BSA NTA 24a ay J. KOSAE Vol. 24, No. (2008) pp.$5~62 Journal of Korean Society for Atmospheric Environment SAT AAA TSA FISTS ALFA] Dust A254 A Study on the Reduction of Particulate Emission Using Oil Soluble Organometallic Compounds as Combustion Improver for Heavy Fuel Oil Use" sae - SAA - ANF - ogy” BAVAASAFA, so AAA ay, Me Lscwho] a. (20074 892 79 842, 20084 14 102 a4) Dong-Chan Kim’, Nam-Sun Nho, Je-Kyung Woo, Jin-Hoon Kim and Young-Sea Lee!) Fossil Energy & Environment Research Department, Korea Institute of Energy Research Techno-bio Co,, Led. (Received 7 August 2007, accepted 10 January 2008) Abstract This study is aimed at substantially reducing the particulate matter (dust) emission during the combustion of heavy fuel in boilers by addition of combustion improver. The combustion improver used were the oil-soluble organometallic compounds that were found to be more effective than the dispersing agents that are generally used for reducing the particulate emi: (metals) as well as on the organic li The dust reduction effect was found to depend on the active materials ind part of organometallic compounds. Acetylacetonoate and naphthenate of Fe and Ca were found to be most effective for dust reduction. Addition of Fe and Ca organometallic compounds as ‘combustion improver in concentration of 30 ppm (metal basis) to heavy fuel oil, caused dust reduction by to 80 wi% Key words : Dust, Particulate matter, Fuel additive, Combustion improver, Organometallic compounds 31 204 ANE, 2006), AAMT SSH LAE 218 BA Dustehst HEeh Bele Fo) Lala AW -SALG AAS AF Dust] Hae Aa B71 MALE Sabo} A) ee GAH alob vba ul ol Abo] SIU] ISAB, 2006), (arcuate matters)2) ABOBEL WA BHS ce wy} BAe] ALA selene, alla?) = = = 2) AAAS AAleho} Dusese Alaa + slo “Tel 48240)42 860-3016, E-mail: dekim@ierseke SAS ARs] de sola cladeaw Lye 7 J. KOSAE Vol. 24, No. 12008)56 Aga MAPA + foal ale oledat et Jat te) Basi. Be a Bas ae Sas) WLS Se] SAR Ut12] Dust WHS SA AFH SAO] heh. BAPE Ta Be S olztelse] HH} a ole BH) AR, VANES 34] (flocculation Jagglomeration) GS 7S} Sal Ygste Se] get. lasted Uehe Ue Sl MS] SF ol) Oe} Abol7t Lor WAC 4:2] 7 1~Twt.% of JST. EA SALE Meo] Babs] oft Rs} Sallzoe else} Qalfol] va] wap yay (droplet?) Jo] at FUR AAjo] YA}s]7] o} qh. tela Agee dade} Yous a SA) viaietee] Wyo 2} Dust] wh eeke] 2 EX PA (soote] BYos wujo] Addo] De °] BOR UAT] Ae 2a aadyje] ARS A WHE 712A Ae Giammar et al, 1977), WH ARS] AAA) wefolj]o] Bap aay + a Isto] S7lesty Set Beas] WAS ae] ateee 4 SU PE MOU o]s} BE PISIA Nakos Geese Hele Poe UA} Nt. Tew Salt Se] SalzRe (pase Sage Ser)e S149) Ass elt aS S ddebl Hse we} Fee Sate wold #44] 94749173 (droplet size =) 3H Vale) 34, ey adage] VQ dawg] Ashe HAAS} Dust®] Sb S71. ols} BE SAH AGOs Mele] Sale Af Bee) ¥]s Dust Wao) B7-e}7] eo) 3417)A) (fuel additives AAB8te] o}ADY gl Bg BAe aes) ahgale BHI} Posy Seve] Dust WIS AVY Sd 4 91e+ (Kazuhiko and Kenichi, 2005; + ##, 2002; Danilov, 1998). BRA HN SLR He] okaatel BY Save] a WAISS YS she wb (dispersan)s} @2B Salshe @ag-la) (com. bustion improver). BF + 912.0] (SB S} ABR, 2005; 8A -S, 1999), 749 AA web F719, -F 748. FES ASAI S HEC (Eliot, 1978). PASE $7148, 771489) AAPA) Bla #839) $71849}4H (oil soluble organometallic compounds)] AFA AVES] $4At Aloe abe} 432 916} (Mitchell, 1991; Somasundaram and Suna- ty cB ot VAI Ne A vala, 1989). 71e43bes] Gaga 71S active materials. *F88HE PHVA] Sse] heh 225} (Witzel et al, 1995), active material] 4187] FE AKEES] SH} YASH (combustion cata- lyst 2A 9] 4h8, 39 ol “7h (flame ionic mechanism), 8}°]£34) ee) (hydroxyl radicals)2] Aas AQ APA Aa 71 BLS aAsley (Fuel Tech Inc., 2003; Howard and Kansch, 1980). BAPE HA THe] ASIST Me + $9 27148 AVS Paste} AS BHR dejo) AAA) Dust 4p BSE Yohwgheh. telat asl AQ heel se 7 G9) $8 WITS Ade] BSH ID 2) 2\ZbE (ligands) Dust 44h s-S LA BtAb aislen, aaealals4e] By aH at A # Dust?) UAPEES watt. 2 ae ee 2.1 Saf Ne Adel AB SHE FAKE LOW. 7189 SHE HD ee SR) WAS & le] =12]32 Thin Layer Chromatograph (TLC-FID)¢i SIE FALE H 20) BALES 2.2 ABe7 Ae 2.2.1 RU ASARS ALE 5U) SAF AsAl7bl Awhesse] F714) ASW OFS Ueto} Dust 24h AUS BA Table 1. Elemental analysis and properties of sample heavy fuel 863 20 w~ N 038 Elementi) ae ° 03 Ash 0.02 Heating value (keal/kg) 10.484 Specific gravity (154°C) 0340 Properties S) 0 Ignition point BI Boiling poine(°C) 2121$A AAA $24) SLBA AAS) Dus qaeg 57 uh A714 ARAZHNS| FA ARLE 2p oHA| ys] AS Yt LOM, AH) A VRS zh Ao AL AMAR SLE anette} alee} 1/1,000~ 12,0008 Ah FLA Basho} AhG shale 2.2.2 FEY PIBSHE| ASA Als BAW datas ote) ‘ AL GTSLES Hate} Dust 1 Ys Tale) OFC. AIALGE Bele} lt 87 ABE Be) Ue. ASSES) Dust 47} LAGS AITSSHEE TAlsh “2 51 $71 (organi HAS Mae ach 2h As] So) Ae aby © A7ESRNE S29] F4(meta) BY 7]HOe $4349) 30 ppm& ahebsaeh 2.3 4a Ba ot ow 2.3.1 SHB Slay 7a W2dds BIE] BS a4) wales BEL SA ODS ALB ISL) of}, wut Heblelet( 29 1). Cyclone Dust measuring hole Feed water Oil Sher # ¥), Ca BAA Hehe, ALG B71 Aas 2} Sa PS = > US, 9) dey 4) ALAS UA $4) wa Bt eg ae} Alesis #94) ¥h9} 7) = Svol.%2A AYS7S USA AVA, Bh BAG! 2kelem’, Lela else] ae DHE ARS lOkghsA BUel Bet APA GeVsheh eA Dust] wh sel £80] upH Ly Aol?) debe 141% 9] AE SWB] AS spo} eu] Ber} dal PH Ss, ans Se7} wore dee eal alas absis Table 2. Composition of sample heavy fuel oil in terms of area % of Chromatograph. Fig. 1. Experimental set up of combustion boller used for dust reduction tests. Heavy Ol Saturated HC Aromaticws Resin Asp SosWOi 47.279 3811S. 62S «GRSS SLOwO; 37522 «43362_—9Si4 9.502 Steam exhaust Water level Buner(Chun-type) Coabustion air controller J. KOSAE Vol. 24, No. 1(2008)58 DBA MAb Fal} gale olla} ABA Dust ASS ASIA. 2.3.3 Dust 55 Aa Sat A2dd Bel PSS] S Dust ee 2] 442, "]5} Clean Air Express*}2] Stack Gas Sampling System (Model: Method 5/17/23 Sampling Train ASI. Aaa Hele Sel A\Z9| (Isokinetic Stack Sampling System) 22. =-42 Fo} st Dust2] ASS BYALBSRA1Y Vel] aisict. 2.3.4 Dust IEE Dust?] YER SALE laser diffraction Qe]oH) AR Coulter Particle Size Analyzer (3.88: LS-230) ALBEIT, 9 SAYS 0.04~2,000 umel eh. 3. dea st aa 3.1 Su SB ALAA] Dust AZ S32} Sue Bessy we f71d aR (organic fuel additive)ol] At Dust A 21a ashe 2Y 2e] BASHA. XH] OF ARAN BD 7B) be HelD lee Ab] ARAW PIE AEE oleh. Dust WS BAS UA) 47 mg/Sm*6]1, TA AIS] 73-39 mg/Sm'=A4 Dust APES 20% GEpae. Tela 7Je}s) WHS Dust 14h) BE BSS GERI. oft LAMAR ashi} Vietes FAN dewey aasldepy] whe dee BISA 7s 7H) ASAPAe|7) We BOs YAS. ae avis] ALS Ahh elas Go Woes FAR LS EPA + Bor 3a 2olja| Tap ae 2 SH 60%, APES 30%, ACSA) ABW Al 5%, BAL SES PAA, WA ABS SH 16.8%, BA I.2%G, WIDE 11.0%, NPE 45%, IEF 45%71 BHA Bos Azz al Ash Sle. else & ALVA] Z}Ap ABS) $7) VA UES BAW Dep Wt 79~87%, pa 13~ 14%, Aa: 0.2~0.3%, LE) HSE ey 0.02 ~0.03%% Wah We Woe yEhtory ols} 2S quakoze Sy 38 asyvbals] SoH ae Dust 4 Vee TASe Yeh Use7iabyesi4| asad ae Table 3. The selection of combustion improver for the experiment of dust reducti No ‘Conbustonimprover wit of etl 1 Ferosene 0 2 trond alte diydate 3 3 Manganese(I) acetylacetonate a7 4 ron( HP scetyacetonate 158 5 Barium acetylacetonate hydrate ” 6 Barium oxalate 9 7 Calcium acetylacetonate hydrate 168 Hon naphibenae, 80% a iniminerl pn (12% Fe) 9 Minot pistes iowa” 619 10 Magnesia naphthenale 5~85%Mp) 35~8 11 Calcium naphthenat, approx. 35% A in mineral spirits (4% Ca) st concentration mg/m) Pad oT GS K WN ‘Domestic commercial heavy fuel ol additives Fig. 2. Dust reduction by domestic commercial heavy fuel oil additives (organic additives). WA} gb ALz LYAdH Poullikkas, 2004), 3.2 FBS F7IBSAHBS| Dust AZ as AV) dade +44 fleet (oil soluble organometallic compounds) A) 3 3] sEA)8 A 71S gab ake 4 A F active materials) BHPY, Le]st HIE 2] SPR Dust 44b Pes AVA a7) ae debs. aby wet).BAR AAA FEY F71eHE aasalals] Dos aH 59 3.2.1 971% SHE Oust 2 BS Wes Sia Dust zt ve AY asks 33} do) epg. 19) 32 naphthenate™) 47) P4SHNE “est 29] Ae acetylacetonate] -f 7lsH PS VE DYAsto eo] hase ae 71S) WS BLE BL S Wppme Bsr}. 14) Fe] Dust WARES SHU BAA) 49.8 mg/Sm'o] BW Dust Wyse] 7} 7% AL calcium naphthenate2| 73-$- 6.1 mg/Sm'zA, Dust 4Z4&2- of 80% UEHAT}. Naphthenateal PISS RTE EHP Dust 22H = 30~80%-F YEO ZA} ols 19} 20] Be) vps} AS #713 ARAZ7b Mo} vYe Dust 42 452] wl HePde tt 4 aleh Active material) 4d & SHel CHE Dust 47hee Bl Ca>Fe>Mn> Mes] €9.3. Uehite}. AcetylacetonateAl 7142422] Dust 12h AL UAE 2Y 4o] Wage. HTS Sa Dust 47 2335-2 naphthenateal $7132} gHES} * Ab2]7} BS274, calcium acctylacetonate7} 74} PR Dust AP PES MSE} ALVA acety- lacetonateA 71243329) H71TS BD Dust A255 naphthenate) 7ERSHES bsp Ca> Fe>Ba>Mn9] 24 uae} HBSS] os} AS Dust 4 7]Fo) a ah AB Ssh ee Ae] 712 BAe} (Fuel Tech Inc., 2003; Howard and Kansch, 1980). (1) Fe, Mn, Nist BE Aol F71SNES Ab AS34412] She Hoey 7s) ASS Slstat me} dash dell] Wasps Pledgha 6] 214) 4b8le} (oxidative mechanism), 2) K, Ba, Cs} BE F71ESSREES s}ehu}ol Al O23} HAJo)] He sehi] Et Beh Ertella] 2} o}23} Agel Sha} TS YAS HE nucleation’ coagulation @4-S B4-4r} (ionic mechanism). 3) Ca, Sr, Bas} BE -A7IGSSHHES HVA SoA} hydroxyl radicas -938}2, hydroxyl radi- calst= EA] soot E> 7}AAL2] soot AFA] + WS3}e] Dust 14 Ee} (hydroxyl radicals pro- duction mechanism). #141 58] Ba®] 73-7-< (2)9} 3)2] BS 7)F-3. aA8le} (Howard and Kansch, 1980). 0,———_— [Ar No additive B: fron nuphens [C: Calcium naphthenate 1D; Maganess naphthenate ]E: Magnesium naphthenate [” ibs A D E Dust concentration (mgm?) ‘A "Naplihenate based organometallic compounds Fi ig. 9. Dust reduction performance of metals in naphthe- nate based organometallic compounds. _ | | | 50 |---| B lon acetylacetonate 1C: Calcium acetylacetonate 1D: Maganess acetylacetonate | E: Barium acetylacetonate ” Dust concentration (mig/St) s A a B c Acetylacetonate based organometallic compounds Fig. 4. Dust reduction performance of metals in acety- lacetonate based organometallic compounds. 3.2.2 $718 (organiotigands)9| A che Dust Ha ds SIS) Se Feal®] 471843 HE iton oxalate, iron acetylacetonate, iron naphthenate@ sto} f-7) USSHHS oF WE 7B] Stel) BE Dust 14 PES Bal Aeleh ze FeAl) 71g SSHHEIAS HALES Sa we} Dust Bol HA VEPs a + eh Rea flee SAMS] $7121 LEA THE Dust AES naphthe nate> acetylacctonate> oxalate 2.3. YEbsECh 6] J. KOSAE Vol. 24, No. 12008)0 AER SMA Sal ALE. ld ArNo additive B: Iron) oxalate dihydrate f-~ (C:fron (if) acetyacetonate D: Iron naphthenate Dust concentration (mg/Sm") Fe hassed organometallic compounds Fig. 5. Effect of organic ligands on dust reduction per- formance of organometallics. Pilea 7 ef — Cama | SeSESR SESE ‘Cumulative percent (%) Differential volume percent (%) © 12 345 10 20304050 100 200300 500 Particle diameter (um) Fig. 7. Particle size distribution in the dust from com- bustion of heavy fuel ol. ust concentration (gS?) 100-600 1000 Concentration of ion acetylacstonate(ppe0) Fig. 6. Efect of dosage of iron acetylacetonate on dust reduction. S} Aho] FIR active materiale) |S. §7]2]27=o] ae} Dust 44 Vee] A YER HS 2S B71 B9] BASES) Apolo else Roe Belaep (Somasundaram and Sunavala, 1989). 3.2.3 M7 w Dust HZ AS 24} 62 iron acetylacetonate 2] 27}3 Dust AI Pek WA). Age] eS Dust AAS RI Fe 718% 50 ppm7talt A7tgo} vlalabe} Dust 271340] S7}3}31.24+ 50 ppm 4b 7b} Dust 414130 AS UEbAeh ©} Fuel Tech Inc. baz age aa a2 ‘Cumulative peroent(%) Ditfetental volume perce ° im 20304050 100 200300 500 T2345 Particle diameter (um) Fig. 8. Particle size distribution in the dust from the com- bustion of heavy fuel oil containing calcium naph- thenate as combustion improver. (2003)2} st AhsLoi) AALS) Dust 717hE IQ dae a2l4) ae) Wess ASS ACh. 3.3 ALSAA] APBoll 21st Dust WAL a] AG 73} 82 DAME eelol] S44) AA) Sale] 242 Dust9] WES YEA) (Coulter Particle Size Analyzer: LS-230 BD)2. 43 Stel FH] WS] 432 (cumulative vol-ume percent)9} =4\32 (differential volume percent)= SAVE Ale. 2G) 72 He AAA) Dust} WAREPF ADM $849 HOESIMHE ALATA Dust VASA 61 ES AIS AY 82 SH ALSVARA cal- cium naphthenateS 30 ppm (Ca 71) 27}s}e} Aa A) WASH S Duste] YAS Yeheh. 3) 73} 2a 8ei]4] Dust] lai} 7h ee] abet aye 9~100um We] SHU UATE: Bel] ¥] ah adele Atte} dase 247} ye % He] DARKS tebe. te] st B47 (arith. ‘metic mean diameter) $4} Qe Dust} 74.3 um, LSA] A7}]2) Dust7} 88.5 pmo24 AAS Alal U7} Dust] Bee] Ssh WHS wal FE ER 10pm fs} PRIS) Psp eS wed s Fhe AAs: BH) va) AAS alas a7} = BS7b a AA Uepse BAT. 4a 2 DsHIA 4ASss|a we Hla aay = ASHEN 1/1,000~1/2,000 A7hs}e] aa A) Dust A2HES AEs Ge} Abo] S Ushou} gh AALS. 0% oH] ARR wae}. Dust az eo] eat 37] 2 Ae assess) 4a Bh: dat Wbleals] Ae] = a Zils ALe. 4A. 2D Bat AA MHF EM HH H7lt 43}913¢ (cil soluble organo metallic compounds) AbBA) Dust 2a SA dekh eed B71 PESTS] Dust AMES ALLS] Sapo) me} A}o]7} 3st, 8 $712] 215 (organic ligands) 2} SH PAS. Dust AA Ese LLL] Aho} 4 BCE Calcium naphthenate, iron naphthenate Ca, Fe E22 Sell 30 ppm aArtsle| Aas} Dust 13H: 50~80 w.%S Yeh weh. UAL Ca, Fe E 50ppm ly A7H1a Dust Azo] e] ol ah Ss 7He Bola) be UASSE Balch. 3) Duste] W242, AS4Alals B7bshe] aa) Bile deste 24) Mal MAE] Ha Urbis Seldel She Bele. 2e)at Dust F 10um ja}2} ozs] wae Aas Ah A471 es Ae wich. 4) Ag ALFA} As} 971025 Dust 414 AVS, ALFA J AKL BW 714, eaFal Al 2739) RAISHa Se] AWebsholok Bh, Ed FH She] SA ALA Dust AAR se] Hat Ad dastalale) tele] 7hs Bbc. HAS] 2 ate P| Sere Ags HAYS OM, oo) AERIS azine YEA, AP, 24 (2006) AGE: Bele] TL ale Sad) Se BA pL oe oat] At “lee, Uda ee zal, Hela) Byes ww}, 011-031.010, AGB, HUE, BS, B41 (1999) GL AL BAA SAS UTD, HEALS $1999. 009206, AHA 2006) AES} VARA 18 7194, eee7] gata, 225), 925-553, PAR TGR AB 2005) era, Bo CMA Ri Hts $3EHe (2002) FFT Guide, Ea MAB. Danilov, A.M. (1998) New additive for fuels: analysis of publications for 1991-1996, Chemistry and Tech- nology of Fuels and Oils, 34(1), 1-58. Eliot, RC, (1978) Boiler fuel additives for pollution reduction and energy saving, Noyes Data Corp., U.S.A. 23- 2, Fuel Tech Inc. (2003) Fuel Additive: Smoke-Out, Fuel Chem, Fuel Tech Ine. Cat. U.S.A, Giammar, R.D., AE, Weller, DW. Locklin, and HLH. Krause (1977) Experimental evalution of fuel oil additives {for reducing emissions and inereasing efficiency of boiler, Battlle-Columbus Lab., U.S. EPA Contract No, 68-02-0262. Howard, J.B. and W.J. Kausch (1980) Soot control by fuel ddlives, Prog. Energy Combust, Sei., 6, 263-276. Kazuhiko and Kenichi Yuge (2005) Effect of fuel additives ‘on reduction of smoke and particulate matter, and stabilization of cycle-to-cycle variation, J. of Japan Petroleum Institute, #814, 229-235, Mitchell, .B. (1991) Smoke reduction from burning crude oil using ferrocene and its derivatives, Combustion and Flame, 86, 179-184, 1. KOSAE Vol. 24, No. 1(2008)62 AB RN - Gold ale: lea Poullikkas, A. (2004) Cost-benefit analysis for the use of additives in heavy fuel oil fired boilers, ELSE- VIER, Energy Conversion and Management, 45, 1725-1734, Somasundaram, G. and P.D, Sunavala (1989) Suppression of SANIT A AUT A Soot inthe combustion of residual furnace oil us- ing organometallic additive, Fuel, 68, 921-927. Witzel, L., P. Moszkowiez, and G. Clausst (1995) Mechanism Of particulate reduction in heavy fuel oil com: bbustion, Fuel, 7412), 1881-1886.