1.
 The Characterization of Zn-based Desulfurization Sorbents on Various Supports

  

    

 * *^†

  

*   

(2001 6 12 , 2002 1 30 )

The Characterization of Zn-based Desulfurization Sorbents on Various Supports

Seok Chan Kang, Hee Kwon Jun, Tae Jin Lee*, Si Ok Ryu* and Jae Chang Kim^†

Department of Chemical Engineering, Kyungpook National University, Daegu 702-701, Korea

*Department of Chemical Engineering, Yeungnam University, Kyongsan 712-749, Korea (Received 12 June 2001; accepted 30 January 2002)



 (TiO2, SiO₂, Al₂O₃)          

 !" # $% & ' () * + ,-  ./(  /0: 480^oC, 12 /0: 580^oC) & /(  /0: 650^oC, 12 /0: 800^oC) () 3 (45. 6 # $% & 78-9  : ;6 <=  >? @ AB CD C +E FGHI  !" ,-9 JKL   : ;6 ;, MH <= >? NOP QR

S5. 800^oC3 T UVQL     W X! Y ZCD,  C

/ & ./36 'C , 12  ,[ ;HI @  \] ^_K` ,-aKY bcC  :

;9 UVQLd eYf 'g : ;P h-A ^ i#L 0jT kl<P h-A S5.

Abstract−Zinc-based desulfurization sorbents supported on TiO₂, SiO₂ and Al₂O₃ and modified by treatment at various temperatures were prepared. Their sulfur removing capacities in a fixed-bed reactor and characteristics of their physical and chemical properties were tested during multiple cycles of sulfidation/regeneration. The best sorbent with high sulfur removing capacity and resistance to the deactivation at high and middle temperature was the alumina supported sorbent pretreated at 800^oC. The active species was the zinc oxide phase coated on the external surface of the alumina support without forming the spinel structure of zinc-aluminate and the change in the physical properties was not found during repeated sulfidation and regeneration.

Key words: Zinc Based Desulfurization Sorbents, Sulfur Removing Capacity, Alumina Support

1.  

IGCC

   !"#. $  % &' (

@ AB C  DE F5 GHI @8J  =#.

 ' KLM, NM, OM, PQM R ='S TU, PQM ' VWX H2S 8 YZ[ \]^  _ *`

a bcd =#[1]. e /0 f *g  ppmh+ i jk TU H2Sl YJ  =' GH =`,  PQ m

*' no `p` @M q r s*g t1 u]v# b

cd =#.  8 8w Fe2O₃, TiO₂, Al₂O₃, SiO₂, CuO R%

x y, zikI ++7 {r .j y, zikI  

*' Qr |} =#[2-15]. ~` ++7r {r€  ` p`' ‚[ ƒi„  …† @,  -‡ ˆ‰Š‹ w ~O

 8 Q' PŽ v o#. TU, n/ -‡
 

 ‘W( 650^oC, /0 800^oC) _ ‘W( 500^oC’, /0 600^oC’) “”] r• _ Z[I –+—˜

 /0I ()U *@ ™ ++7 Œ {r 8 Qr )U v|_ =#.

š Q' PQM  8› ++7 TiO2, Al₂O₃, SiO₂

 ž l ƒi —Ÿ x ++7 +’   &r #†

[ Œ /0 Z[I microreactorl ¢£ t¡*œ -. Œ 

†To whom correspondence should be addressed.

E-mail: kjchang@bh.knu.ac.kr

 40 3 2002 6

 ¤% 2 )i l ¥¦*œ#.  Z[ § Œ ƒi %

I    &, ¨ Œ & ƒi„ Q© —˜ 26*@

™£ Œ /0
 —ª 8 XRD, SEM, Porosimeter, BET t¡ |}«#.

2.  

2-1.
 

š Q 1" ' ¬O bcv kO ­j &*œ

#. Fig. 1 F' “„ x 250-300 mesh   ZnO powder„ x

 ®@ TiO2, SiO₂, Al₂O₃(Ignited) ++7l  {r  ¯@k

“° Bentonitel {r*g 4? Ball mill %I Y± ²³ ­ j—´#. ¯@k “° E µ 17 wt%h+ {r J  =' ¶

 bcd =` {r· ¸rJ¹ ‚[ ;]º bulk density„ average pore diameterr 3ž* BET-surface area„ Mercury

pore volume ¸r*' E»I F#'  %l “¼ *g š Q

' 3 wt% *œ#. ½¾ £ ` ­jkI –@k “

° _ *` Ethylene GlycolI b¿¾ {r*g -À  ŽE 1 mm ®@ ÁB(extrusion)—Â#. ~O muffle furnacel 1*g 3-5^oC/min  à , 250^oC   1—Ä r· ?I Y

*œ>, ? Y" ­jkI #— grinderl 1*g ?Å  700-1,200^oC 12—Ä ž*œ#. Æ à , ' 3^oC/min ÇÇU ן  ƒ¨I µži*œ PQ mI A+

*c *œ#. ž—´  ÈÉ% 7(Sieve)l 1*g 

É®@l 250-300µm

[I Ìr*œ#.

2-2. 

š Q 1 -‡ G:' Í microreactorl 1*œ

>, ÄÎ Ï ' Fig. 2 `p«#. -‡@ /Ð Ñ ‘»

I Ò+ Ó' ԑ –O(Quartz tube)l 1*œ> -‡@ +Õ

1 cm#. t¡ 1"  Ö 1 gI 1*œ space velocity ' s 5,000 hr⁻¹l –+*g %  Á[q* Œ channelingI µži

*œ#. -‡@ „ B line ¸@ ‡×I A+*@ ™*

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¹ 9M}«#. Æ ?Ô 1" column Þ rÚ  Ñ

I A+*@ ™*g Porapak Tr 45" 1/8in teflon tubel 1*œ

#. ß rÚ & Table 1 `pà>  r 650^oC

' /0  l 800^oC t—*œ  t¡ &a ¤¤*œ

#. _ t¡ E  Œ /0  l  480^oC, 580^oC

*g |*œ#.
 B H2S á r -‡@  á

„ Ý< 15,000 ppm < Æ _Î*œ> 2) rÚ Оl âO

• -‡@  l /0  h+ Ã —Â> /0   ã*

¾ }• О äÕI _ǘ 3-5 vol% zžl å– О r Úl 1*g /0 -‡I —|*œ#. š Q' æ

% æ /0
 çª }«I Æl 1 cycle ÄÒ*œ ßè

œ#.

3.  

3-1. Structure of sorbents

Table 2' ziPQ% ++7 TiO2, SiO₂, Al₂O₃ ­j

…a ¨}' é ê  &l bPF@ ™£ ziPQ% ++7

­j Œ &— ë &2„ ž  l ãO*œI Æ `p`' 

  &l powder XRD ?ÔI ¢£ ìíFî#.

Fig. 1. A schematic diagram of preparation for Zn-base sorbents.

Fig. 2. A schematic diagram of experimental apparatus.

Table 1. Experimental conditions for Zn-based sorbents

Sulfidation Regeneration Temperature(^oC)

Pressure(atm) Flow rate(ml/min) Gas composition(vol%)

High: 650 Middle: 480

1 50 H₂S 1.500 H₂ 11.700

CO 9.6 00 CO₂ 5.200 N₂ balance

High: 800 Middle: 580

1 50 O₂ 3-5 N₂ balance

TiO₂l ++7 1 PQM (ZT) E, Zn% Ti 8

ë &2„ ž  …a ZnTiO3(zinc meta-titanate), Zn₂Ti₃O₈ (zinc sesquit-titanate) ~O Zn2TiO₄(zinc ortho-titanate) ïr+ ðñ   &r j"#. …a š Q' Zn% Ti 8 ë &

2l 1.0% 1.5 2ò ó —Ÿ ­j  ž  l 700^oC, 850^oC, 1,000^oC  9*œ#. 700^oC ž ZT  E ZnO„ TiO2 ô y, zik ZnO„ TiO2 ?O}]   

&l ¨* =õI b  =#. ~` ž  r 850^oC o<

E ô y, zik ç5 Zn2TiO₄ &l ³ =õI © öJ  => ë &2r 1.0< E' Zn2TiO₄  & ÷g

*+ ø ùg TiO2r ©ö}«#.

SiO₂l ++7 1 PQM (ZS) E, Zn% Si 8

ë &2l 1.0% 1.5 2ò ó  —Ÿ ­j  ž  l 700^oC, 800^oC, 1,000^oC  9*g ~Æ `p^   &l ì íFî#. Table 2 F'“„ x 700<sup>o</sup>C Œ 800<sup>o</sup>C ž ZS  E ë &2 ©Mú ZnO„ SiO2ô y, zik ­ j …† *`  j &l ¨*+ ø* ZnO„ SiO2 ?O}

]  I ³ =#. ~` ž  r 1,000^oC< E' ­j o Zn2SiO₄„ ùg SiO2r ©ö}«#.

Al₂O₃l ++7 1 PQM (ZA) E Zn% Al ë

&2l 0.5„ 1.0 2ò ó —´  ž  l 800^oC, 1,000^oC, 1,200^oC  9*g ~Æ `p^  &l ìíFî#. Table 2

 F' “„ x 800^oC ž E ZnO„ Al2O₃ ?O}

]  I * =õI b  =>, 1,000^oC ž E

ô y, zik <Ñ ZnAl2O₄ &l ³ =+’, 57

 é ê  & ¨ ÷g*+ ø #· ZnO„ Al2O₃r ? O" Ê  &l ³ =õI ©öJ  =#. *+’ 1,200^oC

 ž E 0.5 2ò ó ë &2 < Æ' ç5 ZnAl2O₄ 

&l ³ 1.0 ë &2< E' 8Ñ? ZnAl2O₄  &

„ åû ü· ZnO  &r åû `pýI b  =#.

„ x  %l ¢£ ô r+ y, zik ­j ’º]v ZT, ZS, ZA

ž   þ ‘» ÿõI b  =#. š Q' ++7 Œ ž

  l ƒi —Ÿ #†   &l rv   8 2 6 Ìr t¡I |*œ#. ZT„ ZS º E Zn/++7 ë

&2l 1.5 
> ZA º E 0.5 *œ#.

3-2. Sulfur removing capacity

oC _ E

480^oC |*œ>, /0
 E' 650^oC  <

Æ' 800^oC 480^oC  ' 580^oC t—*œ#. Fig. 3

ziPQ% ++7 TiO2l 1.5 2ò ó ë &2l 1*g ­j

  700^oC(ZT-700), 850^oC(ZT-850), 1,000^oC(ZT-1,000) ž  

8 ?òI `p ¶, r × , /0
I 1 cycle Ä Ò
I Æ -. l `p ¶#. 23.1% `p Ì ZT

I `p ¶#.  t¡ & ZT-700  E -.

 ¸r …a ‚[ 21-19% sÄ 3ž* =+’ *+

' Ó#. -•, ZT-850  E -‡ @ 22.3%   10 cycle

' 14.6%  ‚[ 8 3žò 35% `p >

ZT-1,000

r 10 cycle' 7.7%  u]d ‚ 8 3žò 57%

`p #. Fig. 3(b)' _ t¡ & 480^oC  Œ 580^oC Table 2. XRD patterns of Zn-based sorbents before reaction

Sorbent Phase

1C.T.(^oC)

2M.R. 700 800 850 1,000 1,200

ZT 1.0 ZnO, TiO₂ Zn₂TiO₄, *TiO₂ Zn₂TiO₄, *TiO₂

1.5 ZnO, TiO₂ Zn₂TiO₄ Zn₂TiO₄

ZS 1.0 ZnO, SiO₂ ZnO, SiO₂ Zn₂SiO₄, *SiO₂

1.5 ZnO, SiO₂ ZnO, SiO₂ Zn₂SiO₄, *SiO₂

ZA 0.5 ZnO, Al₂O₃ ZnO, *ZnAl₂O₄,Al₂O₃ ZnAl₂O₄

1.0 ZnO, Al₂O₃ ZnO, *ZnAl₂O₄,Al₂O₃ ZnAl₂O₄, *ZnO

1C.T.: calcination temperature

2M.R.: Zn/support(Ti, Si, Al) mole ratio

*: small peak

Fig. 3. Sulfur removing capacity of ZT sorbents at high(a) and middle(b) temperature.

 40 3 2002 6

 E 2 cycle' 16%  26  ‚[I F+

’ 10 cycle' 9%  `p` ‚[ 8 3žò 44%

 >, ZT-850  E 2 cycle' 13%  l F#r

10 cycle' 5%  `p` ‚ 8 3žò 62% 

l F =#. e,  &  XRD ?Ô ZT-850% x

[I F#r 10 cycle' 3%  u]d ‚ 8 3

žò 75%l F =#. „ x  #† ž   …a 

 …a H§ 3žåI b  =>  t¡ & F#

_ t¡ & 3žò ®¾ `p` =#. ZT-700  E, ô t¡ & ßô #† ô  2£ o8 

3žòI F =#.

, %H ã —ÄI r+ Mz" ‚[% ãO -‡

@ B á r  á  ã J Æ h+ 57 ‚[I r+

 Z[I Ìr J  ='S,  E  ’PŠa _ t

23.1% rhê 22-23%l `p =#. %H Mz" ‚

[ _F#  #' ¶I c*•   %' ‚

[ Mz 1" %  @@r _ t¡ & F# 

 t¡ & ®#' tI b  => ZT MV ' 5

O …a %Hh+ ‚[ §r `+’   & Œ

& & ©Mú  å" ßè y, PQ -‡ ÷g åI b  =#.

Fig. 4' ziPQ% ++7 SiO2„ ë &2l 1.5 2òó

­j , 700^oC(ZS-700), 800^oC(ZS-800), 1,000^oC(ZS-1,000) ž

  …a & ZS º  Œ _ t¡ &

p ¶#.  t¡ & ZS-700% ZS-800  E

-. r ¸r}] 57 22-23% w" ‚[I F

 =>, ZS-1,000  E' 2 )i' ©ö}+ Óî

` 57 6-7%  ‚[I F =#. e Fig. 4(b)

„ ãO 2 cycle' 18-19%  F#r 10 cycle' 13%  `p` 3žò 28-30%  u]I   =#. e

ZS-1,000

ZS-800

I -.  ©M ú F =+’, ZS-1,000  E 

' 18%l `p _
' 3%   f 

 óI +#. ' ZT „ ãO  -‡ y,PQ /å I  *> _
'  -‡ PQ Ö 

 F# þ /åI b  =#.

Fig. 5' ziPQ% ++7 Al2O₃ 8 ë &2l 0.5 2òó

 ­j , 800^oC(ZA-800), 1,000^oC(ZA-1,000), 1,200^oC(ZA-1,200)

‚[I 26 ~#. 17% `p Ì ZA  &

#. T H ZA-800 ' Œ _ t¡ ‘W

[ 3ž no ©ö}+ Óî 15-16% ‚[I % _

8%    :l F => _' ‚[ @

2-3%

Fig. 4. Sulfur removing capacity of ZS sorbents at high(a) and middle(b) temperature.

Fig. 5. Sulfur removing capacity of ZA sorbents at high(a) and middle(b) temperature.

„ x 17%  l F =` ZA-1,000  E' 9%

ö}+ Óî#.  5O ž  ¸r …† Z[ 3

ž' Table 2 F! ž  r ¸r"¹ ZnAl2O₄  &

r ¸r*' no 9¤"  =>, 1,200^oC ž" E

 ßè   &r ZnAl2O₄l ³@ Æ# ° o Z [ Fg Ò+ Ó'#.

3-3. Characterization of Sorbents 3-3-1. XRD

Fig. 6 5É $% ïr+ ž & & ZT 

8 _ t¡ ‘W
 Π/0
 XRD  %

#. ZT-700  E -‡5  %' ZnO, TiO2r Ò" ?I 

³ => Zn2TiO₄R ­j" é ê ? ©ö}+ ÓõI Table 2

 &*œ#.
  %' ZnS, TiO2r Ò '®l *

 =õI   =>  -‡ ZnO' ©ö}+ Óî#. e 580^oC /0   %l F• -‡5 '®„ Ý<*¾ ZnO, TiO2r Ò '®

(I &J  = ž· Zn2TiO₄ '®r ©ö}]+>  -‡ sulfide

` Ñzk sulfate '®' ©ö}+ Óî#. e ZT-850, ZT-1,000

 E -‡5 Ò"   &' Zn2TiO₄œ,  -‡ ZnO, TiO₂' ©ö}+ Óî#.
 Ò" ¨' ZnS, TiO2œ>

/0   % -‡5 „ x+’ · ZnO„ TiO2r ©ö }«#.  t¡ & XRD  %º _ t¡  %º

% Y <:* =#. #’ ZT-700  E  t¡ &

 /0  r 800^oC ž  F# @ Æ# -‡5 ¨

ZnO, TiO₂ ?O" o )Pr+ ø* /0  é ê Zn2TiO₄ l ¨*' ¶ `p #. …a  t¡ &' _%

% x -‡ ˆ‰Š‹I …*¾ "#.   % Ñ+ ZnO, TiO2

r é ê ­joI ¨*@ ™£' 800 C o  ž &

 !åI b  =#. e,  y,PQ _„ x

 Ñ TiO2„ ?O}] /*Y`(ZT-700), é ê spinel & ­joI ¨*Y` ©M ú
' H2S„ -‡*g ZnS oI ¨åI b  => TiO2' ‚ -‡ © g *+ Ó' ¶ `p #.

Fig. 7A' ž   …a &" ZS(mole ratio 1.5) º 

 ‘W Œ /0
 XRD  %#. -‡5 ZS-700, ZS-800 ' ZnO, SiO2r ?O" o /*>
 

  -‡ ZnO' `p`+ Ó y, PQ 8Ñ? ZnS ƒ¨}

«õI b  =#. e SiO2' 5 -‡ ÷g*+ Óî#. /0

 ßè ZnS' ZnO ƒi}«> -‡5 „ Ý<  

%l -«#. _ % /0
 ZT-700, ZS-800

 -‡5 Ò '®' Table 2 $%
! Zn2SiO₄«> 


 ZnS Ò '®„ åû  -‡ Zn2SiO₄'®r

©ö}«#. _ Œ /0
 ZS-1,000 8 XRD  

%l Fig. 7B `p«'S Ò '®r Zn2SiO₄'®(I ©öJ 

=#.  .Ñ? $%
! ZS-1,000 '  t¡ &

 57 ‚[ 18%œ> _ t¡ &' 3% `

' 72%, _' 12%’ -‡ ÷g
õI #. /, ­ j" Zn2SiO₄

÷g J  =õI `p Ò => 7 650^oCF#   l –+£0 åI #. e  /0 & ZnO „ SiO2

 Ò '®’I ©öJ  =#' t /0 £ š1 -‡5 o Zn2SiO₄ })Pr+ ø* =õI FgÒ = ­joI 

³@ ™£' ] 1,000^oCo  r !åI bc Ò =#.

Fig. 8 ž   …† ZA º  -‡ &

Fig. 6. XRD patterns of ZT sorbents after sulfidation(a)/regeneration(b) at middle temperature.

Fig. 7A. XRD patterns of ZS sorbents after sulfidation(a)/regeneration(b) at high temperature.

 40 3 2002 6

 -‡5 ZnO, Al2O₃¨ ?O}] /åI b  =>

 8Ñ? ZnO' ZnS ƒ* Al2O₃'
 ÷g * + Ó' ¶ `p #. e /0
 zž„  -‡ sulfide

` Ñzk sulfate 0 ú -‡ 5 o )P3I b  =#.

ZA-1,000  E -‡5 ¨' ô Î< zik ?O}]  /*@ *+’ ô kÐ ­jo ZnAl2O₄e /* =õI b  =#.
 ZnAl2O₄ ­jo _ ’ PŠ

a  & `p` ='S, ZnAl2O₄r ‰Ð¹ ‚[

3ž*'  %„ åû y,PQ ­joI J E ‚ -

‡ ÷g * =+ ÓõI b  =#. /, 5É $% 8 ZA- 1,000

’ Î< zik ¨l * => `2+ 47%' ­joI 

* =õI Ä b  =#. ~O 8Ñ? o ZnAl2O₄

 XRD  %r Ý<åI b  =#. …a š Q  &

 Œ D( ?™@' ZnAl2O₄oI ¨J E' 5 -‡

 úõI b  =#.

3-3-2. SEM Morphologies and surface area

Fig. 9' ZA-800  (a)Œ _(b) t¡ & -‡5,

 SEM Morphologiesl `p =#. -‡ 5  É®@'

 300-400 nm  <*¾ `p` =>  -‡

' ‚ £ É®@r 2-33 o 45}] `p` =

#. e  /0 -‡ ' -‡ 5 É ®@ F# sÄ 

¾ ¨€I b  =#. _ -‡'  E„ Ü 6r+ É®@r 2-33 45}«õI b  =#. ~` /0

 Morphologiesl ©ö£ F•  /0%' ãO š1 ®@

)Pr+ ø* 45" ol –+*' ¶ `p 'S 

  %' Siriwardane R[5] ÒG% x
— y, oxide ¨

r y, sulfide ¨ ƒ*• ' 45*¾ } 800^oC

 /0}• 45" ' #— ×*• (1 o

 kO &r / }+’, _ E' 4?: ø

/0  Æ#(580^oC) yž sulfide £ 45" r oxide o ƒ*°a kO & 7•  Æ -‡5  ) Pr+ ø* 45" ol –+*' ¶ 8Î"#. b³` + +7r P tO9(ZS)` pp:(ZT)++7 PQM 

x noI ©öJ  =«#.

 Œ _ -‡5,  º 8 2 ›•I one point BET A 7*œ, ~  %l Table 3 `p«#. ZA- 800  E  t¡ & -‡5 :(5.1 m²/g)„ 26 Fig. 7B. XRD patterns of ZS-1000 after sulfidation(a)/regeneration(b) at

middle temperature.

Fig. 8. XRD patterns of ZA sorbents after sulfidation(a)/regeneration(b) at high temperature.

Fig. 9. SEM morphologies of ZA-800 before/after reaction at high(a) and middle(b) temperature.

£ 10 cycle ' ›• ƒil ©öJ  ú+’ _ 10 cycle -. t¡ ' ›• 23 ¸r
õI b  =«>

 _ t¡ &* 2 ›• ¸r noº ++7 © Mú ZT, ZS, ZA  ßô Ý<*¾ <]` =#. 

2 ›• ¸r' . SEM t¡  % `p`' _ /0 4 5" —ª ¨ @ ¸r no 8Î "#.

3-3-3. Mercury porosimeter SEM, One point BET

 45, ×  kO ƒ¨I ©öJ  =«` -. t

wI Ž 9¤ J  ú«#. …a  ;<  @

®@ Œ @
Ñ'l -‡5,   º 8£ bP Fî#.

Fig. 10  º  Œ _ t¡ & -‡5% 2

cycle, 10 cycle/0 º @
®@ 8 = @
Ñ

'l `p«#. ZT-850  E  10 cycle -. t¡ 

@
®@r P+> @
Ñ'r 25-30% 3ž* =#. _

x  %l F => -. r ¸rå …a @
®@ ?

r >?£d _ @
®@ ?l FgÒ =#. ZS-800   E  t¡ & 10 cycle /0   %l F• -‡5%

26£ ƒil ©öJ  ú#. *+’ _ t¡ & /0 

 @
®@r -‡5% 26£  Æ >? _ @
®@ ?l

³ => ~ ®@r ]v ¶I b  = @
Ñ' -.

r ¸rå …a ZT „ Ü6r+ _ H§ 3

ž* =õI   =#. ZA-800  E  10 cycle 

  %l -‡5% 26£ F• @
®@ Œ @
Ñ'r ƒi*+ Ó Table 3. Surface area of Zn-based sorbents before/after reaction by BET

at high and middle temperature

Surface area(m²/g)

Sorbent *C. T.(^oC) Fresh High temp.

(10 cycle)

Middle temp.

2 cycle 10 cycle

ZT 700 6.9 7.3 11.70 09.5

1,000 3.3 4.1 8.0 -

ZS 700 4.5 6.3 13.90 14.5

1,000 3.2 5.5 - 05.7

ZA 800 5.1 5.8 10.40 11.1

*C.T.(^oC): calcination temperature

Fig. 10. Cumulative pore volume as a function of pore diameter for various sorbents after selected cycles at high(a) and middle(b) temperature.

 40 3 2002 6

 => _ 10 cycle  @
®@' _ ?l

³ =+’ @
Ñ' E ZT ` ZS „' ãO ƒi*+

ÓõI b  =#. TU, _ t¡ & ZT ` ZS  E

 -.  ¸r …a M, @
Ñ'r 3ž* =`, b

³` E' ô æ@  V æ@ -. t¡  A ƒir

©ö}+ Óî#.

 % , ’ PŠa _ -.  …† ‚[

3ž no  kO Ð TU = @
Ñ'„ B ©M r =õI b  =#. /, Œ /0 -. t¡ v|}• =

no ©ö}+ Ó' ¶ `p #.   %' ZS Œ ZT

 E Π/0
 45% × }D }• Y8

@
 E„ þ ï @
 0 9¤} Table 3 Œ Fig. 10

 F! 2 ›• ¸r Œ @
Ñ' 3žl 1*, -‡

k &z ,  ‘»I ± %Hh+ ‚" ‚· 3žl

–*' ¶ F#. TU, %H Mz" ‚[ 3ž*

¶ @
®@ ƒi 8 -‡k &z , r 57 ‚ , 

‘»I : =õI `p =#.

3-4. The effect of metal loadings

y, PQ Ö% ++7 Ö …† Z Œ wI 26*

@ ™£ ZT Œ ZS  Zn/++7 2òI ZA„ x 0.5 

—Ÿ ‚[I & *œ#. Fig. 11 F! _ t¡ &

 ZT, ZS ô  ßô Zn/++7 2r 1.5< Æ F# 

‚[I F =+’, -.  ¸r …† w ®¾ ¸

[% 26£  Æ TiO2„ SiO2l 1 ' -.  …† ‚[ s 16% 3ž* =+’ b³` E 3ž no ©

`l 1 E 95% o y, PQ %H ã*@5

-‡ ¶ `p +’, TiO2l 1  E 80% ©ö

}« SiO2l 1  E 68% `p #. ' b³`

l ++7 1 r SiO2e' TiO2l 1 F# 

 ZI r+' ¶I * -. t¡ Ýw 45, ×

3ž noI C *' ¶ `p #.

4.  

PQM  ++7 1}' TiO2, SiO₂, Al₂O₃l 1*g

[I 26*œ#. ++7 ðñ„ 5O …a ' .j z ikI ¨ *Y` ++7 PQ zik(ZnO) ++" ¨

r & }«#. ZT  E 850^oC o .j zik

Zn₂TiO₄l ¨*œ ZS, ZA  E 1,000^oC o .j zik Zn2SiO₄, ZnAl₂O₄l  ¨*œ#. .j zik _ Ù

Ž Zn2TiO₄’ ‚[ @g *œ Zn2SiO₄, ZnAl₂O₄' š Q

 D( ?™@ Œ -‡   Ñ$  8Î}«#. G

 ž*¾ }• ++7 y, PQ " ¨ l -¾ }'S ppŠP Œ tO9 ++7l 1 ' - .  ¸r …† = @
Ñ' 3ž no% åû 2 )i n o ©ö}«` b³` ++7l 1 ZA-800 ' 

Œ _ ßô  no ©ö }+ Óî#. e ++7 ð ñ ©M ú H}' _ /0  45 no Œ ›• ¸r no Ž ‚[ Œ 2 )i ‘»I :+ Óî#.  ' ãO, µð ðIH( á „ B á r xP+' H) 7

·’ åœ> ' %H µð ðIHh+ @@ / -

‡ , r %H  …a A §l Fg Ò =õI  r P ‚ ,  § @ *œ#.

š Q' Ñ zÉ(Ñ 87K+@L(G7) <D

|}«MŠ#. Q2 +( 3NOŠ#.



1. Schrodt, J. T., Hilton, G. B. and Rogge, C. A.: Fuel, 54, 269(1975).

2. Jun, H. K., Lee, T. J., Ryu, S. O. and Kim, J. C.: Ind. Eng. Chem.

Res., 40, 3547(2001).

3. Gibson, J. B. and Harrison, D. P.: Ind. Eng. Chem. Prod. Res. Dev., 19, 231(1980).

4. Lew, S., Jothimurugesan, K. and Flytzani-Stephanopoulos, M.: Ind.

Eng. Chem. Res., 28, 535(1989).

5. Siriwardane, R.V., Poston, J. A. and Evans, G. Jr.: Ind. Eng. Chem.

Res., 33, 2810(1994).

6. Tamhankar, S. S., Bagajewicz, M., Gavalas, G. R., Sharma, P. K. and Flytzani-Stephanopoulos, M.: Ind. Eng. Chem. Prod. Res. Dev., 25, 429 (1986).

7. Lew, S., Sarofim, A. F. and Flytzani-Stephanopoulos, M.: Ind. Eng.

Chem. Res., 31, 1890(1992).

8. Woods, M. C., Gangwal, S. K., Jothimurugensan, K. and Harrison, D. P.: Ind. Eng. Chem. Res., 29, 1160(1990).

Fig. 11. Sulfur removing capacity of ZT and ZS sorbents with Zn/support ratio of 0.5 at middle temperature.

9. Gupta, R. P., Gangwal, S. K. and Jain, S. C.: Energy Fuels, 6, 21(1992).

10. Jothimurugesan, K. and Gangwal, S. K.: Ind. Eng. Chem. Res., 37, 1929(1998).

11. Ibarra, J. V., Cilleruelo, C., Garcia, E., Pineda, M. and Palacios, J. M.:

Vibrational Spectroscopy, 16, 1(1998).

12. Siriwardane, R. V., Poston, J. A. and Evans, G., Jr.: Ind. Eng. Chem.

Res., 33, 2810(1994).

13. Khare, G. P. and Cass, B. W.: U.S. Patent, 5,439,867(1995).

14. Kidd, D. R., Delzer, G. A., Kubicek, D. H. and Schubert, P. F.: U.S.

Patent, 5,358,921(1994).

15. Khare, G. P.: U.S. Patent, 5,306,685(1994).