DIMINISHING CARBON DIOXIDE EMISSIONS AND ENERGY USE IN

FOUNDRIES VIA INNOVATIVE POLLUTION PREVENTION AND

CLEVER CAPITALIZATION OF HEATCLEVER CAPITALIZATION OF HEATFRED S. CANNONFRED S. CANNON, PROFESSOR, PENN STATE

(Masters and Degree of Ad anced Engineer from Stanford)(Masters and Degree of Advanced Engineer from Stanford)

PENN STATE: BOB VOIGT, SRIDHAR KOMARNENI, TIM CONSIDINE FRANK CLEMENTE ANDRE BOEHMANCONSIDINE, FRANK CLEMENTE, ANDRE BOEHMAN

MIT: TIM GUTOWSKI, LEON GLICKSMAN

NEENAH FOUNDRY: FRANK HEADINGTON STEVE LEWALLENNEENAH FOUNDRY: FRANK HEADINGTON, STEVE LEWALLEN, JEFF GOUDZWAARD

FURNESS NEWBURGE: JIM FURNESS

10-YEAR COLLABORATION: PENN STATE NEENAH FOUNDRY MIT STATE, NEENAH FOUNDRY, MIT,

FURNESS-NEWBURGENeenah ‘98: Green Sand Pollutants and Molding Strength. $25,000Neenah 98: Green Sand Pollutants and Molding Strength. $25,000DOE 98-01: Green Sand Non-Incineration treat. of VOCs. $550,000NSF ‘99: Advanced Oxidation Processes for Foundries. $37,000NSF 00-02: Improve Green Sand with Advanced Oxidation.$250,000p ,DOE 01-05: Less Foundry Emissions and Waste with AO. $525,000EPA/NSF 02-05: Less Materials and Pollutants with AO. $375,000CA ARB ‘03: Non-Incineration removal of VOCs, Odors. $300,000DOE 05-06: Anthracite in Green Sand of Foundries. $70,000NSF 05-08: MUSES Materials Flow of Metal Casting. $1,300,000EPA 07-08: Reclaiming Waste Green Sand in Foundries. $35,000N I U 07 08 Ch t i VOC f C Bi d $20 000N. Iowa U 07-08: Characterize VOCs from Core Binders. $20,000NSF 08-09: Foundry Cores with UV-Toughened Collagen. $50,000DOE 08-09: Anthracite fines bindered with Collagen. $95,000

T t l $3 632 000Total $3,632,000

STRATEGIES FOR DIMINISHING ENERGY, CARBON DIOXIDE

ULTIMATELY, USE ENERGY SOURCE THAT USES NO CARBON, IS SUSTAINABLE, NIMBY-FREEIN INTERIM, BE CLEVER TO DIMINISH ENERGY AND CO2 WHILE USING CARBON-BASED ENERGYFOCUS ON CUPOLA FOUNDRY HEREIN

NEENAH FOUNDRY, WI

CARBON DIOXIDE EMISSIONS CONVENTIONAL CUPOLA IRON FOUNDRY

KG CARBON DIOXIDE / TON IRON POURED295 COKE25 NATURAL GAS AND LIMESTONE 75 OFF-SITE COKING & ELECTRIC POWER

145 HEATING: NATUAL GAS AND ELECTRIC30 GREEN SAND, MOLD BINDER30 GREEN SAND, MOLD BINDER30 SHIPPING: SCRAP, GREEN SAND, ETC.

600 TOTAL FOR CUPOLA FOUNDRY

STRATEGIES FOR LESS ENERGY, CO2% Δ STRATEGY% Δ STRATEGY15 RECIRCULATE H2 AND CO FROM CUPOLA5 REPLACE SOME COKE WITH ANTHRACITE

13 REPLACE SOME COKE WITH NATURAL GAS12 IMPROVE CASTING YIELD VIA HOLLOW RISERS5 RECLAIM GREEN SAND VIA HYDROACOUSTIC5 C G S O COUS C

CLEANING4 LESS VOCS, SCRAP: ADVANCE OXIDATION,

CLEAN BINDERSCLEAN BINDERS20 INDOORS: RE-USE LOW-VOC AIR, SO DON’T

HEAT NEW AIR5 CAPTURE CO2 ON POROUS CARBONS, ASH, ETC

60-80% TOTALS (CUMULATIVE SUM)45 60% TOTALS (COMPOUNDED SUM)45-60% TOTALS (COMPOUNDED SUM)

FOUNDRY SCHEMATIC: MELTING METAL

REPLACE COKE WITH 10-20% NATURAL GAS PLUS OXYGEN; AND 10-20% ANTHRACITE;

ONLY 2 US SUPPLIERS OF COKEWHEN USING COKE MUST HEAT TWICEWHEN USING COKE, MUST HEAT TWICEWITH NATURAL GAS:CH ( IV VALENCE) TO CO (+IV VAL)CH4 (-IV VALENCE) TO CO2 (+IV VAL)MORE ENERGY / CO2 THAN WITH COKE:C (0 ) O CO ( )C (0 VAL) TO CO2 (+IV VAL)WHEN USE CH4 +O2, LESS GAS FLOW UPWARD THROUGH CUPOLA THAN WITHUPWARD THROUGH CUPOLA THAN WITH COKE PLUS AIR; SO BURN MORE H2 AND CO DEEP IN CUPOLACO DEEP IN CUPOLA

CONVENTIONALLY, 35% OF COKE ENERGY IN EXHAUST H AND COENERGY IN EXHAUST H2 AND CO

OPTION A: CONVERT H2 AND CO TOOPTION A: CONVERT H2 AND CO TO POWER VIA OFF-GAS GENERATORB: RECLAIM HEAT DURINGB: RECLAIM HEAT DURING AFTERBURNING FOR INDOOR AIR, MAKING IN SITU POROUSMAKING IN-SITU POROUS CARBONSC RECIRCULATE OFF GAS BACKC: RECIRCULATE OFF-GAS BACK THROUGH CUPOLA TUYERES

GREEN SAND MOLD, METAL POURING ENHANCED BY ADVANCED OXIDATION ENHANCED BY ADVANCED OXIDATION

FOUNDRY WITH SONOPEROXONE SYSTEMTMBLACK WATER (BW)

RECIRCULATION

PLASMA - SILICA

CLAYCAPTURE AND

EXHAUSTAIR

SONO-PEROXONETM

CLARIFIER

DUSTSETTLING

RECYCLE

EXHAUST

BAG HOUSE

FINES

BWWASTE SILICA

DUST

SANDCOOLER

METAL POURINGAND COOLING

MOLDING

EXHAUSTDUST AND

VOCS

SAND MIXER/MULLER

CASTPRODUCT

MOLDING

SHAKEOUT

PRODUCT

RECIRCULATED SAND

MAKE-UP SAND, BOND, WATER

METAL POURING: 40-60% OF MELTED METAL SOLIDIFIES IN

ACCESS-WAY RISERS, ETC.INCREASE PRODUCT YIELD BY EMPLOYING HOLLOW RISERS, ETC.,10-25% LESS ENERGY, CARBON DIOXIDEDIOXIDEULTRASONICS ALSO CREATES STRONGER IRONSTRONGER IRON

LESS IMPORT OF COLD AIR FROM OUTSIDE BY RECIRCULATING

TREATED INDOOR AIR

ALLOW 15-20% LESS ENERGY AND CO2

DURING NORTHERN WINTERS, INDOOR AIR HEATING ACCOUNTS FOR 35-45% OF ENERGY AND CO2

O C C S OTO RECIRCULATE AIR, MUST REMOVE VOCS AND CO, SO WORKERS CAN BREATHE THE AIRBREATHE THE AIRPOLLUTION PREVENTION BY ADVANCED OXIDATION LOW-EMISSION BINDERSOXIDATION, LOW-EMISSION BINDERS, REUSED GREEN SAND

ADVANCED OXIDATION TREATMENT OF BAG HOUSE

DUST / WATER SLURRYBLACKWATER MIXED WITH GREEN SAND. GREEN SAND MAKES THE MOLD THAT MOLTEN METAL IS POURED INTOMOLTEN METAL IS POURED INTOGREENSAND: 85% SILICA SAND, 8% MB CLAY, 4-5% LOI COAL, 2% WATERNEED CARBON IN MOLD TO DRIVE CNEED CARBON IN MOLD TO DRIVE C INTO IRON, AND PREVENT OXIDATIONAO DIMINISHES VOCS BY 30-70% CLAYAO DIMINISHES VOCS BY 30 70%, CLAY AND COAL USE BY 25-35%, AND SCRAP BY 30-50%

BLACK WATER SYSTEM; NEENAH AND 20+ OTHER FOUNDRY LINESAND 20+ OTHER FOUNDRY LINES

Clear view of iron being pou~370 feet from camera

Greensand molds being pushed into shakeout cYOU CAN SEE THE LIGHT AT THE END OF THE TUNNEL

Dust feed from new baghouses

Dust mixer and acoustic systemDust mixer and acoustic system

5000 gallon system retained from replaced wet dust collecting system

EMISSIONS AT NEENAH: WITH AO (SOLID) VS. NO AO (HOLLOW)AO (SOLID) VS. NO AO (HOLLOW)

EFFECT OF ADVANCED OXIDATION:R l Ti T t R ltReal Time Test Results Pouring,

Cooling & Shakeout in Production FoundryStars Pattern - Tap vs A/O

45

30

35

40

15

20

25

ppm Tap

A/O

0

5

10

1 177 353 529 705 881 1057 1233 1409 1585 17611 177 353 529 705 881 1057 1233 1409 1585 1761

Time, sec

WITH AO (WGS), CONDITION GREEN SAND CARBON SO IT HOSTS LESS HAPS BUT CARBON SO IT HOSTS LESS HAPS, BUT

RETAINS CASTING QUALITYBenzene - WGS & Composite

0.005

0.006WGSComposite

0.004

ent (

nA)

0.002

0.003

Ion

Cur

re

0.001

00 100 200 300 400 500 600 700 800 900 1000

Temperature (oC)

WITH AO (WGS), MAINTAIN CO2 AND CO BLANKETS BETWEEN METAL AND CO BLANKETS BETWEEN METAL AND

MOLD, WHICH IS NEEDEDCO2 - WGS & Composite2 p

2.5

3

WGSComposite

2

ent (

nA)

Composite

1

1.5

Ion

Cur

re

0.5

00 100 200 300 400 500 600 700 800 900 1000

Temperature (oC)

TGA-MS / FLASH PYROLYSIS: CELLULOSE BIOMASS RELEASE FEWER VOCS CO IN BIOMASS RELEASE FEWER VOCS, CO2 IN

MOLD (FIRST GENERATION CO2).

50

60

h Py

ro.

AnthraciteS C l

30

40

V/F

lash

%)

. Sea CoalLigniteCellulose

20

30

ro. H

CV

HC

V (% Cellulose

0

10

GA

Pyr

C1-C5 C6-C16TG

WITH COLLAGEN

BINDERBINDER RATHER

THAN PHENOLICPHENOLIC URETHANE

BINDER; GENERATEGENERATE FAR LESS

VOCS, CO2; BUT 2;

NEED ENHANCED STRENGTH

WITH UV

RECLAIMING GREEN SAND BY HYDROACOUSTIC CAVITATION, HYDROACOUSTIC CAVITATION,

ULTRASONICS-AOCONVENTIONALLY, SAND GRAINS ,ACCUMULATE “RAINCOAT” OF RECONDENSED CARBONWITH HYDROACOUSTICS BLAST THISWITH HYDROACOUSTICS, BLAST THIS CARBON OFF, THEN THE SAND GRAINS CAN BE REUSEDALSO RELEASED CARBON CAN BE REUSEDALSO, RELEASED CARBON CAN BE REUSED; AND THIS CARBON SOURCE RELEASES LESS HAPS, WHILE MAINTAINING CASTING QUALITY5-10 FEWER TRUCKLOADS / DAY SAND IN AND OUTALSO CLEAN HEAT EXCHANGE TUBE WITHALSO, CLEAN HEAT EXCHANGE TUBE WITH AO

HYDROACOUSTIC ULTRASONICS-AO SAND RECLAMATIONAO SAND RECLAMATION

REMOVE CARBON COAT

BEFORE TMT AFTER

RECLAIMED SAND: QUALITY CASTING; RETAIN TENSILE STRENGTHRETAIN TENSILE STRENGTH

250

With Anti-Veining Additive

150

200

h (p

si)

100ns

ile S

tren

gt

50

Te

00% 20% 40% 60% 80% 100%

Percent Reclaimed Sand

WITH WASTE HEAT FROM CUPOLA, PRODUCE IN-SITU

POROUS CARBON (FOR NO COST)ADSORB VOCS SO AIR CAN BE RECIRCULATEDFULL-SCALE TRIAL: PAC REMOVED 1/3 OF VOCS WITH <0.5 SEC RETENTION TIME BEFORE BAG HOUSE CLOTHAMINATED POROUS CARBON TO CAPTURE CO2, CO (?)

IN-SITU POROUS CARBONS MADE VIA PYROLYSIS SO ROBUST OVER BROAD PYROLYSIS, SO ROBUST OVER BROAD

RANGE OF TIME, TEMP (KISS)

/g) 0 .1 2

0 .1 4

lum

e (m

L/

0 .0 8

0 .1 0

u. P

ore

Vo

0 .0 4

0 .0 6 0 m in6 0 m in1 5 m in3 0 m in7 5 i

Cum

u

0 .0 0

0 .0 2 7 .5 m in

P o r e W id th (A )1 1 0 1 0 0 1 0 0 0

SORB CO2 IN-SITU INTO SORB CO2 IN-SITU INTO AMINATED POROUS CARBONS

WITH AMINE FUNCTIONALITY ON POROUS CARBON, WET CO2 SORBS TO 10-30% MASS RATIO; PUFF OFF AT HIGHER PARTIAL PRESSURES, THENSORB CO ONTO FLY ASH CUPOLASORB CO2 ONTO FLY ASH, CUPOLA EXHAUST PARTICLES, MAGNESIUM SILICATESSILICATESUSE CARBONATED INORGANICS FOR BUILDING AGGREGATEBUILDING AGGREGATE

SUMMARY LOWER ENERGY AND CARBON DIOXIDECARBON DIOXIDE

% Δ STRATEGY15 RECIRCULATE H2 AND CO FROM CUPOLA5 REPLACE SOME COKE WITH ANTHRACITE5 REPLACE SOME COKE WITH ANTHRACITE

13 REPLACE SOME COKE WITH NATURAL GAS12 IMPROVE CASTING YIELD VIA HOLLOW RISERS5 RECLAIM GREEN SAND VIA HYDROACOUSTIC

CLEANING4 LESS VOCS SCRAP: ADVANCE OXIDATION4 LESS VOCS, SCRAP: ADVANCE OXIDATION,

CLEAN BINDERS20 INDOORS: RE-USE LOW-VOC AIR, SO DON’T

HEAT NEW AIRHEAT NEW AIR5 CAPTURE CO2 ON POROUS CARBONS, ASH, ETC

60-80% TOTALS (CUMULATIVE SUM)( )45-60% TOTALS (COMPOUNDED SUM)

REFEREED JOURNAL PAPERSWang, Y.J., F. S. Cannon, M. Salama, J. Goudzwaard, J. C. Furness (2007) Characterization of hydrocarbon emissions from green sand foundry core binders by analytical pyrolysis. Env. Sci and Tech.y g y y y py yFox, J.T., F.S. Cannon, R.C. Voigt, J.C. Furness, P.B. Smith, S.E. Lewallen, J.E. Goudzwaard (2007) Simultaneous Sand, Clay and Coal Reclamation using Induced Particle Collision, Discretionary Settling, and Advanced Oxidation. American Foundry SocietyMilan-Segovia, N., Y.J. Wang, F.S. Cannon, R.C. Voigt, J.C. Furness (2007) Determination of Advanced Oxidants in Aqueous Solutions: Use of Terephthalic Acid Dosimeter for Measurement of OH* Radical P d ti O S i d E i iProduction. Ozone Science and Engineering. Wang, Y.J.; H. Huang F.S. Cannon, R.C. Voigt, S. Komarneni, J.C. Furness (2007) Evaluation of Volatile Hydrocarbon Emission Characteristics of Carbonaceous Additives in Green Sand Foundries. Env. Sci. Tech. 41 pp 2957-2963. Wang, Y.J., F.S. Cannon, R.C. Voigt, S.Komarneni, J.C. Furness (2006) Study on the Effects of Advanced Oxidation on Green Sand Properties via Iron Casting into Green Sand Molds Env Sci Tech 40 pp 3095Oxidation on Green Sand Properties via Iron Casting into Green Sand Molds. Env. Sci. Tech. 40 pp.3095-3101. Wang, Y., F.S. Cannon, S. Komarneni, R.C. Voigt, J. Furness (2005) Mechanisms of Advanced Oxidation Processing on Bentonite Consumption Reduction in Foundries. Environmental Science and Technology. 39 pp.7712-7718. Wang Y F S Cannon D Neill K Crawford R X Voigt J C Furness C R Glowacki (2004) Effects ofWang, Y. , F.S. Cannon, D. Neill, K. Crawford, R.X. Voigt, J.C. Furness, C.R. Glowacki. (2004) Effects of Advanced Oxidation Treatment on Green Sand Properties and Emissions. Foundry Society Trans. V112 No 04-069 p. 635-648. Land, J.D, F.S. Cannon, R.C. Voigt, J. Goudzwaard (2004) Perspectives on Foundry Air Emissions: A Statistical Analysis Approach. American Foundry Society Trans. V112 No 04-040 p. 1075-1081Glowacki, C.R., G.R. Crandell, F.S. Cannon, R.C. Voigt, J.K.Clobes, J.C. Furness, B.A. McComb, S.M. , , , , g , , , ,Knight. (2003) Emissions Studies at a Test Foundry using an Advanced Oxidation-Clear Water System. American Foundry Society Transactions. No. 03-152 (20 pp.). Goudzwaard, J.E., C.M. Kurtti, J.H. Andrews, F.S. Cannon, R.C. Voigt, J.E. Firebaugh, J.C. Furness, D.L. Sipple (2003) Foundry Emmissions Effects with an Advanced Oxidation Blackwater System. American Foundry Society Transactions. No. 03-079 (20 pp) L d J D V i t R C C F S F J C G d d J L bb H (2002) “P f dLand J.D., Voigt R.C., Cannon F.S., Furness, J.C., Goudzwaard, J., Luebben, H. (2002) “Performance and Control of a Green Sand System During the Installation and Operation of an Advanced Oxidation System.” American Foundry Society Transactions, Vol 110, pp. 705-715. Andrews, J., R. Bigge, F. S. Cannon, G. R. Crandell, J. C. Furness, M. Redmann, R. C. Voigt (2000) Advanced Oxidants Offer Opportunities to Improve Mold Properties, Emissions. Modern Casting September; pp 40 43