United States
                    Environmental Protection
                    Agency
Air and Energy Engineering
Research Laboratory
Research Triangle Park NC 27711
                    Research and Development
EPA/600/S7-86/014  May 1986
£EPA         Project  Summary
                    Environmental  Assessment
                    of  a  Reciprocating  Engine
                    Retrofitted  with  Selective
                    Catalytic  Reduction
                    C. Castaldini and L. R. Waterland
                      This report describes emission results
                    obtained from field testing of a gas-fired
                    lean-burn reciprocating internal combus-
                    tion engine retrofitted with a selective
                    catalytic reduction (SCR) system for NOX
                    reduction. Two series of tests were per-
                    formed: a comprehensive test program to
                    characterize catalyst inlet and outlet ex-
                    haust gas composition at a catalyst NOX
                    reduction performance target of greater
                    than or equal to 80 percent; and a 15-day
                    exhaust monitoring program to measure
                    the catalyst performance under  typical
                    engine operating conditions.
                      Emission measurements  during  the
                    comprehensive test program included con-
                    tinuous monitoring of flue gas emissions;
                    source assessment  sampling  system
                    (SASS) sampling of the exhaust gas with
                    subsequent laboratory analysis of samples
                    to give solid paniculate emissions, total
                    organics in two boiling point ranges, com-
                    pound category information within these
                    ranges, and specific quantitation of the
                    semivolatile organic priority  pollutants;
                    VOST sampling for volatile organic emis-
                    sions at the catalyst outlet; modified EPA
                    Method 6 sampling systems for NH3 and
                    total cyanides; and exhaust gas grab sam-
                    ples for N2O analysis by gas chromato-
                    graphy. Emission measurements during
                    the 15-day monitoring program were
                    limited to  continuous monitoring of ex-
                    haust gas species.
                      Comprehensive test results indicated
                    that during the 1-day test the NOX reduc-
                    tion performance of  the catalyst was
                    maintained relatively constant at 81 per-
                    cent. NOX emissions at the catalyst inlet
                    ranged from 2,200 to 2,600 ppm, as
measured at 11.2 percent O2 (2,400 ppm
average). At the catalyst outlet, NOX rang-
ed from 330 to 560 ppm, also at about
11.2 percent O2 (445 ppm average).
  CO emissions averaged 245 ppm at the
catalyst inlet and 225 ppm at the outlet.
Hydrocarbon emission  data were not
available for the  comprehensive tests;
however, emission results obtained during
the extended emission testing indicated
emissions in the range of about 1,500 to
1,800 ppm at both the inlet and outlet.
Total organic (C6 + ) emissions were ap-
parently reduced across the catalyst from
4.9 to 1.5 mg/dscm (20 to 6.2 mg/bhp-
hr). Emissions of two polynuclear aromatic
hydrocarbon (PAH) species, naphthalene
and phenanthrene, and a nftrophenol were
quantitated. Again, catalyst inlet levels
were higher than outlet levels. Outlet PAH
emissions were at or below 0.4 /ig/dscm
(about 1.6 pg/bhp-hr).
  During the extended 15-day perform-
ance test, the NOX reduction performance
was also maintained relatively constant at
about 80 percent. Only occasionally and
briefly did NOX reduction fall below 80
percent. These brief low catalyst perform-
ance periods were attributed to engine
load surges and an occasional malfunction
in the NH3 injection flowrate.

  This Project Summary was developed
by EPA's Air and Energy Engineering Re-
search Laboratory, Research Triangle Park,
NC, to announce key findings of the re-
search project that is fully documented in
two separate volumes of the same title
(see Project Report ordering information
at back).

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Introduction
  In California, the South Coast Air Quali-
ty Management District (SCAQMD) con-
tinues to be in nonattainment of both
federal and state NO2 standards. Station-
ary reciprocating internal combustion en-
gines (ICEs) are estimated to contribute
about 14 percent of the NOX (about 59
Mg/day (65 tons/day)) from all stationary
sources  and 5.1  percent  of total NOX
emissions in  the  basin.  In  1979,  the
California Air  Resources Board  (CARS)
proposed a control strategy for ICEs that
called for retrofit of these sources with
nonselective and selective  gas treatment
catalysts (NSCR and SCR, respectively).
The proposed  SCAQMD rule 1110 called
for demonstration  of  90  percent NOX
reduction or an emissions limit of 0.28
u.g/J  (0.75  g/bhp-hr)  of  heat  output.
Following this proposed rule, there  has
been a sustained R&D effort to demon-
strate  the  capability  of  commercially
available NSCR and SCR  catalysts  and
identify problems in their application.  In
September 1984, a  modified version of
this rule was adopted by SCAQMD calling
for 80 percent NOX reduction demonstra-
tion with subsequent 70 percent reduction
from existing lean-burn engines.  The re-
trofit schedule calls for 80 percent of all
existing lean-burn engines  with capacity
greater than 500 hp in the South Coast Air
Basin to be  controlled  by December 31,
1987. The remaining lean-burn engines (all
above  50 hp)  are  to  be  controlled  by
December 31,  1994.
  This report describes the results of com-
prehensive emission tests and 15-day ex-
tended monitoring tests of a lean-burn
reciprocating engine retrofitted with an
SCR system. Emissions were measured at
both the inlet and outlet of the catalyst to
quantitate both NOX  reduction  perfor-
mance and the impact of the catalyst on
other  pollutants.
  The tests were performed on an Inger-
soll-Rand 412 KVS (2,000-hp) four-stroke,
turbocharged  gas  compressor  engine
owned and operated by Southern Califor-
nia Gas Company (SoCal).  In April 1984,
the engine was retrofitted with an Engle-
hard SCR catalyst system. A similar sys-
tem was previously tested on a slipstream
of the engine and found capable of 90 per-
cent NOX reduction. The catalyst, based
on a proprietary metal oxide formulation,
has an upper temperature limit of 427 °C
(800 °F). The slipstream tests by SoCal
had shown that 90 percent NOX reduction
was achieved using an NH3/NO injection
rate of 1.0 (molar ratio) and an exhaust
temperature of about 400°C (750°F).
Summary and Conclusions

Engine  Operation
  The test program called for the evalua-
tion of NOX reduction performance of the
catalyst and its effect on organic and in-
organic gaseous pollutants during 1 day
of comprehensive tests with the engine
NH3  injection rate adjusted  for NOX re-
duction of greater than 80 percent at con-
stant power output. In addition, the test
program  called  for a continuous 15-day
emission monitoring program to evaluate
the NOX control  capability with the engine
operating under typical conditions with
varying load and NH3 injection rate.
  Table 1 summarizes engine  operating
characteristics during the comprehensive
tests. Engine load was maintained relative-
ly constant, at about 1,270 kW (1,700 hp),
throughout this portion of the test pro-
gram.  Brake-specific  fuel  consumption
was 9.4 MJ/kWh (6,600 Btu/bhp-hr) bas-
ed on fuel lower heating value. This is at
the low end of representative four-stroke
turbocharged engines. The NH3 injection
rate ranged from about 4.4 to 4.9 l/s (565
to 620 scfh),  representing  an NH3/NO
    molar ratio of about  1.0. The NH3 injec-
    tion rate was controlled by a feedback
    system which monitored NOX at the en-
    gine outlet and  set NH3 injection rate to
    maintain a target NOX reduction of  80
    percent.
      Note that, prior to the test period, pro-
    blems were experienced with  the NH3
    control  system,  specifically  the NOX
    analyzer and the NH3 control valve.

    Emission Measurements and
    Results  — Comprehensive Tests
      The sampling and analysis procedures
    used in this test conformed to a modified
    EPA  Level 1 protocol.  The  exhaust gas
    measurements included the following at
    both the catalyst inlet  and outlet:
      •  Continuous monitoring for O2, C02,
         CO, NO/NOX, NH3, and TUHC.
      •  SASS sampling.
      •  VOST sampling for volatile organics.
      •  Modified EPA Method 6 train sampl-
         ing for NH3 and total cyanide.
      •  Gas   grab   sample    for  N2O
         determination.
    The analysis protocol included:
      • Analyzing  SASS train  samples  for
Table 1.    Engine Operation — Comprehensive Tests
            Parameter                         Range
                          Average
Ambient

Dry bulb temperature, °C (°F)
Wet bulb temperature, °C (°F>
Relative humidity, percent
Barometric pressure, kPa (in. fig)

Engine Operation

Engine load, kWt ibhpf
Fuel flow, m3/h (scfh)
Heat input, MW (mi/lion Btu/hrf>
Specific fuel consumption, kJ/kWh
  (Btu/bhp-hr^
Air manifold pressure, kPa (psig)
Air manifold temperature, °C (°F)
Engine speed, rpm
Exhaust manifold temperature, °C (°F)

Catalyst/NH3 System

Catalyst inlet temperature, °C (°F)
Catalyst outlet temperature, °C (°F)
NH3 flowrate, l/s (scfh)

Gas Compressor

Suction pressure, MPa (psig)
Interstage pressure, MPa (psig)
Discharge pressure, MPa (psig)
Suction temperature, °C (°F)
Interstage temperature, °C (°F)
Discharge temperature, °C (°F)
22 to 33 (72 to 92)
19 to 21 (67 to 72)
45 to 55
25 to 28 (3.6 to 4.0)
68 to 70 (154 to 158)
320 to 333
380 to 382 (716 to 720)
390 to 400 (740 to 750)
344 to 382 (652 to 720)
4.44 to 4.88 (565 to 620)
26 to 35 (78 to 95)
88 to 93 (180 to 200)
107 to  118 (225 to 245)
29 (84)
20 (68)
50
96.2 (28.5)
1270 (1700)
327 (11,550)
3.29 (11.2)
9390 (6610)

26.5 (3.85)
69 (156)
325
380 (718)
396 (745)
362 (683)
4.64 (590)
4.02 (583)
7.86 (1,140)
18.87 (2,898)
29 (85)
91 (195)
113 (235)
aEngine load obtained from engine performance curves.
bHeat input based on low heating value (LHV) of natural gas. Specific fuel
 consumption based on LHV of fuel.

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     total organic content in two boiling
     point ranges: 100 to 300 °C by total
     chromatographable  organics (ICO)
     analysis, and greater than 300 °C by
     gravimetry (GRAV).
  •  Analyzing the SASS train  sorbent
     module extract for  58  semivolatile
     organic species including many of the
     PAH compounds.
  •  Performing infrared (IR) spectrometry
     analysis of organic sample extracts.
  •  Analyzing VOST traps for  34 volatile
     organic priority pollutant  species.
  Table  2  summarizes  emissions mea-
sured at the engine muffler outlet (catalyst
inlet) and the catalyst outlet. Continuous
monitored emissions  (O2,   C02, CO,
NO/NOX, and TUHC) were measured up-
stream of the  NH3 injection,  located
upstream at the engine muffler. Emissions
are presented in milligrams per dry stan-
dard cubic meter, nanograms per Joule
heat  input,  and milligrams  per  brake
horsepower-hour shaft output.
  As shown  in Table 2,  NOX  emissions
were reduced 81 percent on the average,
from  2,760 to 513 ng/J (19.2 to 3.57
g/bhp-hr). Actually,  NOX  reductions did
not vary significantly from this average
throughout the test, indicating  a relatively
constant NOX reduction  performance of
the catalytic  system.
  NH3 emissions measured  at the cata-
lyst  outlet with an  extractive sampling
system averaged 39 ng/J  (0.27 g/bhp-hr),
corresponding to a volumetric gas concen-
tration of 93  ppm. NH3  emissions, also
measured at this location  by a continuous
monitoring system, confirmed these  re-
sults. Total cyanide increased significantly
across the catalyst to a concentration of
2.4 mg/dscm at the catalyst outlet. Both
TCO and GRAV organics were apparently
reduced  by the catalyst by about 46 and
82 percent, respectively. This performance
coincides with relatively low CO levels that
were also measured at the catalyst outlet.
Solid paniculate emissions were not de-
tectable within the accuracy of the analy-
tical procedure.
  Table 3 summarizes the emissions of
volatile and  semivolatile organic com-
pounds detected by GC/MS analyses of
VOST traps and SASS sorbent extract
samples. Volatile organics were measured
only at the catalyst outlet.  These data
show benzene and toluene as the principal
compounds with concentrations of about
900 and 250 (jg/dscm, respectively, at the
catalyst outlet. Other volatiles detected
were xylenes, chlorobenzenes,  and ethyl-
benzenes with concentrations below 100
ug/dscm. Naphthalene and 2-nitrophenol
were the  major  semivolatile  organics
detected at the catalyst inlet. Their con-
centrations of 8.4  and  5.3  ug/dscm,
respectively, were reduced at the outlet to
undetectable levels (^0.4 ug/dscm).

Emission Measurements and
Results  —  15-Day Monitoring
  The sampling and analysis protocol for
this portion of the test program consisted
of continuous monitoring of inlet and out-
let exhaust gas for 02, C02, CO, NO/NOX,
NH3/ and TUHC with certification of NOX
analyzer readings  using  EPA Method 7.
Since both engine  power output and NH3
injection rate were not restricted  to spe-
cified ranges, the  data obtained  can  be
 considered reflective of typical operating
 practice. Figures 1 through 6 summarize
 emission results. Each data point in these
 figures represents an hourly average. The
 data indicate  relatively  steady engine
 operation with exhaust O2 levels at about
 11 percent and CO2 at about 5.5 percent.
 NOX emissions ranged  between  1,200
 and 1,600 ppm corrected to 15 percent
 O2 at the inlet and about 100 to 400 ppm
 at 15  percent 02 at the catalyst outlet.
 NOX reduction  efficiency translates to
 nearly constant 80 percent as shown in
 Figure 3. The two data points indicating
 reduced or no NOX reduction were gen-
 erally  caused by an occasional loss of
 NH3 flow or a surge in engine load. These
 Table 2.    Summary of Exhaust Gas Emissions
                              Catalyst inlet3
                  Catalyst outlet3
    Specie             mg/dscm    ng/J    mg/bhp-hr  mg/dscm     ng/J    mg/bhp-hr
NOX (as NO2)
CO
NH3b
Total cyanide (as C/W
N2O°
Total chromatographable
organics (C7 to C16)
Total GRA V organics
(C16+l
4,630
287

0.007
180

1.7

3.2
2,760
171

0.004
108

1.0

1.9
19,200
1,190

0.03
750

7.0

13
860
265
65
2.4
79

0.9

0.6
513
158
39
1.4
47

0.54

0.34
3,570
1,100
270
10
327

3.7

2.4
aAverage exhaust gas O2 and C02 were 11.2 and 5.5 percent, respectively, at both
 catalyst inlet and outlet.
bNH3 emissions at the engine outlet were not measured by wet chemical analysis.
°N2O emissions were measured after the comprehensive test period.  Catalyst inlet and outlet
 NOX during these tests were similar to levels measured during the comprehensive tests.
Table 3.    Volatile and Semivolatile Organic Emissions
      Compound                       Catalyst Inlet
                                        fag/dscm]
                   Catalyst Outlet
                     (ng/dscm)
Volatile organics:3

    Benzene
    Chlorobenzene
    Chloroethane
    1,1,dich/oroethane
    Ethylbenzene
    Tetrachloroethane
    Toluene
    Acetone
    Total xylenes

Semivolatile organics:

    Naphthalene
    Phenanthrene
    2-Nitrophenol
    Di-n-butyl phthalate0
    Bis(2-ethylhexyl)phthalatec
NAb
8.4
0.4
5.3
3.1
1.9
                       915
                        61
                        1.8
                        1.5
                        20
                        2.4
                        247
                        17
                        85
 0.4
<0.4
<0.4
 5.5
 1.0
a Volatile organic emissions measured only at the catalyst outlet. Values
 presented are blank corrected average of two measurements.
bNA  = Not available. No measurements for volatile organics performed
 at the catalyst inlet.
0Suspected contaminants, commonly found in laboratory blanks.

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         60-
         40-
         20-
               O

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                                                              10
            024         6         8
                                            Test Day

Figure 3.     Catalyst NO* reduction efficiency for the extended monitoring period.
                                                                        12
                                                                                  14
        500 -i
        400-
        300-
     Q.
    10
    I
    i
    ;:  200-
    o
    a  100-
                  o
Figure 4.     Catalyst outlet NH3 emissions for the extended continuous monitoring period.

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Figure 6.    Exhaust hydrocarbon levels for the extended continuous monitoring period.



                                         6
                                                                          U. S. GOVERNMENT PRINTING OFFICE:! 986/646-116/20845

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    C. CastaldiniandL. Water/and are withAcurex Corp., Mountain View. CA 94039.
    Joseph A. McSorley is the EPA Project Officer (see below).
    The complete report consists of two volumes, entitled "Environmental Assess-
      ment of a Reciprocating Flame Retrofitted with Selective Catalytic Reduction:"
      "Volume I. Technical Results," (Order No. PB 86-183 779/AS; Cost: $ 11.95)
      "VolumeII. Data Supplement,"(OrderNo. PB86-183 787/AS; Cost: $11.95)
    The above documents will be available only from: (cost subject to change)
            National Technical Information  Service
            5285 Port Royal Road
            Springfield,  VA 22161
            Telephone: 703-487-4650
    The EPA Project Officer can be contacted at:
            Air and Energy Engineering Research Laboratory
            U.S. Environmental Protection Agency
            Research Triangle Park, NC 27711
United States
Environmental Protection
Agency
                   Center for Environmental Research
                   Information
                   Cincinnati OH 45268
Official Business
Penalty for Private Use $300

EPA/600/S7-86/014
                                                                   ...".iN."" 36
                                                                 \
0000329

„
                                            OH  AGENCY
                 CHICAGO

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