A Study on the Reactivity of Zinc-based Sorbents for Hot Gas Desulfurization using Natural Zeolite as the Support

HWAHAK KONGHAK Vol. 41, No. 5, October, 2003, pp. 667-674 *, 712-749 214-1 * 702-701 1370 (2003 5 6, 2003 8 11 ) A Study on the Reactivity of Zinc-based Sorbents for Hot Gas Desulfurization using Natural Zeolite as the Support No-Kuk Park, Yong-Kgil Jung, Jong-Dae Lee, Tae-Jin Lee and Jae-Chang Kim* National Research Laboratory, School of Chemical Engineering and Technology, Yeungnam University, 214-1 Dae-dong, Gyeongsan, Kyungpook 712-749, Korea *Department of Chemical Engineering, Kyungpook National University 1370 Sankeuk-dong, Bukgu, Daegu 702-701, Korea (Received 6 May 2003; accepted 11 August 2003)! "#$ %. & ' ()*"+,- 480 o C/580 o C(.//01)23 4 567 89 ():; ()<1 =#> $?@! ABC +,:; ABC1 %. & "# +,DE F GH.()<1' F I% JK!, 10 cycle23 = #> 20 gs/100 g sorbent L M NO%. ABC"- AI(BC P)Q 14.7%81%. R S23T U '#"$ VW%. Abstract Two types of zinc-based sorbents using alumina and natural zeolite as the supports for hot-gas desulfurization were prepared, and investigated their desulfurization capability. Their reaction rate and sulfur capacity were compared by Cahn balance and over the fixed bed reactor system at 480 o C/580 o C (sulfidation/regeneration). The attrition resistance was measured by ASTM method. The initial sulfidation rate of ZnO/natural zeolite sorbent was higher than that of ZnO/alumina, and the sulfur capacity of ZnO/natural zeolite sorbent was maintained above 20 gs/100 g sorbent for 10 cycles. A attrition index was 14.7%. The use of natural zeolite as a support of sorbents may be possible for hot gas desulfurization. Key words: Desulfurization, Zinc-Based Sorbent, Natural Zeolite, IGCC, Support 1.! "# $ %&' ()* +,-.. /0 12 34 56 789$ : "# () ; < 8= >?@% +.. 789$ :56 8 9A$ ()* +B CD EF GHIB AJ K $ ()5B 7LA MN OAP(IGCC)Q RS TU 8V OAP(PFBC) W +!, :XL)Y 89 (MCFC) ZB %)[ 89(SOFC)$ :56 $ ()5 To whom correspondence should be addressed. E-mail: tjlee@yu.ac.kr B A 89(IGFC) W 8= @% +B\, ] D ^_ `% +.. 789 Q#4 (5B H 2 S, SO 2, COS, CS 2 WQ a bn[ c# JK d 89 efd gh i + j kl m n Sop q ry S* +.[1-3]. s S 789$ :56 "#$ ()5 t4b 89A n usv.w bxy z{o }t-~.. 789 Q#4 (5B bn[ }5B @% +B %ƒ bc# % y b $ :56 450 o C h %ƒ4 bn[ ˆ Š }5 &' Œ% Ž kl 2E ry (5 B.. Z : b $ cy 4 (* +, x q5.b 6s % +.[4]. 667

668 %ƒ b B ^ )[, +B\, š œ, = Žœ, œ, k8œž a.ÿ x b 8= @! ] n4 )k8 ^ z [ D k8œ b B bn[q z x q56 1 DOE(department of energy) )5 RTI(research triangle institute), METC(morgantown energy technology center) W4.Ÿ x b $ 8= 5!?v +.. ª, )k8q )«L ^ xy 5B MN )[D zinc titanate b B #x q56 650 o C h %ƒ b N b +.[5-12]. /0 123 6s 8= ] %ƒ bc# 650 o C h % ƒ4 ±p q e²œh ³ ž ±, µ³ 500 o C # nƒ ± 5 5 B ¹ 5% +.. ± ƒ 5 ºm nƒ b x» ± Q o@ O¼½.. >1Q 12 8= ] t4 x¾ v zinc titanate b B 650 o C h %ƒ4 q x¾ j~ klm ^z [ D )k8 #x Œ 6^B À +~ nƒ ± 4B Á [ # zã z x Ä À @.. ž a MN ) [(zinc titanate) ³ tå5 56 #x Ä ) k8 Æ Ç VÅÈh /V OÉÃ4 nƒ ± 4 z x q b $ 5 ¹ d ZB Ž Ê W :5% z x 5 56.Ÿ Ë $ : 8= < >?@! 14B. Ì dž +B #.[13-18]. %ƒ bc# z OAP %#U, TU, STU @, +! ÍÍ Î +d /0 @% +B %ƒ bc# z 56 ƒ, SŽ STU bc# Ï @% +.[19]. STUc# :5 t4b 2ÐÑx - 5! 8 (zm :O x¾ S@ t4b 2=x qt-.. Ò 8=4B dž ŽÊ$ TO us5% +B 12) Ó 8 Ôm I$ :56 b $ 5! d$ : b ž z x Ç 2ÐÑ x ÁÂ5.. Õ b z x, 2=x, 2ÐÑx 5% ] ÅQ $ Ö 12) Ó8 Ôm I$ STU: k8œ b x¾»± O5% 5.. 2. 2-1. Ò 8=4B %)[ N (solid oxide mixing method) % ƒ k8œ b $ 5.[17]. Ø Ù 20 µm 5D ) Table 1. Composition of natural zeolite Elements Composition of natural zeolite, wt% SiO 2 65.0 Al 2 O 3 14.8 K 2 O 1.61 Fe 2 O 3 2.64 MgO 0.78 CaO 4.44 Na 2 O 2.65 TiO 2 0.36 MnO 0.08 P 2 O 5 0.33 ZnO 0.15 BaO 0.07 k8q $ 75:25 Ú Á' ÛÜ(ball mill) Ý% 24 OÞ T yß Ç N à Sx ÅN D E.G(ethylene glycol) á w Ë56 Æ9[ âyª zã56 ä,> % N[ Ro x å5.. µ B d(aldrich)ž Ó8 Ôm I(Tæ)ç, ^))$ :5.. Roxå v èé ÑŸ xå$ 150 o C4 24 OÞT 5% 750 o C4 2 OÞT Ž5! á Ù yß56 150-300 µm Ù Ø ~ yž à 750 o C4 2 OÞT.O Ž5.. Z : ºê k 8œ b Æ x ÁÂ5 56 $ :5 % ë )k8~ Tì b $ 5.. 2-2. - z B 2 15 mm 7í; :5! O9$ ÝB sample capacity tubeb 7í î :5 % O9 â>w 50 mg # 56 Æ, b, (?5.. Æ, b, (O Table 2 dï2.. k8œ b nƒ 4 Æ x 5 56 ð-ñò A$ :56 Æ?5.. ë )k8~ b ž Ó8 Ôm I$ N b 56 bv us@ 7LÑ A ÍÍ 10OÞó ¹oOô Ú õ$ ;ö5.. µ ƃ B 480 o C! 7LÑ A S 250 ml/min z 5 4 h øù ú 5.. b z x b Ç ( J û5! z B z OÞ ð-ñòa(cahn instrument) ü# Ú õ J z $ ÁÂ5.. bz cyúå A4 ()@B 7LAž x S Ñ A$ :5! ( AB 5% )V usv V ý7 c$ :5.. µ S Table 2. Experimental conditions for reactivity and durability tests by micro-reactor system Conditions Temperature ( o C) Pressure (atm) Flow rate (ml/min) 41 5 2003 10 This work KRW Reduction Sulfidation Regeneration Sulfidation Regeneration 480 1 250 480 1 250 580 1 250 650-750 15 690-760 Gas composition - H 2 S 1.0 O 2 5.0 H 2 S 0.55 O 2 2.0 (vol.%) H 2 CO CO 2 H 2 O N 2 11.7 19.0 6.8 10.0 balance H 2 CO CO 2 H 2 O N 2 11.7 19.0 6.8 10.0 balance H 2 O N 2 10 balance H 2 CO CO 2 H 2 O N 2 11.65 18.97 6.75 5.12 56.95 N 2 98.0 R P (reducing power) 2.6 2.6 2.58

!"#$ 669 Ø@B z AB 5 4 h 250 ml/min S þ ^! b Ç (z ƒ B ÍÍ 480 o Cž 580 o C S5.. 2-3. Micro-reactor b 8 zm 2=x %#U z 4?5! b b Ç (z ÿ Þ^ 56 ÿ zm u ºê b :¾(sulfur capacity) õ# J 2=x û5.. z B 7í 2 10 mmd %#U øz $ :5 % SØ@B Ñ A ø 250 ml/min 5.. Ò 8=4 : 89A x Table 2 dï ž a KRW cyúå A4 ()@B 7LA x Ñ 5.. (AB 5vol% )Vž u 10 vol% [ N5! b Ç (z ƒ B ÍÍ 480 o C, 580 o C4?5.. z o=b T.C.D.(thermal conductivity detector) Ç PFPD(plused framable photometric detector, O.I Analytical) v G.C.(gas chromatograph, Donam DS6200A)ž ƒ-md 8Å56 z à A x y75 B\, y7: š Chromosil-310 (Supelco) šq GS-GASPRO ÑF; š ÍÍ TCDž PFPD 8Å56 :5.. bz z o=4 H 2 S 2,000 ppm @à 95 % cž V Ž% [ N (A$ SØ5Ã4 bv b $.O (O! z o= A x y756 SO 2 o@ µ (z 95.. 2-4. b 2ÐÑx ASTM[20] ¼v 2ÐÑx O e(attrition tester)4?5.. STAB V(N 2 )$ :5! 2ÐÑü# ST y b 50 g â> 5% STA$ 10 l/min S þ ^! S AJ(wet gas meter)$ :56 ü#5.. µ S Ch (0 o C, 1 atm) #5! û B 30%# S 5.. B 2ÐÑü# e2 #$ }5 À! D ^Ø [ hƒ R t4 (5 ú e5.. F y : I 1OÞ Î Â56 v Fy Ú $ ü#5.. 2-5. b z à [xõ B BET Cà ü#(micromeritics Gemini 2375), XRD(X-Ray Diffractometer, RIGAKU, D/May-2500), EDX (Energy Dispersive X-ray, FISONS, KEVEX SIGMA), SEM(Scanning Electron Microscope, Hitachi, S-4100)W :56 y75! C Ã[xõ CÃ, Å#x, k8 uw, CÃåh W ;ö5.. Fig. 1. Reduction of ZnO and ZnO/Natural zeolite with H 2 at 480 o C. s ÅQ Û µ k8œ b 7LA t4 480 o C # 4 Æ >? D* +!, $ :u4 Æ * +.. )k8 Æ@à ÆV k8(zn) 5 @B\, ÆV k8!b 419.5 o C # Ò 8= b z ƒ. Ä µ³ %ƒz 4 VÅ(sintering)v.. Æv k8 VÅ b z x 5 ÆD p +B\, Ó 8 Ôm Iž a $ : k8œ b (ZnO/natural zeolite) q $ :5 ë )k8 b (ZnO) Á56 Æ " #$ D* +.. Æ "Ž.B À ÆV k8 Æ@,% µ³ VÅK $ VO &Q TO VÅ k8œ b x¾5$ * +.. 3-2.! Õ $ : b b Ç (z O z OÞ Ú õ$ ð-ñòa ü# ÅQ$ Fig. 2ž Fig. 3 dï2.. dž Ó8 Ôm I$ : Õ b bz $ Á ÅQ d$ : ZnO/Al 2 O 3 b Á56 Ó8 Ôm I$ : ZnO/natural zeolite b Öz ž ûå ' h4 b Šw é Œ À dï(.. d q bz 4 bvž z x )d Ó8 Ôm IB bvž z x +B.Ÿ xy 3. 3-1. ZnO Ò 8= bz ƒ D 480 o C4 7LA )k8 (ZnO) Æ x 5 56 ð-ñòa ÅQ$ Fig. 1 dï2.. ë )k8q Ó8 Ôm I$ Ë b $ 480 o C4 ÍÍ 10OÞ T ÆO ÅQ ë )k8 15%#, Ó8 Ôm I$ : b B 3.4% # Æ@.. µ Æ B ÍÍ b us ZnO )V w Ú w Á$ y' œ)5.. Æ Ú Vw Æ (degree of reduction, %)= 100 OÆ w ZnOuw ZnÆ w+oæ w Fig. 2. Sulfidation rates of zinc-based sorbents. HWAHAK KONGHAK Vol. 41, No. 5, October, 2003

670 Fig. 3. Regeneration rates of zinc-based sorbents. Fig. 4. H 2 S breakthrough curve for the sulfidation of ZnO/Al 2 O 3 sorbent at 480 o C. *+ us@, + µ³ Öz ž b:¾ é q À,Îv.. Kim, Lee W[21-23] k8œ b ), ) l-, ).I WQ a )[ Ë :* q z x Ç 2=x * +.% % +.. Ó8 Ôm I us Fe 2 O 3 (2.64 wt%)q Na 2 O(2.65 wt%)b (1-3)Q a z 400 o C 5 ƒ 4 bvž z x q5 µ³ k8œ b Ö z x Q b:¾ í eb Ë ¼:* À,Îv.. 3Fe 2 O 3 +H 2 /2Fe 3 O 4 +H 2 O (1) Fe 3 O 4 +3H 2 S/3FeS+4H 2 O (2) Na 2 O+H 2 S/Na 2 S+H 2 O (3) Õ b (z x z OÞ Ú õ ;ö ÅQ, Fig. 3 dï ž a Ö 80y0 (z B ZnO/natural zeolite b 12d 80y àb ZnO/Al 2 O 3 b Ú õ é 1Ž >?@.. Õ b ÑÕ 250y 2 ( 39@.. 3-3. " b- ( 14 Ov À 1 ÿ 56 ZnO/Al 2 O 3 b ž ZnO/natural zeolite b b- ( 8 ÿ? 5.. bƒ ž (ƒ $ ÍÍ 480 o Cž 580 o C %#OÉ% 10 ÿ O ÅQ H 2 S 5Q6 Fig. 4ž Fig. 5 dï 2.. ZnO/Al 2 O 3 b q 6 ÿ b- ( zm@b T 1 ÿ z O¼ à 150 min, 2 ÿ 180 min, 3 ÿ 220 min, 4 ÿ 210 min, 5 ÿ 200 min, 6 ÿ 170 min0 z o=4 H 2 S 7 o@ 8! 5Q6 9 Á 5.. ZnO/natural zeolite b q 9 ÿ >?@B T 1 ÿ bz O¼ à 140 min, 2 ÿ àb 200 min # 0 H 2 S 7 o@ 8! 5Q6 9 5.. ìz b ž a Š B Š ºê z o= Oõ 5Q6 9 *ú & '! ^xy z :65B Á' Œ.. Õ b ÑÕ Á b&' Œ% ^z [D )k8 z :65B Á' Œ À dï(.. ; Õ b ÑÕ ÿ ºm ÖB b:¾ 5B À dï(b\, s ÆD 1 ÿ4 b Ø 2 0 3ª z :65 8 µ³.. %ƒ b Fig. 5. H 2 S breakthrough curve for the sulfidation of ZnO/natural zeolite sorbent at 480 o C. -% z Szekely W[24] grain model ²f @B\, GibsonQ Harrison W[25] nƒ4 grain )<(grain diffusion resistance) Œ µ³ H 2 S b Ø n= y0 )@ µ³ b >x Ä dï?.% % +.. ; Kang W[18] b- (z zm@b Q#4 b Ø @ AB56 Fc åx@% CÃ.% % +.. ] 8=ÅQ$ ÁÂt Û µ Ö ÿ bz 4 b b:¾ Ä À H 2 S 2 ) "è À ÆD! b- ( zm@ã4 c (x J 2 ) SŽt# µ³ b:¾ 5B À ²f* +.. bz 4 b Š b $ 580 o C, 5vol%)V(O 2 ) (Q#4 (5B SO 2 Oõ$ ;ö 5Q6 Fig. 6Q Fig. 7 dï2.. ZnO/Al 2 O 3 b q (z O¼ à 3%# SO 2 So@! z O¼ à 50-100 min# 4 SO 2 So V5 O¼5B\, SO 2 5Q6 9 3~5! z ÿ *ú 5Q6 9 3~t % TO (9OÞ 8@, 6 ÿ4b 300 min# 4 ( 9@ 8.. ZnO/natural zeolite b qb (z O¼ à 100 min # 0 3%# SO 2 So@! 5Q6 9 5% 250 min àb SO 2 ;ö@ 8.. ž a b ( "è À b)y (x ^ ÆD +.[26]. C, bk8(zns) )V t4 ) 41 5 2003 10

!"#$ 671 Table 3. Sulfur capacity of Zn/natural zeolite and ZnO/Al 2 O 3 sorbents Sulfur capacity(gs/100g sorbent), Number of cycles Sorbents 1 2 3 4 5 6 7 8 9 ZnO/Al 2 O 3 21.1 25.3 27.2 26.1 25.2 22.2 ZnO/natural zeolite 20.2 26.1 25.3 23.2 25.1 26.3 27.4 26.2 26.1 Fig. 6. SO 2 breakthrough curve for the regeneration of ZnO/Al 2 O 3 sorbent at 580 o C. :¾ Table 3 dï2.. ZnO/Al 2 O 3 b q 1 ÿ 4 b:¾ 15 gs/100 g sorbent #, 3 ÿ4 25 gs/ 100 g sorbent#!, 5 ÿ à 20 gs/100 g sorbent # $ S5B À dï(.. ZnO/natural zeolite b B 1 ÿ 4 b:¾ 20 gs/100 g sorbent #! 2 ÿ4 26 gs/ 100 g sorbent # Sv à 4 ÿ0 V@..O 5 6 26 gs/100 g sorbent S@B À dï(.. ÿ º ê b:¾ ZnO/Al 2 O 3 b q 4 ÿ0 5. à V5B dï2! ZnO/natural zeolite b q 25 gs/100 g sorbent h 10 ÿ 0 S@B À dï(.. 2=x q À v ZnO/natural zeolite b 5 6 10 ÿ à x¾ D5% x¾ b- ( 30 ÿ?5.. Fig. 7. SO 2 breakthrough curve for the regeneration of ZnO/natural zeolite sorbent at 580 o C. (@B Q#4 Õ $ B\, 5dB (4)ž a SO 2 )@B À!.ê B (5)ž a b)y(znso 4 ) (x v à b)y %ƒ yt t4 SO 2 @B.. Ò 8 =4 b ( ÐD y4 ( " B SB b )Y (x D5B À,Îv.. 3-4. 30 #$% &'" Ó8 Ôm I$ : ZnO/natural zeolite b 30 ÿ x¾ b :¾ Fig. 8 dï2.. Fig. 8 4 dï ž a 10 ÿ4 b :¾ G 5@ B\, 7íz b â>u y ;ö ÅQ, b AB t4 ÏHI Èh ( À b ž z 5 % JQ 5B bv t4 Ðe b x¾ 5v À D À D@.. b $ â> ÅQ, 10 ÿ4 18 gs/ 100 g sorbent V5 K b :¾ 11 ÿ.o 4M@ B\ b:¾ L(29.6 gs/100 g sorbent) 05B # h@.. sd 4M@ K b :¾ 15 ÿ0 S@. 16, 20, 24 ÿ4 Îœ V@B dï(.. b: ¾ V5B ÿ4 z 2 â>u D5 d ÏH I Û +B M@ 8.. Áú b&' V@ ~ 30 ÿ0 b:¾ 15 gs/100g sorbent h S@ B\, s ÅQB Nª Ë $ :5 % ) k8q Ó8 Ôm I ~ v k8œ b 4B k ZnS+3/2O 2 /ZnSO 3 /ZnO+SO 2 (4) ZnS+3/2O 2 /ZnSO 3 +1/2O 2 /ZnSO 4 /ZnO+SO 2, SO 3 (5) h ÅQ4 ZnO/Al 2 O 3 b Á56 ZnO/natural zeolite b ( ÿ ºm Á #D ( x S 5 B\, Ó8 Ôm I us ) Q a w )[ b ( í ^B Ë E* 5 µ³d À, Îv.. Kim, Lee, Jun W[21-23] b (x 5 5 6 )[ Ë :5 B\, ] 8=ÅQ4 ) (Fe 2 O 3 ) Ë :* q (x @.% % +.. )k8 Á56 ) 450-600 o C=Þ4 ( Fù! k8œ MN)[D zinc titanatež zinc ferrite q zinc ferrite ( é Fê À @.. Ò 8=4B %ƒ b b Ç ( 8 >?p q b:¾ ì#5 S@B # $ b 2=x m #5.. Ò 8=4 Õ k8œ b 8 -z MD b- ( ÿ 4 ÿ ºê b b Fig. 8. Sulfur capacity of ZnO/natural zeolite during 30 cycle reaction. HWAHAK KONGHAK Vol. 41, No. 5, October, 2003

672 Table 4. Attrition resistance of zinc-based sorbents Sorbents AI(5), CAI(5), Initial Flow rate, RH, [%] [%] weight, [g] [slpm] [%] Temp., ZnO/Al 2 O 3 43.1 34.5 50 10 28.3 22 ZnO/natural zeolite 14.7 9.1 50 10 30.2 26 STA S 10 slpm(standard liter per minute) ì µ 20% # D\, Ó8 Ôm I$ : b q Nª Å N $ :5 8$ O=5% Œ 2ÐÑx > À d ï(.. ìz b Ø $ S5 56 UVd I (bentonite)ž V(clay) WQ a Úx ÅN $ :5B\, Ò 8 =4 : Ó8 Ôm I q UVd Id V ž ÐW.Ÿ X+ xy MN Nv Ó8Y[4 OZIž S xy u5% +.. 4 E*Q Úx ÅN E* TO B À,Îv.. ª Ó8 Ôm I 4.44 wt%# usv )š (CaO) dž ŽÊ ^x yd OZI )k8, Yk8WQ u us@, Å ¼:.. )š usv Ó8 Ôm I$ :* q 2ÐÑ x 5B\ í i + À,Îv.. Fig. 9. SEM photography of ZnO/natural zeolite sorbent, (a) fresh, (b) 30 cycle reacted. 3-6. XRD Õ b b- ( 8 z? z à [ŽS x õ$ ;ö5 56 XRD$ :56 b Å#= õ$ 5! ] ÅQ$ Fig. 10Q Fig. 11 dï2.. ZnO/Al 2 O 3 b B z q 2θ L 31.7, 34.3, 36.2D ZnO x@ù~ dï(d z àb ZnOž 2θL 31.22, 36.8D ZnAl 2 O 4 x@ù u dï(.. z >?@B T ^z [ D ZnOž D Al 2 O 3 ÅN56 MN)[D ZnAl 2 O 4 ž a ^ q x¾ ûv.. ; x¾ 4 ;ö@b Á>x ÆD 5 56 z à b Cà ü#5! SEM/EDX$ :56 C Ã[xõ$ ;ö5.. Cà ü#åq, b- ( 8 zm à b Cà 3.7 m 2 /g4 9.4 m 2 /g 5 $ O=5% b:¾ 5@.. EDX y7 b Cà k 8uw z 86.4%# B\, 24 ÿq 30 ÿ z à ÍÍ 90.2%, 94.6% @.. Z 30 ÿ à b Cà SEM ;ö ÅQ Fig. 9(b) dï ÀQ a P[ Q6 + B åh Û +.. h Cà xõ y7åq J k8œ b $ Þ 8 zm : * q 7LA n Nx A(CO, H 2 ) t )k8 Æ@, ÆV k8 @%, ] Cà T(migration) Ç VÅ t Á>x ì,r +$ D* +.. 3-5. # Ó8 Ôm Iž d$ :56 Õ k 8œ b 56 5OÞT Air jet STO b ÐÑ g Ÿ J ä,> ÐÑC(AI: attrition index)ž #ÐÑC (CAI: collected attrition index)$ Table 3 dï2.. d$ : b B 5OÞT ST ÐÑC 43.1%, #ÐÑCB 34.5%#! Ó8 Ôm I$ : b B ÐÑC 14.7%, #ÐÑCB 9.1%#.. 7SS c STU Tz c# :@B FCC T ÐÑg # B Fig. 10. XRD pattern of ZnO/Al 2 O 3 sorbent. 41 5 2003 10

!"#$ 673 m I us.ÿ xy bx¾ eb í hf5 * q %&' %ƒ b h: Ç 1)O$ ^á_ + À v.. Ò 8=B QS 1#8= ç t4?@! 8 =Á Æ {`l.. Fig. 11. XRD pattern of ZnO/natural zeolite sorbent. A@X= [ (x@.. sd ZnAl 2 O 4 B [ [5% #x Œ [ŽS x ~ H 2 Sž z x } )B À +B\, Ò 8= b- (8 z 4 b :¾ E V5B 6s ÆD n 5d Û +.[27]. zã ZnO/natural zeolite b B z Q à XRD y7åq ZnO ~ ;ö@! 8 z t4 ZnO Å#x 5@, @ÙF V À 3.ê Å#= $ \k Û ).. Á d Á56 Ó8 Ôm I 4 #D À,Î v.. 4. dž Ó8 Ôm I$ k8œ b = #x 5 :56 b $ 5!, ] b x ¾ û5 56 z x, 2=x, 2ÐÑx ÁÂ5! ÅQ J.$Q a ÅQ$ ä.. k8œ b b- (8 z x 5 t4b )k8 VÅ * +B $ :5B À SŽ5! Ó 8 Ôm I$ :* q d$ : qž ÐW )k8 VÅ * +.. Z Ó8 Ô m I us Fe 2 O 3, Na 2 O, CaO WQ a )[ Ë Ç ÅN ¼:56 z x, 2=x, 2ÐÑx hoéb í + $ Ó8 Ôm Iž a Ó8Y[ b x¾ SŽ u D5.. Ò 8=4B 12) Ó8 Ôm I$ :56 k8œ b $ u] 5Ã4 x¾ q %ƒ b 1) ¾x D* +B xq$ ä.. Eà Ó8 Ô 1. Park, Y. S., Rhee, Y. W. and Son, J. E., Chemical Industry and Technology, 11(5), 366(1993). 2. Rhee, Y. W. and Son, J. E., Chemical Industry and Technology, 13(1), 53(1995). 3. Yi, C. K. and Wi. Y. H., Chemical Industry and Technology, 13(5), 466(1995). 4. Rutkowski, M. D., Klett, M. G. and Zaharchuk, R., Assesment of Hot Gas Containment Control, Proceeding of the Advanced Coal- Fired Power Systems 96 Review Meeting, METC(1996). 5. Copeland, R. J., Cesario, M., Dubovik, M., Feinberg, D. and Windecker, B., A Long Life ZnO-TiO 2 Sorbent, Proceeding of the Advanced Coal- Fired Power Systems 95 Review Meeting Volume I, 394(1995). 6 Copeland, R. J., Cesario, M., Dubovik, M., Feinberg, D., NacQueen, B., Sibold, J., Windecker, B. and Yang, J., Long Life ZnO-TiO 2 and Novel Sorbent, Proceeding of the Advanced Coal-Fired Power Systems 96 Review Meeting(1996). 7. Rhee, Y. W., Lee, T. J. and Yi, C. K., Chemical Industry and Technology, 15(3), 273(1997). 8. Rhee, Y. W., Lee, T. J. and Yi, C. K., Chemical Industry and Technology, 15(4), 342(1997). 9. Ayala, R. and March, D. W., Cheracterization and Long-Range Reactivity of Zinc Ferrite in High-Temperature Desulfurization Processes, Ind. Eng. Chem. Res., 30(1), 55(1991). 10. Woods, M. C. and Gangwal, S. K., Kinetics of the Reactions of a Zinc Ferrite Sorbent in High-Temperature Coal Gas Desulfurization, Ind. Eng. Chem. Res., 30(1), 100(1991). 11. Gibson, J. B. and Herrison, D. P., The Reaction between Hydrogen Sulfide and Spherical Pellets of Zinc Oxide, Ind. Eng. Chem. Pro. Des. Dev., 19, 231(1980). 12. Sa, L. N., Focht, G. D., Ranade, P. V. and Harrison, D. P., High- Temperature Desulfurization Using Zinc Ferrite: Solid Structural Property Changes, Chem. Eng. Sci., 44(2), 215(1989). 13. Kidd, D. R., Nickel-promoted Absorbing Compositions for Selective Removal of Hydrogen Sulfide, U.S.Patent No. 5,094,996(1992). 14. Kidd, D. R., Delzer, G. A., Kubick, D. H. and Schubert, P. F., Selective Removal of Hydrogen Sulfide over a Zinc Oxide and Silica Absorbing Composition, U.S.Patent No. 5,358,921(1994). 15. Khare, G. P. and Cass, B. W., Fluidizable Sulfur Sorbent and Fluidized Sorption Process, U.S.Patent No. 5,439,867(1995). 16. Kidd, D. R., Selective Removal of Hydrogen Sulfide over a Nickelpromoted Absorbing Composition, U.S.Patent No. 4,990,318(1991). 17. Lim, C. J., Cha, Y. K., Park, N. K., Ryu, S. O., Lee, T. J. and Kim, J. C., A Study of Advanced Zinc Titanate Sorbent for Mid-Temperature Desulfurization, HWAHAK KONGHAK, 38(1), 111-116(2000). 18. Kang, S. C., Jun, H. K., Lee, T. J., Ryu, S. O. and Kim, J. C., The HWAHAK KONGHAK Vol. 41, No. 5, October, 2003

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