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

        

 ^† *

  ,  

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)



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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^oC/580^oC (sulfidation/regeneration). The attrition resistance was mea- sured 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.  

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†To whom correspondence should be addressed.

E-mail: tjlee@yu.ac.kr

 41 5 2003 10

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AB 5% )V uSv £V ý7 c$ :5¤.. µ S Table 1. Composition of natural zeolite

Elements Composition of natural zeolite, wt%

SiO₂ 65.0

Al₂O₃ 14.8

K₂O 1.61

Fe₂O₃ 2.64

MgO 0.78

CaO 4.44

Na₂O 2.65

TiO₂ 0.36

MnO 0.08

P₂O₅ 0.33

ZnO 0.15

BaO 0.07

Table 2. Experimental conditions for reactivity and durability tests by micro-reactor system

Conditions This work KRW

Reduction Sulfidation Regeneration Sulfidation Regeneration

Temperature (^oC) Pressure (atm) Flow rate (ml/min)

480 1 250

480 1 250

580 1 250

650-750 15

690-760

Gas composition - H₂S 1.0 O₂ 5.0 H₂S 0.55 O₂ 2.0

(vol.%) H₂

CO CO₂ H₂O N₂

11.7 19.0 6.8 10.0 balance

H₂ CO CO₂ H₂O N₂

11.7 19.0 6.8 10.0 balance

H₂O N₂

10 balance

H₂ CO CO₂ H₂O N₂

11.65 18.97

6.75 5.12 56.95

N₂ 98.0

R_P (reducing power) 2.6 2.6 2.58

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2-3. Micro-reactor

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3.  

3-1. ZnO   

Ò 8= †bz¢ƒ¶D 480^oC 4 7LA  )k8

(ZnO) Æ©x  5 56 ð-ñòA ¥§ÅQ$ Fig. 1

b|$ 480^oC 4 ÍÍ 10OÞ T­ ÆO ÅQ ë )k8

  15%#¶, Ó8|Ôm I$  : †b|B  3.4%

#¶ Æ@¡.. µ ƶB ÍÍ †b| uS ZnO )V w  ڒw Á$ y' œ)5¤..

ƶ(degree of reduction, %)= ×100

s ÅQ Û µ k8œ †b| 7LA t4 480^oC #

¶ 4 Æ >? D*  +¡!, $ :u4

Æ |*  +¡.. )k8 Æ@Ã ÆV k8(Zn)

“5’ @B\, ÆV k8 !B• 419.5^oC #¶ Ò 8= †b z¢ƒ¶. Ä µ³ %ƒz¢ „ 4 ‘’ VÅ(sintering)v..

Æv k8 VÅ †b| z¢x 5 ÆD p  +B\, Ó

zeolite) q $ :5  ë )k8 †b|(ZnO)

Á56 Ɨ¶ "¯#$ D*  +¡.. Ɨ¶ "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

¡.. ®˜
dž Ó8|Ôm I$  : Õ  †b|

2O₃

†b| Á56 Ó8|Ôm I$  : ZnO/natural zeolite

†b| Öz¢—¶ž ûå ¶' h 4 b Šw é Œ

 À dï(.. ®˜
d q bz¢ 4 bVž z¢x )d Ó8|Ôm IB bVž z¢x +B .Ÿ xy

Æ  ڒVw ZnOuw× OÆ°w

ZnÆ°w+OÆ°w

Fig. 1. Reduction of ZnO and ZnO/Natural zeolite with H₂ at 480^oC.

Fig. 2. Sulfidation rates of zinc-based sorbents.

 41 5 2003 10

*+ 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 Fe2O₃(2.64 wt%)Q Na2O(2.65 wt%)B … (1-3)Q a z¢

400^oC 5 ƒ¶ 4 bVž z¢x q5 µ³ k8œ

†b| Ö z¢x Q b:¾ ¦ í·
eB Ë

| ¼:* À ,Îv..

3Fe₂O₃+H₂/2Fe3O₄+H₂O (1)

Fe₃O₄+3H₂S/3FeS+4H2O (2)

Na₂O+H₂S/Na₂S+H₂O (3)

Õ  †b| “(z¢©x z¢OÞ  ڒõ ;ö ÅQ, Fig. 3 dï ¨ž a Ö 80y0 “(z¢—¶B ZnO/natural zeolite †b| 12d 80y à B ZnO/Al2O₃†b

| ڒõ é 1Ž >?@¡.. Õ †b| ÑÕ 250y 2 “ ( 39@¡..

3-3. " 

b-“( 14 ¥Ov À 1  ÿ 56 ZnO/Al2O₃†b|ž

ZnO/natural zeolite †b|  b-“( 8—  ÿ ¥§ ?

5¤.. †bƒ¶ž “(ƒ¶$ ÍÍ 480^oCž 580^oC %#OÉ% 10

 ÿ ¥§ ¥O ÅQ H2S 5Q6 Fig. 4ž Fig. 5 dï 2¡.. ZnO/Al2O₃†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 H2S 7 ¿o@ 8

! 5Q6 9¶ ÁÂ 5¤.. ZnO/natural zeolite †b|

q¶ 9  ÿ >?@B T­ 1  ÿ bz¢ O¼ à 140 min, 2  ÿ à B  200 min #¶0 H2S 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 ÁÂ

 †b&' Œ% ^z¢[D )k8 z¢ :65B Á' Œ

 À dï(..

; Õ †b| ÑÕ  ÿ ¦ ºm Ö B b:¾ ¦

5B À dï(B\, s ÆD 1  ÿ 4 †b|Ø°

2÷0 3ª z¢ :65 8 µ³ .. %ƒ„… †b|

-%   z¢ Szekely W[24] |­ grain model ²f

@B\, GibsonQ Harrison W[25] nƒ 4 grain )<(grain diffusion resistance) Œ µ³ H2S †b| Ø°n=÷y0

)@  µ³ †b| >x Ē dï?.% % ¨ +..

; Kang W[18] b-“(z¢ zM@B Q# 4 †b|Ø°

+.. ] 8=ÅQ$ ÁÂt Û µ Ö  ÿ bz¢ 4 †b|

 b:¾ Ä À H2S 2÷)—¶ "è À ÆD ! b-“( zM@Ã4 c (x÷J 2÷) SŽt#

µ³ b:¾ ¦5B À ²f*  +..

bz¢ 4 b Š †b|$ 580^oC, 5vol%)V(O2) „ “ (Q# 4 (5B SO2 Oõ$ ;ö 5Q6 Fig. 6Q Fig. 7 dï2¡.. ZnO/Al2O₃†b| q “(z¢ O¼ à  3%#¶ SO2 So@¡! z¢O¼ à  50-100 min#¶ 4 SO2

So¶ V5 O¼5B\,  SO25Q6 9

 3~5! z¢  ÿ ¦*ú 5Q6 9 3~t

% TO “(9OÞ 8@, 6  ÿ 4B 300 min#¶ 4

¶ “( 9@ 8.. ZnO/natural zeolite †b| q B “ (z¢ O¼ à  100 min #¶0  3%#¶ SO2 So@¡

! 5Q6 9 5% 250 min à B SO2 ;ö@

8.. ž a †b| “(—¶ "è À b)Y (x ^ ÆD ®¯™ +.[26]. C, bk8(ZnS) )V t4 )“

Fig. 3. Regeneration rates of zinc-based sorbents. Fig. 4. H₂S breakthrough curve for the sulfidation of ZnO/Al₂O₃ sor- bent at 480^oC.

Fig. 5. H₂S breakthrough curve for the sulfidation of ZnO/natural zeo- lite sorbent at 480^oC.

(@B Q# 4 Õ  $ B\, 5dB … (4)ž a SO2

 )@B À ! .ê B … (5)ž a b)Y(ZnSO4) (x v à b)Y %ƒ ¬yt t4 SO2 @B  .. Ò 8

= 4 †b| “( ÐD ÷y 4 “(—¶ "¯B SB b )Y (x D5B À ,Îv..

ZnS+3/2O₂/ZnSO3/ZnO+SO2 (4)

ZnS+3/2O₂/ZnSO3+1/2O₂/ZnSO4/ZnO+SO2, SO₃ (5) h ÅQ 4 ZnO/Al2O₃†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=ÅQ 4¶ )

(Fe₂O₃) Ë| :* q “(x @¡.% % ¨ + .. )k8 Á56 ) 450-600^oC=Þ 4 “(—¶ 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

:¾ Table 3 dï2¡.. ZnO/Al2O₃†b| q 1  ÿ 4 b:¾  15 gS/100 g sorbent #¶, 3  ÿ 4  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  ÿ 4 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/Al2O₃ †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¤..

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  ÿ 4 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  ÿ 4  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  ÿ 4 Μ V@B · dï(.. b:

¾ V5B  ÿ 4 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 Fig. 6. SO₂ breakthrough curve for the regeneration of ZnO/Al₂O₃ sor-

bent at 580^oC.

Fig. 7. SO₂ breakthrough curve for the regeneration of ZnO/natural zeolite sorbent at 580^oC.

Table 3. Sulfur capacity of Zn/natural zeolite and ZnO/Al₂O₃ sorbents Sorbents Sulfur capacity(gS/100g sorbent), Number of cycles

1 2 3 4 5 6 7 8 9

ZnO/Al₂O₃ 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. 8. Sulfur capacity of ZnO/natural zeolite during 30 cycle reaction.

 41 5 2003 10

^ 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 m²/g 4 9.4 m²/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| CÃ

SEM ;ö ÅQ Fig. 9(b) dï ÀQ a P[ Q6 + B åh Û  +¡.. h Céxõ y7ÅQ÷J k8œ

†b|$ ”Þ 8— zM : * q 7LA n Nx

A(CO, H2) t )k8 Æ@, ÆV k8 @%, ]

 CÃ 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$ 

#ÐÑCB 34.5%#¶¤! Ó8|Ôm I$  :

†b|B ÐÑC 14.7%, #ÐÑCB 9.1%#¶¤.. 7SS c” STU Tz¢c# :@B FCC T ÐÑg¥#¶B

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| ض$ 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..

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/Al₂O₃†b|B z¢ q 2θL 31.7, 34.3, 36.2D ZnO

©x@Ù~ dï(d z¢ à B ZnOž 2θL 31.22, 36.8D ZnAl₂O₄ ©x@Ù u dï(.. z¢ >?@B T­ ^z¢[

£D ZnOž D Al2O₃ ÅN56 MN)[D ZnAl2O₄ž a Fig. 9. SEM photography of ZnO/natural zeolite sorbent, (a) fresh, (b)

30 cycle reacted.

Fig. 10. XRD pattern of ZnO/Al₂O₃ sorbent.

Table 4. Attrition resistance of zinc-based sorbents

Sorbents AI(5),

[%]

CAI(5), [%]

Initial weight, [g]

Flow rate, [slpm]

RH, [%] Temp.,

ZnO/Al₂O₃ 43.1 34.5 50 10 28.3 22

ZnO/natural zeolite 14.7 9.1 50 10 30.2 26

 A@X=  [£ (x@¡.. sd ZnAl2O₄B [¶ [5%

¬­#x Œ [ŽS ©x ~ H2Sž z¢x }

)B À ®¯™ +B\, Ò 8= b-“(8—z¢¥§ 4 b

:¾ •E V5B 6s  ÆD n 5d Û  +.[27].

zà 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  )¡.. ÁÂ ®

˜
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 Fe2O₃, Na₂O, 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

* q %&' %ƒ„… †b| h: Ç 1)O$ ^á_

 + À v..

Ò 8=B QS÷ 1#8=¥ç t4 ?@¡! 8

=Á Æ {`l..



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