Korean Chemical Engineering Research

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(1)Korean Chem. Eng. Res., Vol. 43, No. 1, February, 2005, pp. 66-70. ?÷¿+£ ã÷ £§ SiC Ï÷£ KïM/ |. §

(2) ´\* `]?** †. ³¬H/ @dHàHê { Q G} zD- 33 *KDÑw(,¬õCò ¤Ñw(õC« 305-343 ¬MQ K C ß 71-2 **(¬H/ dHàHê 449-728 , Ä¯Q 38-2 (2004¸ 11ö 12³ [¤, 2004¸ 12ö 28³ >) 712-701. Gas Permeation Characteristics of the Prepared SiC Membrane through Polyimide Carbonization Treatmemt Ho-Sang Choi†, Gab-Jin Hwang** and An-Soo Kang* Department of Biological & Chemical Engineering, Kyungil University, 33, Buho-ri, Hayang-up, Gyeongsan, Gyeongbuk 712-701, Korea *Hydrogen Energy Research Center, Korea Institute of Energy Research, 71-2, Jang-dong, Yuseong-gu, Daejeon 305-343, Korea **Department of Chemical Engineering, Myongji University, San 38-2, Nam-dong, Yongin 449-728, Korea (Received 12 November 2004; accepted 28 December 2004). ß È. IS é³§) HI ~g äÑ JÄs .g Ê~Éé0(·-«ÂÃ)õ «ÄGñ !d Ls fÊGÊ, « !d LÑ SiOõ I-Wk³ SiC Ls fÊG. ·-«ÂÃ !dÑ K O

(3) Ý2 u 50% _«Ê, !d 5 Í ÍO¤´ O

(4) Ý ÍG. !dLo !d5Í 9G

(5) Í) ·êÍ ÝGÊ L jÊdÍ ,} æÉ. SiC Lo SiO I- Í ÍG

(6) Í) ·ê 2 ÍGÊ, ,Z ·ê èn o l dÑw( ~ý Ñ Knudsen ~ýk³ ¡dK2 as < ¤ ÀÉ. Abstract − For the application in HI decomposition reaction of thermochemical water-splitting IS process, the carbonized membranes using the polymer material (polyimide) were prepared, and SiC membrane was also prepared by SiO treatment on those carbonized membranes. The weight change by the carbonation of polyimide was about 50%, and the weight decreased with an increase of carbonation temperature. The gas permeance (H2 or N2) of carbonized membrane decreased with an increase of carbonation temperature led to the pore closing. The gas permeance (H2 or N2) of SiC membrane increased with an increase of SiO treatment concentration, and the gas permeation mechanism was changed from the activiation energy flow to Knudsen flow. Key words: Thermochemical Water-Splitting, IS Process, SiC Membrane, Carbonized Membrane, Hydrogen Permselective Membrane. 1.. C «. Q õ @G2 é³§A G÷³ ùê èù dHä k³ g ê dH «Ç« f8æÉ. « é³§AÍ ‘ùdHJ ¤ fÆr’k³ -, *³Ò Ñw( (energy carrier)¯ ¤ õ @G2 D¬ G÷³ òÉtÑ @D2 ùÑw( Eo = 4ùD Ê5 ùÑw(õ «ÄK. IS(iodine-sulfur)à_[1, 2]ê UT-3(Ca-Fe-Br)à_[3]o òÉt Ê5 h ùs «ÄK ùdHJ ¤fÆ é³§A G÷³ õ gÍ ,}æÊ À. U¾, GA(General Atomic) [4]Ñ g Mð ³ f8æÊ, ³áòÉtõg(Japan Atomic Energy Research Institute)[5]Ñ × äH ßjÑ g - «Ç ¤ @Ñ àK IS à_o {ê ço äk³ g æ´ À.. ¤2 ÂÖ _ 2ó Ñw( G÷³ Î s çÊ Àk, Ñ w( (energy carrier)¶Ê 1. ¤2 (g bzK í ³z »s ¤ ÀD AéÑ ís ò0³ Gñ ¤õ fÆG2 D ¬s e?G2 ao O®K êf«. ís )[ ù~g Gñ ¤ õ @GD .g2 u 4,000 K Ê5 ùs 1®³ G2) « ao Jk³ kÎ ´ . « 5 «GÑ ís ~gGñ ¤ † To. whom correspondence should be addressed. E-mail: [email protected]. ‡. « øéo õ§¬0/ 6ÎR /¤ _¸s ,Ä/ñ ·ÊæÉ5n. 66.

(7) SiC. ~-L Í)·ê 7 . I2(l)+SO2(g)+2H2O(l)→2HI(aq.)+H2SO4(aq.) H2SO4(g)→H2O(g)+SO2(g)+(1/2)O2(g). (1) (2). 2HI(g)→H2(g)+I2(g). (3). ~jä«¶ -2 (1)o èùJ¯ SO ÍA ¤äk³, Ñ ÉõJk³ ,}ê. (2) z~g äo 2 ª « k³ ,}æ, zo 400-500 CÑ ÉèJk³ H OQ SO k³ ÉõJk³ ~gæ, ~-ê SO ÍA2 u 850 CÑ Ê ñkÑ g SO Q O ÍA³ ~gê. (3) ®1Ãd¤(HI) ~g äo ÍA Eo U k³ ,}ê. HÇ dHí0o Î ä Ñ ¨hG2 - «Çs g GÊ, z ~g äo HTGR(Ê 5ÍA³, high temperature gas-cooled reactor)Ñ g àæ2 Ê 5 h ùs «ÄGD âo 5òÑ o MhSê o ÕT ³)(entropy) ¡dQ Wÿ dH ·Jk³ ,}ê. HI ~g äo é³§A ùÁSs ¿j æÎG2 ä«. HI ~g äÑ2 ~jäÑ @ ê HIx ÄU(HI-I -H O H YÄU)k³z HI ÍAÍ ~-æ´ ù~gÑ g ¤õ @K . «6K dH äo HIx ÄU ÍQ HI ÍA ù~g(ñk «Ä)Ñ g Ñ¾ ,}ê. 6÷ ~jäÑ àæ2 HIx ÄUÑ2 HI-H Oª(H O/HI P92 u 5) HY9Ñ à9Æ (azeotropic composition)[6]« æÊ, ÍÑ g HIõ ~g GD .g2 Í/ ¤ dÑ !ñ L¬K Ñw(õ 1 ®³ K. K, HI ÍA MhS« 4(450 CÑ u 20%)

(8) HI ÍA2 ª ¨hæ´ é³§A ¨hí0(HIx ÄU)« ¬æ

(9) 1® ù

(10) «

(11) Ï ÍG2 éfY« À[7]. «Q ço HI ~g äÑ éfYs gGD .g ~- L D ¬s á à_Ñ ½Gñ HI ~gà_s íGD .K õgõ ,}G Ê À. G÷2 HIx ÄU« C à9Æ (quasiazeotropic composition) k³ HI Aè2 Æ Ñ !¶ ¿j ¡dG2 U [6]s «Ä Gñ Ñ ÊG( :2 ~- L D¬(Mg MD·, electroelectrodialysis)Ñ g HIx ÄUs C à9Æ s 2 Æ k³. E Íà_ Ñ g Ñ¾ ¨¤K HI ÍAOs ~-G 2 D¬«Ê[8, 9], ñ G÷2, ¤ > ·ê §¶Ã ~-Ls «ÄK L äD(membrane reactor)Ñ g HI ÍAõ Ý o MhS³ ¤õ »2 D¬«[10, 11]. áÉ Î, - (Si) Eo º¶³(Pd)ª ¤ ~-L« KÄGÊ ¶æ(O, Pd ª Î HI ÍA Ñ g « ©´,2 éfY« À[12]. á õgÑ2 §¶Ã é0Ý Í« £ ·-Ë é0(·-«Â Ã)õ «ÄGñ !dLs fÊG. !dLo ù o æ( O 500 C « Ê5ê h Ñ Äo ´ . !¶ «6K Ys ÞGD .g !dLÑ SiCõ ªGñ SiC ~-L s fÊGÊ, ¨¤ ÍA ·ê s +_Wk³ L äDÑ J ÄÑ ¬K ÍD s ]G.. 67. 2. 20-100 oC. o. 2. o. 3. 3. 2. 2. 2. 2. 2. 2. o. o. 2.. / . 2-1. ·-Ë é0³2 £³ Kapton-400 V(KAP-100, &ÿ 100 µm) Ú 500H(KAP-125, &ÿ 125 µm)õ ÄG. !d2 He Eo Ar ÍA ~.DÑ ,àk³ ÝFG

(12) ,}G. W5 2 3 C/mink³ GÊ K(Ñs ¡dÿ

(13) ×s G. o. Fig. 1. Carbonization furnace diagram.. o 0 ³ jQ !d ³õ ÷. 1,000 Cb( !dÑ2 K- äîê IR³õ «ÄGÊ, 1,400 Cb( !dÑ2 <PÂ÷ äîê MD³õ «ÄG. !d 52 500-1,400 C³ GÊ, 5 K(Ño 5Ñk³ G. !dO A @D2 ù~g öÍA ~Ñ2 GC(gas chromatography)õ «ÄGÊ, !dMá O

(14) ¡dõ +_G. !dÑ2 ÎÎ 4ß Kapton ·-«ÂÃõ ÄGÊ, O

(15) o Kapton-400 VÍ u 0.28 g, Kapton-500 HÍ u 0.4 g«Ê, O

(16) Ý 2 èàs ÄG. 2-2. SiC SiC fLs .K uo aY« 1,700 C « «Ê, u 1,280 C Ñ èGD Ò SiOõ «ÄG. ¶ SiO(¨ 99.9%)õ ~Sd , ) u 25 mm ò¶¯ !dLê äZ. Fig. 22 SiC äßjõ ÷ a«. ~S SiOõ He ¨ -´ ÍAÑ g 1,300 CÑ DdÿÊ, 1,380 CÑ ÍùGñ !dL ,

(17) Ú §àzÑ {ê ço äÑ g SiC @s G. o. Fig. 1. o. o. o. o. o. o. SiO(g)+2C(s)→SiC(s)+CO(g). (4). ÍAd 5 1,300 C Ú SiCd ä 5 1,380 C2 õ SiC s- ä[13]õ ÊsGñ 0 Kaptons !dK ! dL« 1Ñ¢ O

(18) ÍS« 1% _Í æ´ _K a«. 2-3. {ÿ M/ | Fig. 3o ¨ ÍA ·ê × ßjõ ÷ a«. ¨ ÍA ·ê ×o Aº¯-A e ¯(O.D 40 mm, I.D. 38 mm, SiO. o. o. Korean Chem. Eng. Res., Vol. 43, No. 1, February, 2005.

(19) MD özß,öã&¤. 68. Fig. 2. The preparation apparatus of SiC membrane.. Fig. 4. Weight change in each carbonization temperature.. Fig. 3. The measurement apparatus of the pure gas permeation.. L« 500 mm)s «ÄGñ, 25-250 CÑ ,}G. fÊK !dL Ú SiCLo (í n4 4(O.D 10 mm, I.D. 8 mm, L« 400 mm) .Ñ §¶Ã [ôfõ «ÄGñ Ê_G. ¨ ÍA2 He, H , N , CO õ ÄGÊ, ·ê2 Ft W r[10]s «ÄGñ { Ñ g G. o. 2. 2. 2. K dP Q = -------------- ⋅ -----A ⋅ ∆P dT. (5). ñD, Q2 ·ê, ∆P2 ·ê +ê à + Ftó(Pa), 2 L KÁ

(20) J(m ), K2 Ý_ _¤«. 2. A. 3.. ûG Z +{. Fig. 42 Î !d 5Ñ !ñ O

(21) Ýõ ÷. He, ,à ÆQÑ O

(22) Ý2 !d5Í ¡dGñ M ç o às ä2. «2 !d Ft¡dÍ O

(23) ÝÑ s Â j( :22 as ÂK. Kapton-400 V O

(24) ÝSo Kapton-500 HQ 9GGñ ¿j ¡dG. «2 0 &ÿÍ s¤´ O

(25) ÝS« (D A é«¶ @Îê. =s Ý

(26) < ¤ À×«, Ê5« î¤´ O

(27) Ý (Ê 1,380 CÑ Qo O

(28) Ýõ Ý. «2 !d5Í s¤´ 3-1.. o. ¤@¤ C43× C1 2005 2. Fig. 5. The amount of the product gas during carbonization of Kapton-500H.. O

(29) Ý ,2 as ÂK. Fig. 52 Kapton-500 Hõ !dGs A 5Ñ !¶ æ2 ÍAõ ÷. =s Ý

(30) < ¤ À×«, 410 C zÑ ³d!(CO)Q «d!(CO )Í è@GÊ, 550 C zÑ è!(CH )ê ¤ (H )Í è@GÊ, 800 C zz 0(N )Í Gj è@GÊ À. Jk³ Ý

(31) CO, CO , H ÍAÍ ?³ ê. o. o. 2. 4. o. 2. 2. 2. 2.

(32) SiC. ~-L Í)·ê 7 . 69. Fig. 7. Permeance of H2 and N2 gas on carbonized Kapton-500H at 1,380 oC and each environment. Fig. 6. Permeance of H2 and N2 gas on carbonized Kapton-500H at each temperature and He gas environment.. £ {ÿ M/ | o õ Î 5Ñ He ~.D³ !dK !d L ÍA ·êQ 5Ê s ÷É. 800 CÑ !dK CH-18 Î, ¤ ·ê2 5 Wê Wÿ ÍG2 s ÷Ê, 0 ·ê2 5 Wê Wÿ ÝG2 s ÷É. 1,000 CÑ !dK CH-5 ÎÑ ¤Q 0 ·ê2 5 Wê Wÿ ÍG2 s ÷ ,. 1,380 CÑ !dK CH-31 Î, ¤ ·ê2 5 Wê Wÿ ÍG2 s ÷Ê, 02 5ê 80 C(298 K Q 353 K)Ñ ·êÍ ]æ( :I. =s Ý

(33) < ¤ À×«, !d5Í ÍG

(34) ÍA ·ê 2 ÝG2 s ÷Ê À. «2 5Í WG

(35) !d à_Ñ ·-«ÂÃ ù ¤« lè¾ æ´ L« jÊGj æÉ D Aé«¶Ê @Îê. CH-31 25 C(298 K)Ñ 0Ñ ¬K ¤ ~-ª¤2 0 ]Kªõ ÊsG

(36) 40« s ÷Ê, 150 C(423 K)Ñ 0 Ñ ¬K ¤ ~-ª¤2 5.18³ Knudsen ~ý « ~-ª ¤ 3.74Ý o às ÷,. Fig. 7o Kapton-500 Hõ 1,380 CÑ !dK !dL H , N ÍA ·êQ 5Ê s ÷. ,à~.DÑ ! dK CH-38ê He ÍA ~.DÑ !dK CH-31 ¤ Ú 0ÍA ·ê2 5 Wê Wÿ ÍG2 s ÷ É. -Ê !d ~.DÑ !ñ ¤ Ú 0 ·ê 2 Î +_ 5Ñ uÑ ó«2 À(O ¿j ¡dG2 ao Ý«0 :Ê M ço às ÷É. « êÑ !¶ !d ~.DÑ !ñ ÍA ·êÑ o M Ç2 ak³ ¶ ê. 3-2.. Fig. 6 Kapton-500 H H2, N2. o. o. o. o. o. o. o. 2. 2. Fig. 8. Permeance of H2 and N2 gas on SiC membrane at each temperature.. £ {ÿ M/ | o L H , N ÍA ·êQ 5Ê s ÷ É s-K SI-1 ¤Q 0ÍA ·ê 2 ço 5Ñ(1,380 C)Ñ !dK CH-31ê 9GG

(37) , 150 C(423 K)Q 250 C(523 K)Ñ M ço às ä(O 25 CQ 80 CÑ o às ÷É. «ao SiO s-õ ,}O A !d @H L jÊdÍ

(38) Ï ,}æÉD Aé«¶Ê @Îê. ÍA ·ê 5Ê o SI-1LÑ2 ¤Q 0 ·ê 2 5Í WWÑ !¶ ÍG2 s Ý«2 äg, 2% SiO s-õ ,}K SI-2LÑ2 5Í WO¤´ òk³ ·ê 3-3. SiC. Fig. 8 SiC . 1% SiO. 2. 2. o. o. o. o. o. Korean Chem. Eng. Res., Vol. 43, No. 1, February, 2005.

(39) MD özß,öã&¤. 70. Í ÝG2 s ÷,. «ao SiOÑ K s-Í Qs¤ ´ ÍA ·ê2 ÍGÊ 5Ê o ò Ê s ÷ 2 as ÂK. , D ·ê èn o l dÑw( ~ ýÑ Knudsen ~ýk³ ¡dK2 as ÷. «6K ò¯ o õ ÎÑ porosityÍ ¬G2 ak³z ·G

(40) , §à « è³Gj ßG2 ak³ _Gñ ¶O ¤ À. Ks k³2 õ OÑ SiC Í (÷jj 4(j æ

(41) , ,

(42) z Ñ Âä Si 2 SiO-CÍ zJGñ ² s ³k ÍD « £ ~¾ À. «ao §à ² ò¯« æD G2), «Q ço ² Ñ D¯K ¿× è@k³ ~-æ( :o HI Ú I D ÍD @ÎO ¤ À[13]. SiO s- _Í 1%Q 2%Ñ ÍA ·ê « eGj í2 ao SiC L fÊ« ÂÅGÊ, Ö

(43) eK U s <D . g2 ñ6 ä ÆQÑ ª À2 õgÍ 1®G. 4)o ]gt O ]« Q« 4 À(O, HI ~É (4.21Å) ê I ~É (5.16Å)s Ý8O A Jo ~-ª¤³ £~¾ HI Ú I ~-Í ÍDGÊ[10], ·êÍ ~-Ñ ¿j s Ân 2 as[11] ÊsK

(44) SiC L o ¤ ·ê2 £~¾ ISé³§AÑ HI ~-Ñ «Ä ÍDG-¶ @ÎæÊ, Ok³ × ~.DÑ 8_ Ñ ¬K ] Ú ~-ª¤ ¬Ñ îK õgÍ 1®G. 2. 2. 2. 4.. û «. ·-«ÂÃ !dQ SiC L fLê ÍA ·êU Ñ îg { ê ço ·s »É. (1) á ×Ñ ÄK 0¯ ·-«ÂÃ !dÑ K O

(45) Ý2 u 50% _«Ê, !d 5Í ÍO¤´ O

(46) Ý ÍG. K, &ÿÍ o 0 O

(47) ÝÍ

(48) Ï ÍWs < ¤ ÀÉ. (2) !dO A æ2 ÍA2 CO, CO , H Í ?õ «P2 a s < ¤ ÀÉ. (3) !dLo l dÑw( ~ý U s Ý«Ê, !d5Í WG

(49) ÍA ·êÍ ÝGÊ L jÊdÍ ,}ê2 as < ¤ ÀÉ. (4) !d He ÍA ~.DQ ,à~.D Ù !ds- ör« ¶, ÍA ·ê o M çIÊ, ~.DÑ !ñ o M Ç2 as < ¤ ÀÉ. (5) SiC Lo SiO s- Í ÍG

(50) ÍA ·ê 2 ÍGÊ, D ·ê èn o l dÑw( ~ýÑ Knudsen ~ ýk³ ¡dK2 as < ¤ ÀÉ. (6) Ok³ ]gt O ]o Q« À(O, SiC L o ¤ ·ê2 £~¾ ùdHJ í ~g IS é³§A HI ~g à_ Ñ «ÄO ÍD « ÀÊ ·G. 2. ¤@¤ C43× C1 2005 2. 2. [ ÷. á õg2 2004¸ êHD¬z òÉt¤ D¬íè Æ ( òÑ g ¤}æÉSn. õg9 (òÑ Ý Ã?n.. +S 1. Onuki, K., Nakajima, H., Ioka, I., Futakawa, M. and Shimizu, S., “IS Process for Thermochemical Hydrogen Production,” JAERIReview, 94-006(1994). 2. Hwang, G.-J., Choi, H.-S., Kang, A.-S., Kim, J.-W. and Onuki, K., “Thermochemical Water Splitling IS(iodine-sulfur) Process for Hydrogen Production,” J. Korean Ind. Eng. Chem., 13(6), 600-605(2002). 3. Kameyama, H. and Yoshida, K., “Test of One-Loop Flow Scheme for the UT-3 Thermochemical Hydrogen Production Process,” Proceeding of 2nd World Hydrogen Energy Conference, Aug., Zurich, 2, 829(1978). 4. Norman, J. H., Besenbruch, G. E. and O’Keefe, D. R., “Thermochemical Water-Splitting for Hydrogen Production,” GRI-80/0105 (1981). 5. Nakajima, H., Ikenoya, K., Onuki, K. and Shimizu, S., “Closed cycle Continuous Hydrogen Production Test by Themochemical IS Process,” Kagaku Kogaku Ronbunshu, 24(3), 352-355(1998). 6. Neumann, D., “Phasengleichgewichte von HJ/H2O/J2 Loesungen,” Diplomarbeit, RWTH Aachen(1987). 7. Hwang, G.-J., Onuki, K., Shimizu, S. and Ohya, H., “Hydrogen Separation in H2-H2O-HI Gaseous Mixture using the Silica Membrane Prepared by Chemical Vapor Deposition,” J. Memb. Sci., 162(1-2), 83-90(1999). 8. Onuki, K., Hwang, G.-J., Arifal and Shimizu, S., “Electro-electrodialysis of Hydriodic Acid in the Presence of Iodine at Elevated Temperature,” J. Membr. Sci., 192(1-2), 193-199(2001). 9. Hwang, G.-J., Onuki, K., Nomura, M., Kasahara, S. and Kim, J.-W., “Improvement of the Thermochemical Water-Splitting IS (Iodine-Sulfur) Process by Electro-Electrodialysis,” J. Membr. Sci., 220(1-2), 129-136(2003). 10. Hwang, G.-J., Onuki, K. and Shimizu, S., “Separation of Hydrogen from a H2-H2O-HI Gaseous Mixture using a Silica Membrane,” AIChE J., 46(1), 92-98(2000). 11. Hwang, G.-J. and Onuki, K., “Simulation Study on the Catalytic Decomposition of Hydrogen Iodide in a Membrane Reactor with a Silica Membrane for the Thermochemical Water-Splitting IS Process,” J. Membr. Sci., 194(2), 207-215(2001). 12. Yeheskel, J., Leger, D. and Courvoisier, P., “Thermal Decomposition of Hydroiodic Acid and Hydrogen Separation,” Adv. Hydrogen Energy, 2(1), 569-594(1979). 13. Fujii, K., Nomura, S., Imai, H. and Shindo, M., “Oxidation Behavior of Boronated Graphite in Helium,” J. Nucl. Mater., 187(1), 3238(1992)..

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