CATALYTIC OXIDATION TECHNOLOGY TRANSFER PROGRAMJohnson Matthey CatalyK6 Sample 400 Cells/in2. CATOX CBR Filtration Team Technology Transfer Program (TTP) Catalyst oxidation of CO by

CATOX CBR Filtration Team Technology Transfer Program (TTP)

Dr. Alex Balboa

Mr. Michael Parham

Research and Technology Directorate

Edgewood Chemical Biological Center

US Army, Research Development and Engineering Command

CATALYTIC OXIDATION TECHNOLOGY TRANSFER

PROGRAM

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4. TITLE AND SUBTITLE Catalytic Oxidation Technology Transfer Program

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14. ABSTRACT

15. SUBJECT TERMS

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Standard Form 298 (Rev. 8-98) Prescribed by ANSI Std Z39-18


• Design, construct and evaluate a catalytic air purification system for collective protection applications

– Demonstrate Broader Protection of Catalytic versus Single Pass Filtration Technology

– Optimize Power, Weight and Size of Catalytic Process

Overall Objective


-Incorporate commercial/newly developed catalysts for chemical, biological and TICs destruction (leverage w/

Advanced Adsorbents Program)

-Establish design relationships for predicting system size and energy requirements for potential applications

CATOX Reactor

Post-Treatment Abatement

CO2

Air

CWA

TIC

Heat ExchangerH2O

Approach


DARPA Investment ECBC/INDUSTRY

COLLABORATIONTECHNOLOGY READINESS LEVELS

LAB-SCALE TESTING

(COMPONENT)

SYSTEM-SCALE TESTING

- evaluation of commercial catalysts

- identification and evaluation of acid gas abatement strategies

- evaluation and optimization of catalyst system components- integration of system components

- determine size and energy requirements of scalable AP system

Program Leverage


– Objectives

• Technology maturity level/Technology readiness level

• Applicability/relevance to DoD CB Defense Acquisition Program

• Potential to mature for evaluation in field environment

• Availability of other funding to leverage Technology Transition investment

• Availability to government of data bases, methodology details, and design concepts

DARPA Investment


Chemical delivery sensitivities

• Single pass filters have their capacity defined in terms of CT (conc x time).

• This is a misleading indicator for CATOX.• CATOX challenges must be as close to the application’s

threat to account for performance sensitivities to:– # of attacks– Dosage per attack– Peak concentration– Frequency of attacks

• CATOX systems can succeed or fail for a given CT if any of these variables are changed.


Current filter technology • limited capacity for agents that are removed by chemical reaction and/or weakly

adsorbed• minimal protection versus several of the toxic industrial chemicals (TICs)• prolonged environmental exposure has been shown to reduce the capacity of these

filters for agents that are removed by chemical reaction

Catalytic oxidationAn alternative air purification technology

(1) broad and universal protection against the chem-bio threat, (2) reduced logistics due to long operational life,(3) greatly increased capacity for CB agents and TICs compared to current NBC

collective protection technologies and (4) lower energy costs relative to other regenerative filtration technologies. (5) Catalytic oxidation is a destructive technology, converting CB agents and TICs to

CO2 (catalysts exist that are capable of decomposing nitrogen-containing compounds with minimum NOx formation), H2O and haloacids (should halogens be associated with the parent compound).

Benefits


Issues Toxic By-productsCatalyst StabilityEnergyPost treatment

State of the ArtHigh activity Stable catalystsNOx, acid retentionImproved acid abatement technologies

• Mitigation of reaction product emissions• Maximize heat recovery to minimize energy

utilization

Challenges


Material Development

Downselect (light-off curves and selectivity)

-Incorporate commercial/newly developed catalysts for chemical, biological and TICs destruction


Monolithic Bed Catalyst Suppliers

Manufacturer Catalyst Designation Cell Density

Engelhard Corporation Engelhard Catalyst 200 Cells/in2

United Emissions Catalyst NB001-73-01 200 Cells/in2

United Emissions Catalyst NB001-73-02 200 Cells/in2

Sud Chemie Prototech LS02-03145 400 Cells/in2

Sud Chemie Prototech Misc-03144 400 Cells/in2

Guild Associates No-NOx 400 Cells/in2

Guild Associates 3X 400 Cells/in2

Johnson Matthey CatalyK6 Sample 400 Cells/in2


Catalyst oxidation of CO

by catalytic materials under

low and high humidity conditions(materials

improvement)

Lab-scale results

• good indicator of catalyst

activity (very clean parent and

byproduct)• poor effective

filtration by current NBC

systems

0 %

2 0 %

4 0 %

6 0 %

8 0 %

1 0 0 %

0 5 0 1 0 0 1 5 0 2 0 0 2 5 0 3 0 0

T e m pe rature , oC

Con

vers

ion,

%

U EC -0 1 C a ta ly s tEng e lha rd C a ta ly s tN o -N O x C a ta ly s tS C P-0 1 C a ta ly s tJ M C a ta lK 6 S a mpleU EC -0 2 C a ta ly s t3 X Ca ta ly s tS PS M IS C -0 3 1 4 4 N o -N O x plus 3 X

M on ol i thG H S V = 9,00 0[C O ] = 2,0 00 m g/m 3

(16 50 ppm ))[H 2O ] = 4.1 % vo l u m e

0 %

2 0 %

4 0 %

6 0 %

8 0 %

1 0 0 %

0 5 0 1 0 0 1 5 0 2 0 0 2 5 0 3 0 0

T e m pe rature , oC

Con

vers

ion,

%

U EC -01 C ata lys tEnge lhard C ata lys tSC P-03145 C ata lys tN O -N O x C ata lys tJM C ata lK 6 SampleU EC -02 C ata lys t3X Cata lystSC P M ISC -03144 C ata lys tN o-N O x plus 3X

M o no l i thG HS V = 9 ,0 00[C O ] = 2 ,00 0 m g /m 3

(1 65 0 ppm ))[H 2O ] = 0 .34 % vo l u m e


Schematic representationof catalytic reactor

Thermocouples

Gas Inlet

Inlet Flange

Packing

Frit

Catalyst

Gas Outlet

Gas Inlet

Inlet Flange

Packing

Frit

Catalyst

Gas Outlet


0%

20%

40%

60%

80%

100%

150 200 250 300 350 400

Temperature, oC

Con

vers

ion,

%

UEC-01 CatalystNO-NOx CatalystEngelhard CatalystSCP LS02-03145JM CatalK6 SampleUEC-02 Catalyst3X CatalystSCP MISC-03144No-NOx plus 3X

MonolithGHSV = 9,000[NH3] = 2,000 mg/m3

(2,650 ppm)[H2O] = 0.34% volume

Dry NH3 tests


Humid NH3 tests

0%

20%

40%

60%

80%

100%

150 200 250 300 350 400

Temperature, oC

Con

vers

ion,

%

UEC-01 CatalystNO-NOx CatalyatEngelhard CatalystSCP LS02-03145JM CatalK6 SampleUEC-02 Catalyst3X CatalystSCP MISC-03144No-NOx Plus 3X, Layered

GHSV = 9,000[NH3] = 2,000 mg/m3

(2,650 ppm)[H2O] = 4.1% volume


1

10

100

1000

200 220 240 260 280 300 320 340 360 380 400

Temperature, oC

[NO

x], p

pm

UEC-01 CatalystNo-NOx CatalystSCP LS02-03145Engelhard CatalystJM CatalK6 SampleUEC-02 Catalyst3X CatalystSCP MISC-03144No-NOx plus 3X

5 ppm NO2 Effluent NIOSH Requirement

GHSV = 9,000[NH3] = 2,000 mg/m3

(2,650 ppm)[H2O] = 0.34% volume

25 ppm NO Effluent NIOSH Requirement

30 ppm NO2 Effluent CHPPM MEG Guidelines

9 ppm NO Effluent CHPPM MEG Guidelines

Selectivity (NOx): NH3 tests (dry)


1

10

100

1000

200 220 240 260 280 300 320 340 360 380 400

Temperature, oC

[NO

x], p

pm

UEC CatalystNo-NOx CatalystSCP LS02-03145Engelhard CatalystJM CatalK6 SampleUEC-02 Catalyst3X CatalystSCP MISC-03144No-NOx Plus 3X, Layered

5 ppm NO2 Effluent NIOSH Requirement

GHSV = 9,000[NH3] = 2,000 mg/m3

(2,650 ppm)[H2O] = 4.1% volume

25 ppm NO Effluent NIOSH Requirement

30 ppm NO2 Effluent CHPPM MEG Guidelines

9 ppm NO Effluent CHPPM MEG Guidelines

Selectivity (NOx): NH3 tests (humid)


0

200

400

600

800

1000

200 220 240 260 280 300 320 340 360 380 400

Temperature, oC

[NO

x], p

pm

UEC-1 CatalystNo-NOx CatalystSCP :S02-03145Engelhard CatalystJM CatalK6 SampleUEC-2 Catalyst3X CatalystSCP MISC-03144No-NOx plus 3X

GHSV = 9,000[NH3] = 2,000 mg/m3

(2,650 ppm)[H2O] = 0.34% volume

Selectivity (N2O): NH3 tests (dry)


Selectivity (N2O): NH3 tests (humid)

0

200

400

600

800

1000

200 220 240 260 280 300 320 340 360 380 400

Temperature, oC

[NO

x], p

pm

UEC CatalystNo-NOx CatalystSCP LS02-03145Engelhard CatalystJM CatalK6 SampleUEC-02 Catalyst3X CatalystSCP MISC-03144NO-NOx plus 3X, Layered

GHSV = 9,000[NH3] = 2,000 mg/m3

(2,650 ppm)[H2O] = 4.1% volume


Dry C3F6 tests

0%

20%

40%

60%

80%

100%

100 150 200 250 300 350 400 450 500

Temperature, oC

Conv

ersio

n, %

UEC-01 CatalystEngelhard Catalyst3X CatalystUEC-02 CatalystSCP-01 CatalystSCP-02 CatalystJM CatalK6 Sample3X Plus No-NOx CatalystGuild NO-NOx

GHSV = 9,000

[C3F6] = 2,000 mg/m3

(300 ppm)[H2O] = 0.34%


Humid C3F6 tests

0%

20%

40%

60%

80%

100%

100 150 200 250 300 350 400 450 500

Temperature, oC

Conv

ersio

n, %

UEC-01 CatalystEngelhard Catalyst3X CatalystUEC-02 CatalystSCP-01 CatalystSCP-02 CatalystJM CatalK6 Sample3X Plus No-NOx CatalystGuild No-NOx

GHSV = 9,000

[C3F6] = 2,000 mg/m3

(300 ppm)[H2O] = 4.1%

Table showing T95?


Catalyst PerformanceCatalyst performance summary information

Catalyst Design Lim. Temperature2 Ammonia Ammonia Chemical1 [NOx]3 [N2O]3

Guild No-NOx C3F6 T > 500°C > 500 ppm > 300 ppm

Guild No-NOx Plus 3X C3F6 350°C 15 ppm 160 ppm

Guild 3X C3F6 310°C 400 ppm 550 ppm

Engelhard #164217005 C3F6 440°C > 1,000 ppm ~ 300 ppm

UEC NB001-73-001 C3F6 T > 500°C > 1,000 ppm ~ 300 ppm

UEC NB001-73-002 C3F6 T > 500°C > 1,000 ppm ~ 300 ppm

SCP LS02-03145 C3F6 450°C > 1,000 ppm ~ 300 ppm

SCP MISC-03144 C3F6 450°C > 1,000 ppm ~ 300 ppm

JM CatalyK6 Sample C3F6 T > 500°C > 1,000 ppm ~ 300 ppm 1Chemical requiring greatest temperature to achieve 99% destruction 2Temperature required to achieve 99% destruction of design limiting chemical 3NOx or N2O concentration formed during destruction of NH3 at temperature


Catalyst Bed

Heater/Precooler

ContaminatedAir In

CleanAir Out

PostTreatmentFilter

AmbientAir Out

Fan

Fan

Targeted for:FCS ApplicationScalable for building protectionTransportable shelters (JECP)

NBC Subsystem Summary


Ammonia (HC): Feed TemperatureECBC 50 SCFM CATOX UNIT

Feed Conditions

0

10

20

30

40

50

60

70

80

90

100

0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000

Time (min)

Tem

pera

ture

(C)

TC 10 - Water NozzleTC 11 - Chemical NozzleDew Point @ 4.2 psig


ATD Experimental Design

• 6 x 2000 mg/m3 x 10 minutes (CT = 120,000 mg-min/m3)

• 6 x 200 mg/m3 x 100 minutes (CT = 120,000 mg-min/m3)

______________________________

CT = 240,000 mg-min/m3

(under 2.5% water (volume) and 50 cfm)


ECBC 50 SCFM CATOX UNITNH3-HW-BHc Ammonia Feed Chart 5-6-04

6 x 10 minute pulse

0

500

1000

1500

2000

2500

0 50 100 150 200 250 300 350 400 450

Time (min)

Am

mon

ia (m

g/m

3)

A1 - Feed (Pre-Heater)

A3 - Feed (Post Heater)

Ammonia (HC): Feed Concentrations


Ammonia (HC): TemperatureECBC 50 SCFM CATOX UNIT

Temperature Plot

0

50

100

150

200

250

300

350

0 50 100 150 200 250 300 350 400 450 500

Time (min)

Tem

pera

ture

(C)

TC 1 - Feed

TC 2 - HeatEx HotOut

TC 3 - Heater Out

TC 4 - MAP Inlet

TC 5 - MAP Outlet

TC 6 - PTF Outlet

TC 7 - HeatEx HotIn

TC 8 - HeatEx ColdOut

TC 9 - Guard PTFInlet


ECBC 50 SCFM CATOX UNITAnalog Signal Chart

0

5

10

15

20

25

30

35

235 245 255 265 275 285 295 305 315 325

Time (min)

Am

mon

ia (m

g/m

3)

A4 - Post MAP A5 - Post PTF

Ammonia (HC); Parent compound


Ammonia (HC): By-productsECBC 50 SCFM CATOX UNIT

Analog Signal Chart

0

50

100

150

200

250

300

350

400

450

500

235 245 255 265 275 285 295 305 315 325

Time (min)

NO

x co

ncen

trat

ion

(ppm

)

NOX 2 Post MAP

NOX 3 Post PTF


ECBC 50 SCFM CATOX UNITFeed Conditions

0

10

20

30

40

50

60

70

80

90

100

0 100 200 300 400 500 600

Time (min)

Tem

pera

ture

(C)

TC 10 - Water NozzleTC 11 - Chemical NozzleDew Point @ 4.2 psig

Ammonia (LC): Feed Temperature


ECBC 50 SCFM CATOX UNITNH3-HW-BLc P3-5Feed Chart 5-10-04

0

20

40

60

80

100

120

140

160

180

200

0 100 200 300 400 500 600

Time (min)

Am

mon

ia (m

g/m

3)

A1 - Feed

A3 - Feed

Ammonia (LC): Feed Concentrations


ECBC 50 SCFM CATOX UNITTemperature Plot

0

50

100

150

200

250

300

350

0 100 200 300 400 500 600

Time (min)

Tem

pera

ture

(C)

TC 1 - Feed


TC 3 - Heater Out

TC 4 - MAP Inlet

TC 5 - MAP Outlet

TC 6 - PTF Outlet

TC 7 - HeatEx HotIn



Ammonia (LC): Temperature


ECBC 50 SCFM CATOX UNITNH3-HW-BLc P3-5

Effluent Chart (NH3) 5-10-04

0

5

10

15

20

25

30

35

40

45

50

0 100 200 300 400 500 600

Time (min)

Am

mon

ia (m

g/m

3)

A4 - Post MAP

A5 - Post PTF

Ammonia calibration +/- 50% below 12 mg/m3

Ammonia (LC): Parent



EO-HW-BHc 6-18-04

0

50

100

150

200

250

300

0 10 20 30 40 50 60 70 80

Time (min)

Tem

pera

ture

(C)

TC 1 - Feed


TC 3 - Heater Out

TC 4 - MAP Inlet

TC 5 - MAP Outlet

TC 6 - PTF Outlet

TC 7 - HeatEx HotIn



Ethylene Oxide (HC): Temperature


Ethylene Oxide (HC): Feed ConcentrationsECBC 50 SCFM CATOX UNIT

EO-HW-BHc 6-18-04EO Feed - CO2 Effluent

0

200

400

600

800

1000

1200

1400

1600

1800

2000

0 10 20 30 40 50 60 70 80

Time (min)

Con

cent

ratio

n (p

pm)

A1 - EO Feed

A4- CO2 Effluent


Ethylene Oxide (HC): By-productsECBC 50 SCFM CATOX UNIT

EO-HW-BHc 6-18-04EO - CO Effluent

0

1

2

3

4

5

6

7

8

9

0 10 20 30 40 50 60 70 80

Time (min)

Con

cent

ratio

n (p

pm)

A4 - CO Effluent

A4 - EO Effluent (FID)



0

50

100

150

200

250

300

0 20 40 60 80 100 120 140

Time (min)

Tem

pera

ture

(C)

TC 1 - Feed


TC 3 - Heater Out

TC 4 - MAP Inlet

TC 5 - MAP Outlet

TC 6 - PTF Outlet

TC 7 - HeatEx HotIn



Formalin (LC)


ECBC 50 SCFM CATOX UNITHCHO-HW-DLc 7-14-04

A1 - HCHO A4 - CO2

0

100

200

300

400

500

600

700

800

900

0 20 40 60 80 100 120 140

Time (min)

Con

cent

ratio

n (p

pm)

A4 - CO2 (ppm)

A1 - HCHO (ppm)

Formalin (LC)


ECBC 50 SCFM CATOX UNITHCHO-HW-DLc 7-14-04

A3 - CO2 A4 - CO A4 - HCHO A5 - HCHO

0

10

20

30

40

50

60

70

80

90

100

0 20 40 60 80 100 120 140

Time (min)

Con

cent

ratio

n (p

pm)

A4 - CO (ppm) A4 - HCHO (ppm)

A5 - HCHO (ppm) A3 - CO2 (ppm)

Formalin (LC)


Chemicals tested:Carbon Monoxide

AmmoniaEthylene Oxide

FormalinChemical underway:

AcetonitrileChemicals left:

ChloroformCKCS2

Nitric AcidCEES

HFHFP

DMMP


Power and weight optimization

In a fielded system, one catalyst bed operating at one flow rate and one operating temperature will be employed.

Field conditions impacting CATOX

C a t O x D e m o n s tra t o r I m p a c t o f A ir f lo w o n A v e r a g e P o w e r D e m a n d

[ 8 0 % H X e f f , 5 0 S C F M a i r f l o w , 2 5 0 C C a t a l y s t T e m p e r a t u r e , 8 1 0 0 W M a x P o w e r D e m a n d , 8 0 k g Th e r m a l M a s s ]

0

5 0 0

1 0 0 0

1 5 0 0

2 0 0 0

2 5 0 0

3 0 0 0

3 5 0 0

4 0 0 0

4 5 0 0

5 0 0 0

5 5 0 0

6 0 0 0

0 2 5 5 0 7 5 1 0 0 1 2 5 1 5 0 1 7 5 2 0 0 2 2 5 2 5 0

A ir f l o w (S C F M )

Ave

rage

Pow

er D

eman

d (W

)

C a t O x D e m o n s t r a t o rM C P E ( M 4 8 )C a t a ly s t T e m p e r a t u r e R e d u c t io n o f 2 5 C a n d 5 % I n c r e a s e in H e a t E xc h a n g e r E f f ic ie n c y

Sy s t e mO p t i m i z a t i o n


Improvement of SubcomponentsNext Generation PTS

Catalyst Improvements

Heat Exchanger (greater 90% heat recovery efficiency

Modular System

Lighter, Smaller Overall Footprint


AcknowledgementsJoseph Rossin, Ph.D., Guild Associates

Russell W. Johnson, Ph.D., Honeywell, Inc.

Peter M. Michalakos, Ph.D., Honeywell, Inc.

Brian Elmiger, Honeywell, Inc.

Documents

CATALYTIC OXIDATION TECHNOLOGY TRANSFER PROGRAMJohnson Matthey CatalyK6 Sample 400 Cells/in2. CATOX CBR Filtration Team Technology Transfer Program (TTP) Catalyst oxidation of CO by