Emissions of nitrogen oxides NO(x) are a significant problem in the United States. NO(x) are formed in any combustion process, therefore it is not surprising that NO(x) are emitted from the boilers at KSC. Research at UCF has shown (in the laboratory) that injecting H2O2 into hot simulated flue gases can oxidize the NO and NO2 to their acid gas forms, HNO2 and HNO3, respectively. These acid gases are much more water soluble than their counterparts, and theoretically can be removed easily by wet scrubbing. This technology was of interest to NASA, both for their boilers at KSC, and for their combustion sources elsewhere. However, it was necessary to field test the technology and to provide pilot-scale data to aid in design of full-scale facilities. Hence this project was initiated in May of 1996

Cooper, C. David

English

NASA Technical Reports Server

NASA-CR-203?|8
A PILOT-SCALE EVALUATION OF A NEW TECHNOLOGY
TO CONTROL NOx EMISSIONS FROM BOILERS AT KSC:
HYDROGEN PEROXIDE INJECTION INTO BOILER FLUE GASES
FOLLOWED BY WET SCRUBBING OF ACID GASES
Annual Progress Report
Submitted to
National Aeronautics and Space Administration
Kennedy Space Center
by
Dr. C. David Cooper, PE
Professor of Engineering
Principal Investigator and Project Director
Civil & Environmental Engineering Department
University of Central Florida
February 25, 1997
https://ntrs.nasa.gov/search.jsp?R=19970012789 2020-06-16T02:57:00+00:00Z

STATEMENT OF THE PROBLEM
Emissions of nitrogen oxides (NOx) are a significant problem in the United States. NOx are
formed in any combustion process, therefore it is not surprising that NOx are emitted from the
boilers at KSC. Research at UCF has shown (in the laboratory) that injecting H202 into hot
simulated flue gases can oxidize the NO and NO2 to their acid gas forms, HNO2 and HNO3,
respectively. These acid gases are much more water soluble than their counterparts, and theoretically
can be removed easily by wet scrubbing. This technology was of interest to NASA, both for their
boilers at KSC, and for their combustion sources elsewhere. However, it was necessary to field test
the technology and to provide pilot-scale data to aid in design of full-scale facilities. Hence this
project was initiated in May of 1996.
OVERVIEW OF PROGRESS
The project is making good progress, and is on schedule (see Table 1). The main objectives
for the past year were to select a boiler on-site at KSC for the construction and operation of the pilot
plant and for the conduct of the experimental program, to make appropriate contacts between UCF
personnel and KSC personnel, to plan out the experimental methodology and procedures, and to
design/select/purchase all the major equipment needed for the experimental phase. Highlights of
progress made during this first year of the project are as follows:
* A boiler was selected and contact was made with operating and technical personnel at
KSC regarding this project. A good working relationship has been established between UCF and
KSC personnel.
* A significant amount of time was spent in the design of both the experimental plan and of
the pilot scale equipment in order to ensure success of the pilot plant operation.
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* An industrial partner was found who is participating in the project in a very meaningful
way. EKA Nobel, Inc., of Marietta, Georgia, is supplying considerable engineering expertise, and
will supply all the hydrogen peroxide and some equipment to this project free of charge.
DISCUSSION OF WORK PROGRESS
Several major tasks have been accomplished since the start of this project. First, the project
team has made good contacts with NASA and contractor support personnel at KSC, mostly due to
the efforts of Michelle Collins. The team has made several trips to KSC to meet the technical people
who will be involved, and to meet the operating personnel who will be responsible for the boiler
operation during the testing. Michelle's knowledge of the individuals at KSC has proved invaluable
in establishing good contacts for the entire team. In addition, contact was established between Dr.
Cooper and Mr. Joel Tenney of EKA Nobel, a world-wide supplier of hydrogen peroxide (among
other chemicals), in regards to their supplying some of the materials to be used in this project. Mr.
Tenney's response was gratifying in that EKA became enthusiastic about this project and have been
contributing their time and expertise in a most helpful manner.
Much time and effort was expended on the process design of the pilot plant equipment. In
addition to various UCF project team members devoting significant portions of their time, our
industrial partner, EKA Nobel, made substantial contributions of engineering time and expertise to
this phase of the project. The analytical needs of the project were assessed and a plan for measuring
the various species of NOx in the gases was devised. The need for a research-grade ion
chromatograph became obvious, and one was ordered. The team has developed a process flow
diagram, a material balance table, detailed sketches of equipment for the pilot plant, a list of
equipment,andasketchof theanalyticalsamplingsetup.Theseitemsareall includedin AppendixI
aspartof thedocumentationfor this report.
Boilernumber2 hasbeenselectedastheboiler to whichmodificationswill bemadein order
to testthis newtechnology.Thesiteis indoors,andhassufficientroomfor constructionand
operationof thepilot plant,andhasanaturalgassupply,andwaterandelectricityfor thepilot plant.
Sketchesof how thepilot plantwill fit into theboilerhousearealsoprovidedin AppendixI.
Thepurposesof thepilot plantareto confirm thelaboratoryresults,to gatheradditional
chemicalreaction(kinetic) data,andto developlargerscaleinformationsuitablefor designof full-
scalefacilitiesanda detailedeconomicanalysesof theprocess.A draftexperimentaldesignplanwas
devisedandis presentedin AppendixII. Thefinal "treatmentlevels" for all variableswill beset
afterfinding theactualNOx levelscomingfrom Boiler 2.
MAJOR JOBS REMAINING AND WORK PLANNED FOR NEXT QUARTER
The major tasks planned for the coming year are as follows:
1. Finish ordering all equipment for the pilot plant
2. Construct the pilot plant
3. Write start-up and operating procedures for the pilot plant
4. Start up and operate the pilot plant to obtain all required data
5. Analyze the results obtained from the pilot plant
6. Document our work with a final report
7. Ensure technology transfer through publication of peer-reviewed papers, through
presentations at conferences, and through meetings at KSC.
5
PERSONNELSTATUS
Dr. CooperremainsasProjectDirectorandPrincipalInvestigator.Dr. ClausenandDr. Dietzare
co-PrincipalInvestigators.MichelleCollins is thePhDstudentin charge,andQuangNguyen,
LoubnaTazi,andJohnCollins (no relationto Michelle)aremastersstudentsinvolvedin thisproject.
Dr. Pwu-ShengLiu (researchassociate)is doingcomputermodelingof thekinetic reactions.
FINANCIAL STATUS
The project is a cost-reimbursable federal demonstration project, but expenditures to date are
somewhat behind the timeline of work accomplished as shown previously in Table 1. This is
because it took a while to get the design to the state where equipment could be ordered. The
purchase of materials and equipment for the construction and operation of the pilot plant will soon
increase the expenditures, and we expect to fulfill our budget. In addition, a significant portion of
the faculty release time will be charged during the summer semester. Table 2 shows the current
status of expenditures vs budget by major category.
Category
Personnel
Capital Equipment
Supplies/Materials
Travel
Total Direct Costs
Indirect Costs
Total Project
TABLE 2
Project Expenditures vs Project (Two-Year) Budget
(As of Jan 31, 1997)
In Thousands of Dollars, rounded
Budgeted
160
42
32
4
244
53
Expended/Encumbered
37
22
0
1
60
9
Balance
123
20
32
3
184
44
297 69 228
(This page not used)
APPENDIX I
MATERIAL BALANCES, DRAWINGS AND OTHER DOCUMENTS RELATED TO
PILOT PLANT EQUIPMENT DESIGN AND SELECTION
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Summary Design Tables
System Point 1, Figure 1 - Boiler Stack Gas
Constituent Ib-moles/hr
5.82
210.52
25.07
50.13
0.021135
0.002348
Totals 291.56
%wet basis % dry basis Mole Fraction
02 2.00 2.41 2.00E-02
_12 72.20 87.20 7.22E-01
CO2 8.60 10.38 8.60E-02:
H20 17.19 N.A. 1.72E-01
NO 0.007249 0.008754 7.25E-05 I
NO2 0.000805 0.000973 8.05E-06
100.00100.00 1.00E+00
Gas flow rate (cfm) = 3406
Temperature (deg. F) -- 500 Pressure (atm) = 1
ppm
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System Point 2, Figure 1 - Slip Stream Gas Before Heater Coils (Note: NO injection
is included in this summary)
Constituent Ib-moles/hr %wet basis % dry basis Mole Fraction ppm
02 0.85 1.99 2.40 1.99E-02
x12 30.92 72.21 87.20 7.22E-01
CO2 3.68 8.59 10.38 8.59E-02
420 7.36 17.19 N.A. 1.72E-01
klO 0.008565 0.020004 0.024156 2.00E-04
NO2 0.000345 0.000805 0.000972 8.05E-06
Totals 42.82 100.00 100.00 1.00E+00
Gas flow rate (cfm) = 500
Temperature (deg. F) = 500 Pressure (atm) = 1
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System Point 3, Figure 1 - Slip Stream Gas After Heater Coils
Constituent
O2
N2
CO2
H20
NO
NO2
Totals
Ib-moles/hr
0.85
30.92
3.68
7.36
0.008565
0.000345
42.82
%wet basis
1.99
72.21
8.59
17.19
0.020004
% dry basis
2.40
87.20
10.38
N.A.
0.024156
0.000805
100.00
0.00097_
100.00
Mole Fraction
1.99E-02
7.22E-01
8.59E-02
1.72E-011
2.00E-04
8.05E-06
1.00E+00
Gas flow rate (cfm) = 725
Temperature (deg. F) = 932 Pressure (atm) = 1
ppm
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SummaryDesignTables
SystemPoint4,Figure1- SlipStreamGasAfterReactionZone (Note:H202injec-
tion& resultantrxnsareincludedinthistable.Injection= 0.02Ib-molesH202/hr.)
ConstituentIb-moles/hr%wetbasis %drybasis MoleFraction ppm
02 0.86 2.00 2.42 2.00E-02
N2 30.92 72.12 87.18 7.21E-01
CO2 3.68 8.58 10.37 8.58E-02
H20 7.40 17.27 N.A. 1.73E-01
NO 0.000857 0.001998 0.002415 2.00E-05
NO2 0.002914 0.006797 0.008216 6.80E-05
HNO2 0.002570 0.005993 0.007244 5.99E-05
20
68
60
60HNO3 0.002570 0.005993 0.007244 5.99E-05
Totals 42.87 100.00 100.00 1.00E+00
Gas flow rate (cfm) = 710
Temperature (deg. F) = 900 Pressure (atm) = 1
System Point 5, Figure 1 -
Constituent
O2
Ib-moles/hr
0.86
Slip Stream Gas After Quenching
%wet basis % dry basis l Mole Fraction
1.44 2.42 1.44E-02
N2 30.92 51.66 87.18 5.17E-01
CO2 3.68 6.15 10.37 6.15E-02
H20 24.39 40.74 N.A. 4.07E-01
NO 0.000857 0.001431 0.002415 1.43E-05
!NO2 0.002914 0.004868 0.008216 4.87E-05
HNO2 0.002570 0.004293 0.007244 4.29E-051
HNO3 0.002570
59.86Totals
0.00 0.0072 4.29E-05
100.00 100.00 1.00E+00
Gas flow rate (cfm) = 458
Temperature (deg. F) = 168 Pressure (arm) = 1
ppm
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EQUIPMENT LIST
Section I - Boiler to Quencher:
1. 304 stainless steel duct & fittings (4", 12", and 18"), stainless steel clamps, and
flexible ducting. Bolts, nuts, and washers.
2. Shut-off valve with manual actuator and auto controls from the NG regulator and
temperature probe downstream of the quencher. Power supply for actuator.
3. NG burner, striker, and two air ports. Power supply for striker.
a. KAO wool for interior of burner section (pins to attach to roof), opt.
b. Pressure regulator.
c. Flow valve with manual control and auto control from computer and temperature
sensor downstream of the quencher. Power supply for auto control.
d. Sight glass.
e. Tapping valve for NG main line, screwed plug (for disconnection), piping (3/4"),
and piping connectors.
f. Manual isolation valve upstream from solenoid valve.
g. Solenoid valve, N.C.. Power supply for actuator.
h. Pressure gage (visual indicator only) up stream of regulator valve.
4. Minimum of three temperature probes. See how many ports we put in for
concentration measurement (possibly 14 total). Bushings. Transducers? Power
supply for probes.
5. Threaded 2-piece bushings or bulkheads (Swagelok) and quick connects for
concentration measurement device (12 total).
6. Power Supply.
7. Insulation with sheathing for outside of duct and clamps for sheathing or duct tape.
8. High temperature gasket material.
9. Flow meter.
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Section II- Overall Process:
1. Piping for hydrogen peroxide.
2. Transmitter for peristaltic pump and power supply.
3. NO and SO2 cylinders, regulators, and cylinder mounting brackets.
4. Flow meters for NO and SO2 piping, transmitters (?), and power supply.
5. NO and SO2 piping and isolation valves mounted to ductwork.
6. Spiral-cut cable wrap and cable mounts for running the cables.
7. Variable speed fan, transmitter, and power supply.
8. Gas flow meter, transmitter, and power supply.
9. Rainhat for exhaust and metal flanged slip for running exhaust through metal wall or
valve, controls, and flange to run exhaust back into the boiler.
10. Labview software and connectors.
11. Metal signs saying "Test in progress - DO NOT TOUCH", "Caution caustics in use -
Locate eyewash in emergency", "Hot surfaces - DO NOT TOUCH", and post sign
with testing period and points of contact.
12. Yellow and black tape for marking off the area.
13. Portable eyewash.
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Section III - Scrubber Desiqn:
1. Piping from water line to quencher, visual pressure gage, and flow meter with
transmitter, power supply, and isolation valves.
2. Spray nozzles for quencher.
3. Tower casing, packing and supports, piping and valves, and spray nozzles.
4. Reservoir with liquid level sensor (tied into the pump controller) optional.
5. Indicating magnahelic pressure transmitters (3), Dwyer Series 604D, or 605, and
power supply.
6. Liquid flow meter, transmitter and power supply.
7. Pump, controller, and power supply.
8. Minimum of two temperature probes (or will we need one at every conc. point) one
for liquid and one for gas. Bushings. Transducer? Power supply for probe.
9. Threaded 2-piece bushings or bulkheads (Swagelok) and quick connects for
concentration measurement device (3 total).
10. Power Supply, Dwyer, Model A-700 (110/120/220/230-240 to 24-28VDC) or Model
A-701 digital panel meter with power supply.
11. Pallet for scrubber and associated equipment with support stands.
12. Caustic supply, metering pump with controller and power supply, piping, and
isolation valve.
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Section I - Boiler to Quencher:
Variables:
1. Nitrogen oxide Concentration (100 ppm, 200 ppm, and 300 ppm).
2. Sulfur dioxide Concentration (0 ppm, 800 ppm, and 1600 ppm ).
3. Hydrogen peroxide Concentration 33% and 50%, (400 ppm, 500 ppm, and 600 ppm.
4. Temperature (830 °F, 930 °F, and 1030 °F).
5. Reaction Time or Rxn Zone Length. This will not be varied; it will be measured at
discreet points along the length of duct for all tests.
Notes:
1. Sequence of experiments should be randomized.
.
3.
.
Determine if any of the variables
cannot not be accurately changed within a short period of time, i.e. temperature may
require unacceptable long cooling down period in order to change from high to low
values in two successive tests. The number of individual tests listed int he table
are 81
Duplicate tests will be conducted at the midpoint (approx. 8 each).
Tests will be conducted up front for more than three temperatures and three
hydrogen peroxide concentrations to determine the sensitivity of these variables
and to narrow down the optimum three points at which to run the formal testing
(approx. 15 total).
Need to determine a basis for selecting the sulfur dioxide concentrations to be used.
Will start with values shown as they relate to power plant concentrations.
Section I - Boiler to Quencher:
Parameters To Be Measured:
1. Flow rate of the gas stream.
2. Temperature of the gas stream.
3. Flow rate of Natural Gas.
4. Flow rate of Nitrogen oxide.
5. Flow rate of Sulfur dioxide.
6. Flow rate of Hydrogen peroxide.
7. Nitrogen oxide concentration (from the NOx Analyzer) upstream of the Hydrogen
peroxide injection, upstream of the quench, and downstream of the scrubber.
8. Concentration of the gas stream upstream and downstream of the Hydrogen
peroxide injection (NO, NO2, HNO2, HNO3, and pressure/flow).
9. Indirect measurement of the reaction zone length of reaction time, f(conc.).
Measured Parameter Units Auto/Manual Output
CFM AutoFlow rate of the gas stream
Temperature of the gas stream oF Auto
Flow rate of Natural Gas CFM Auto
Flow rate of Nitrogen oxide Liters/min Auto
Flow rate of Sulfur dioxide Liters/min Auto
Flow rate of Hydrogen peroxide
Nitrogen oxide concentration
upstream of H202 injection
Nitrogen oxide concentration
upstream of the quench
Nitrogen oxide concentration
downstream of the scrubber
Liters/rain Auto
ppm Manual
ppm Manual
ppm
ppm
ppm
Concentration of the gas stream
upstream of H202 injection
Concentration of the gas stream
downstream of H202 injection
Manual
Manual
Manual
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APPENDIX II
EXPERIMENTAL DESIGN
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A Pilot-Scale Evaluation of a New Technology to Control NO(x) Emissions from Boilers at KSC: Hydrogen Peroxide Injection into Boiler Flue Gases Followed by Wet Scrubbing of Acid Gases

A Pilot-Scale Evaluation of a New Technology to Control NO(x) Emissions from Boilers at KSC: Hydrogen Peroxide Injection into Boiler Flue Gases Followed by Wet Scrubbing of Acid Gases

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