at fuel
on; approximately 190°F at 10
seconds after fuel on;
approximately 150°F at end of
heating
Gas out of dissociator
75°F at end of test

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                              -7-

     Fuel flow  to  the injector  was  varied from a  high rate of
140  cc   for  a  30-second period  (approximately 3.7  grams  per
second)   to  35cc over  30 seconds  (approximately 0.9 grams  per
second).    Even  the   lowest  flowrate  tried  here   should  have
provided a  sufficient flow of  fuel  to start  and  idle  the test
engine.   Liquid temperature of the fuel was  70-72°F during this
testing.

     Midbed  gas   temperatures   varied  considerably   over  the
duration of  the test.   Typically,  this  temperature  would rise
to approximately 300°F after  10 seconds  of heating with no fuel
injected.  At  10 seconds after  beginning the  injection of fuel
(20  seconds  into the test) temperatures  had  fallen linearly to
approximately 190°F.   At the end of heating,  or  40  seconds into
the  test,  midbed gas temperatures  had fallen to  150°F.   These
temperatures   were  consistently   noted   regardless   of   fuel
flowrate into the dissociator.

     Gas  temperatures out  of  the  dissociator  remained  almost
constant,  at 70-72°F, during this  testing.   This  temperature
did  not  change when  fuel  flowrate   into  the  dissociator  was
varied.   The dissociator product line  was made of  clear plastic
tubing;   the  product  after  40  seconds  of  heating  remained
liquid.   Not enough gas  was generated  to  enable  bag sampling to
determine if any methanol dissociation to H2/CO had occurred.

     It  is  difficult  to  determine why the desired  reactions did
not  occur and why the dissociator product stream appeared to be
liquid.   Much  more  about  the heat transfer  characteristics of
the  material contained  in  the  housing would  have to  be known
from the manufacturer.   Methanol  vaporized  in  the  resistively
heated   section of  the housing   may  be  condensing  in  the
non-heated monolith.

     It  was  clear  that  the  particular  configuration  was
incapable  in   its   present  form to   efficiently   transfer  the
necessary   energy   in   a   40-second   timeframe  to  dissociate
methanol at  the required flowrate.

     B.    Evaluation of Single-stage  Unit

     The dual-stage  dissociator  did not  produce  a gaseous
product  stream under the conditions given in Table 1.   We next
evaluated a  single-stage configuration to determine if a  single
heated   monolith  would  transfer   heat   to  the   fuel  more
efficiently.

     Some    results   and   conditions    of   testing    in.  this
configuration  are given  in Table 2.

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                             -8-

                            Table 2

              Single-Bed Configuration Evaluation
     Variable
    Specification or Result
   flowrate
Battery voltage
Voltage across monolith
during heating
No N2 gas used


12 volts


9 volts
Current to monolith
Heating scheme
315 amps at start of heating,
210-230 amps at finish
Heat on for 10 seconds prior to
fuel on; heat on for 30 seconds
after fuel on
Fuel to injector
23-27 cc over a period of 30-32
seconds
Gas Temperatures:
Fuel into dissociator
 70-72°F
Midbed gas temperature
Gas out of dissociator
Approximately 390°F at  fuel on;
approximately 250°F at  10
seconds after fuel on;
approximately 145°F at  end of
heating
 138-145°F at end of test

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                               -9-

     N2  gas  was  not  used during  testing  in  order  to  better
simulate  actual  cold  start conditions.   The  battery used  to
electrify the  substrate was fully  charged to  12  volts;  during
testing,  voltage  drop across  the  substrate  was  measured  at  9
volts.   At  the  start  of  heating  a  current  of  315  amps was
measured  in the  heating circuit; 40  seconds into the test,  at
finish,  the  current had dropped linearly  to 210-230 amps.   The
same  heating  scheme that  was  used  in the  dual-bed  evaluation
was   also  used   here  (heat   10  seconds,  fuel  on,  heat  30
seconds).  Fuel  flow was  measured  at 23-27  cc  over  a period of
30 seconds,  or 0.66 grams per second.

     Midbed gas  temperature rose to  390°F  after  10 seconds of
heating.  This was  a considerable  improvement from  the  300°F
temperature noted  during  the  dual-bed evaluation.    Near the end
of each test,  midbed  gas  temperatures dropped to 145°F.  This
temperature  is  consistent with  a   flow  of  vaporized but not
superheated methanol vapor.

     Gas  temperature  out   of  the   substrate was  approximately
145°F   after   30   seconds  of  heating.   This  temperature  is
consistent with  a  flow of vaporized methanol.  This was  again
an  improvement over  the  72°F~ temperature  experienced with the
dual-stage unit.

     We  then  piped the product gas from  the resistively heated
monolith to  a  4-cylinder  light-duty engine  and attempted a cold
start  at 70°F.  A complete description of  the test  engine is
given  in Appendix  B.

     Approximately  4   feet of  plastic   tubing   connected the
vaporizer to the EGR port.  A  valve to allow emissions sampling
and  a  flame  arrestor  were also located  in this  line.    These
restrictions,  however, did not  combine to  reduce  fuel flow to
the   point  that   engine   performance   at   idle  was  noticeably
affected.  Although the fuel  entry  passageway to the  combustion
chambers was  not  standard (via  EGR  chamber  to  cylinders), it
proved sufficient  to  allow a  start and  idle  at  the  conditions
in Table 2.

      The engine  started   and  idled without hesitation.    Crank
time   to  start   was   1-1/2   seconds.    This   experiment   was
successfully   repeated  several  times.   Cranking  was  attempted
after  30 seconds  of  heating  time  had  elapsed  (the  final 20
seconds   of  that  period   involved  sending  fuel  to  the  heated
monolith).   The  four  engine fuel  injectors were  electronically
disabled during  this testing;  fuel entered  the engine only from
the single-injector/heater system.

      We tried repeating  this cold  start  experiment  with  this
same   hardware    but   without  heating   the   monolith.    Gas
temperature  out  of the  catalyst  housing  did  not  exceed  72°F
under  the conditions  in Table 2, and  the engine did  not start.
Disassembling   the  catalyst  housing  after  this  test,  we
discovered it  filled with  liquid methanol.

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                              -10-

     The  resistive  heating  had  the  effect  of vaporizing  the
incoming  methanol  stream.   The  vaporized methanol,  under  the
conditions  in  Table  2,  was  sufficient  to start  and  idle  the
test  engine in  spite  of  the  less  than optimum  fuel  intake
system.

     C.    Evaluation of Single/Dual-Stage Configuration

     The  dual-bed  configuration  was not successful under  the
conditions  in Table 1,  probably because  the  methanol vaporized
in  the first,  heated stage,  had condensed on  the  metal foil in
the  second,  unheated stage.  The  time  period  of  interest here
was  40  seconds;  during that time current dropped significantly,
from  290  to 220  amps, due to discharge of the battery.  It may
have  been difficult  to transfer  sufficient  energy  effectively
from  the  heated to  the unheated monolith  in  the  timeframe of
interest   to  permit   the  desired  reaction  to  occur.   The
single-bed  configuration heated  and vaporized the methanol  feed
stream.   The energy  transferred here  in the  time of  interest
was  sufficient  to  srart  and  idle  the  test  engine  on  methanol
fuel   alone.   Midbed   gas  temperature  recorded  with   this
configuration  10 seconds  after the  introduction  of  methanol,
250°F,  was still too low to permit  methanol  dissociation  with
the  noble metal catalyst we used in the dual-bed configuration.

      We next combined  the  single and dual-bed monoliths in an
attempt  to   increase  the   product  gas   temperature.   The
single-bed  monolith was placed  first in this new configuration;
the  injector sprayed  on  this heated monolith.  The  single-bed,
non-catalyzed unit  would therefore act as a  vaporizer  ahead of
the  dual-stage unit.   The  catalyzed dual-stage unit would  then
be  the dissociator, receiving a vaporized product  gas  from the
single-bed unit.

      Two   uncertainties  still   remained  with  this  approach,
however.   Though we  measured midbed gas temperature,  we  were
unable  to  measure  the  metal   substrate   temperature   during
resistive  heating.    This   measurement   would  give   a   good
indication  of  the  actual  boundary  layer   temperature   during
heating.   We were  also unable  to generate  enough product gas
during the  timeframe  of  interest  to  permit sampling  by gas
chromatograph,  given our  current  bag sampling methods.

      Details of  the conditions  of this  testing   are  given in
Table 3.

      We   constructed   two    separate    circuits   for    this
vaporizer/dissociator  configuration;   each   resistively   heated
element  was powered  by a  12-volt battery.   We  preheated the
vaporizer and dissociator  simultaneously for  10  seconds prior
to   fuel  on.   The  fuel  was  then  allowed to  flow  through the
heated system for  an additional  10 seconds  (total heating  time

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                              -11-

                            Table 3

           Sinqle/Dual-Staae Configuration Evaluation
     Variable
    Specification or Result
No flowrate
No N2 gas used
Battery voltage
12 volts
Voltage across monoliths
9 volts
Current to monoliths
300 amps at start of heating,
230 amps at finish
Heating scheme
Heat for 10 seconds prior to
fuel on; heat for 30 seconds
after fuel on
Fuel to injector
25 cc over a period of 30
seconds
Key on
Key on after 20 seconds of
heating  (fuel on for  10 seconds
prior to start)
Gas Temperatures:
Fuel  into single-bed
unit  (liguid)
 70-72°F
Midbed gas temperature
(dual-stage unit)
Approximately 400°F at  fuel on
136°F  at  10  seconds after fuel
on
 Gas  out  of  dissociator
 130°F  at  end of test

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                              -12-

20 seconds).   The  product gas  was  piped to  the  engine through
the EGR port  as  mentioned in  the discussion of  the single-bed
unit evaluation.   A cold start  was then attempted;  the engine
started  immediately,  without  hesitation.   Repetition  of  this
test without  resistive  heating  gave  the same result  as in the
single-bed  evaluation;   the   engine   refused  to  start  after
repeated cranking.

     At a voltage  drop  across  a heated substrate at 9 volts and
a  current  of  300  amps,  power  at  2700 watts  is  generated.
Assuming  that  heat  transfer   from  the heated substrate to the
methanol  fuel   occurred  at   maximum   efficiency,   the  power
requirement of roughly  2500  watts for dissociation would appear
to have  been exceeded  with  the single-dual  bed  configuration.
Gas  temperatures   out   of   the  dissociation  reactor  suggest
however,   that  dissociation   did   not   occur   (product   gas
temperatures  in  excess   of 400°F were  not recorded).[7]  At 230
amps,   power   output   falls    to   approximately   2000  watts.
Obviously,  dissociation becomes much  more  difficult at a lower
power  output  assuming   heat  transfer  to the  methanol  is  not
improved.

     Heat   transfer  to  the   surroundings   and   the   catalyzed,
nonresistively  heated  element in  the  dissociator  may account
for  significant   heat   losses   in  the  30-second  timeframe  of
interest.   The engine started  and idled without hesitation when
the  monoliths  were  resistively heated,  however;  the cold start
assist may  have  been provided  by vaporized methanol.

     Several ways  to assist  the dissociation reaction with this
technology  are  now mentioned.    First,  a platinum/palladium
mixture  may not  be an  optimum catalyst with which to  coat the
resistively heated  substrate.   An  optimized  low  temperature
dissociation  catalyst  could.be  on technique  to  minimize the
reactor  power requirement.  Second,  the metal foil bed may not
be of  sufficient size to provide the  amount of energy  required
over  the  short  time   period  of  interest.   A  larger heated
monolith may  provide  additional   reaction  surface  area.   The
rectangular brick  may not   be the   optimum  shape  for  this
application;  the  fuel   injector  may  distribute  the  fuel  very
unevenly across   the  surface  area,   causing puddling  and hot
spots  to occur.   A cylindrically  shaped unit  may  be  a better
geometry.   Though  we  insulated the  vaporizer  and  dissociator
housings with ceramic  fiber   insulation, a  considerable amount
of heat  transfer  (therefore  energy loss) may be occurring with
the   surrounding  air.    This  condition   was   also   probably
aggravated  by the location of  the dissociator approximately  3
feet from the  engine EGR port.  Finally, a very  large  amount of
energy may have to  have been  transferred from the hot  vapor to
the  catalyzed,  unheated monolith in  the dual-stage  dissociator
to  bring  this  bed  to  catalytically  active  temperature.   An
improvement on the dual-bed configuration may be the use of two
single-bed  resistively heated  monoliths.   The  first  would be
used to vaporize the incoming methanol feed  stream.   The second
bed, located downstream,  would be  catalyzed and would  serve as
a resistively heated dissociator support.

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                              -13-

VII  Future Effort

     Our   immediate   plans   for   future   efforts  with   this
technology  in   the   methanol  dissociator   cold  start  assist
application concern:

     1.    Additional energy  provided  to  the fuel ahead  of the
dissociation reaction; and

     2.    The  use  of a  more appropriate methanol dissociation
catalyst.

     We are procuring a Bosch flame  glowplug capable of burning
fuel at  a  volumetric rate of 290 cc/minute.  This hardware will
be  mounted ahead  of the  catalyst  to  superheat  the  vaporized
methanol.

     We  are   evaluating   a  noble  metal/rare  earth  methanol
dissociation  catalyst formulated  by Nissan  Motor Corporation.
This   catalyst  may  provide  a   significant  yield  at   lower
temperatures;  if the  initial  evaluation of  this  catalyst   is
successful,  we  will  try to  have the  resistively heated* metal
monolith substrate coated with this formulation.

     W.  R.  Grace has  agreed to provide  EPA with a  base metal
formulation  for use  as  a  methanol   vehicle   catalyst.   This
catalyst  will   have  been   applied   to  a  resistively  heated
substrate.   We  will  test   this  formulation   as  a  potential
dissociation catalyst when  it is received.

     We  are   also   requesting  Camet   to  supply  EPA  with   a
platinum-catalyzed  single-bed  unit  for  use as a dissociator.
This unit will  eliminate  the  catalyzed,  but unheated bed in the
dual-bed configuration  that may have been  causing the vaporized
methanol to  condense or cool to a  lower, inactive temperature.
This   unit  will   be  tested  together   with   the  single-bed
uncatalyzed vaporizer.

VI11. Acknow 1 edojnent s

     The  catalyst used  in  this  test   program  was  supplied   by
Camet,  located in Hiram,  OH.  Camet is a manufacturer and  sales
agent  for  W.  R.   Grace  and Company.   The   test  engine  was
supplied by the Nissan Motor  Corporation.

     The  authors  appreciates the  efforts  of   James  Martin   of
ECTD who served as the primary technician  and  greatly assisted
in this work.

     In   addition,   the  author   appreciates  the  efforts   of
Jennifer  Criss  and  Marilyn Alff  of the  Control Technology and
Applications    Branch,   ECTD,   whose   cooperation   and   able
assistance  during the preparation  of  this  report,  tables, and
figures was greatly  appreciated.

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                              -14-

VII.  References

     1.    "Development  of  Methanol  Lean  Burn  System,"  SAE
Paper  860247,  Katoh,  K. ,  Y.  Imamura,  and  T.   Inoue,  February
1986.

     2.    "Interim  Report  On  Durability  Testing of  Low Cost
Catalysts  For Methanol-Fueled  Vehicles,"  EPA/AA/CTAB/TA/84-4,
Wagner, R. and L. Landman, August 1984.

     3.    "Using  Methanol Fuels  in Light-Duty  Vehicles,"  SAE
Paper  872071,  Brown,  D.,  F.  Golden,  E.  Gons,  R.  Potter,
November  1987.

     4.    "Unassisted  Cold Starts  to  -29°C  and Steady-State
Tests  of  a  Direct-Injection   Stratified-Charge  (DISC)  Engine
Operated  On  Neat Alcohols," SAE  Paper 872066,  Siewart,  R.  and
E. Groff, November 1987.

     5.    "Evaluation  of   Coloroll  Methanol   Dissociator  For
Cold  Start Assist Application,"  EPA/AA/CTAB/87-08, Piotrowski,
G., December  1987.

     6.    "Resistively  Heated Methanol Dissociator  For Engine
Cold   Start  Assist   -   Interim   Report,"  EPA/AA/CTAB/88-02,
Piotrowski, G., March  1988.

     7.    "Decomposed    Methanol   Workshop    Report,"   U.S.
Department  of  Energy,  Windsor  Ontario  Meeting,   June  9, 1983
(published October 1983).

     8.     "Engine   Cold  Start  with   Dissociated   Methanol,"
Greiner,   L.   and   E.   Likos,   Proceedings   of   the  Third
International  Symposium  on Alcohol  Fuels Technology,  May  29-31,
1979.

     9.    Dissociated  Methanol  Fuel   Requirements  to  Start   A
Four-Cylinder   Engine,   Memo   from  Gregory   K.  Piotrowski,
OAR/OMS/ECTD/CTAB, Ann Arbor, MI, 1986.

     10.   Private   Communication,   Karpuk,  M.  E.,   Technology
Development Associates,  Inc.,  to U.S. EPA,  1987.

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                             A-l
                           APPENDIX A

         RESISTIVELY HEATED METAL MONOLITH DISSOCIATOR
             SPECIFICATIONS AND POWER REQUIREMENTS
Construction
Dual-bed element composed of
two metal monolith catalysts,
a smaller resistively
beatable one and a larger one
with no provisions for
resistive heating
Catalyst material/loadings
Platinum/palladium;
proprietary
Shaue
Rectangular
Overall outer dimensions
(excluding mounting flanges)
10-3/4" X 4-1/4" x 2-3/4"
Length:  flange to flange
14-3/4"
Heated brick dimensions
3" x 4-1/4" x 2-3/4"  (approx)
Unheated brick dimensions
4" x 4-1/4" x 2-3/4"  (approx)
Power supply
 12-volt automotive battery
Current delivered to dissociator  300-230 amps at 10-11 volts
Heatup time  to  600°F
with no gas  flow through
the converter
Less than 20  seconds  from  70°F

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                             B-l


                           APPENDIX B

                   TEST ENGINE SPECIFICATIONS
Manufacturer
Nissan Motor Company, Ltd.
Basic engine designator
CA18E
Displacement
1809 cc
Cylinder arrangement
4-cylinder, in-line
Valvetrain
Single, overhead camshaft
Combustion chamber
Semi-spherical, 2 spark plugs per
cylinder
Bore x stroke
83 mm x 83.6 mm
Compression  ratio
 Compression pressure
 Fuel  control  system
 11.0
 17.0 kg/square cm  (350  rpm,  80°C>
Electronically  controlled  fuel
injection
 EGR
 EGR not used
 Valve clearance
 0.30 mm HOT,  intake  and  exhaust
 Idle speed


 Engine oil
 700  rpm
 Special  formulation  supplied  by
 Nissan for methanol  engine
 operation
 Fuel
 Ml00  neat  methanol
 Engine cranking speed
 240  rpm

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