以混合醇胺溶液(MEA/AMP)去除二氧化碳溫室氣體之可行性研究

  

MEA/AMP   Removal of CO₂ Greenhouse Gas Using Mixtures of MEA/AMP Solutions

NSC 88-2621-Z-009 –001  87/08/01 88/07/31     !"#$%&#'() E-mailhlbai@green.ev.nctu.edu.tw  *+,-./0123,-4123, -560123,-789:;+,-<=> ?@CO2 A3BC#A3DE3F#GHIC 4JKLMNOPQRSFTUVW+XY8Z [+ MEA/AMP JKN\]^_`a5b612 3,-78cdAef:;JKLMgDN+X Yh6ij123,-k8lmnopAqr Fst.u8v`awxy=+z-{|8H/ }
QR~+€^5
      Abstract

In this project semi-continuous as well as continuous experiments were conducted using MEA/AMP mixtures to remove CO₂ greenhouse gas. In the semi-continuous experiment, the operation parameters which may affect the absorption capacity and the CO₂ removing efficiency were discussed. These included inlet CO₂ concentration, inlet gas flow rate, operation temperature and amines mixing ratio. The best composition of MEA/AMP mixing ratios was then determined. In the continuous flow reactor, the effect of liquid-gas ratio on the absorption capacity and the CO₂ removing rate was further discussed. The correlation equation for the mass transfer coefficient in the absorber was obtained by a multi-variate regression analysis and was used to design the full scale absorber.

KeywordsGreenhouse Effect, Carbon Dioxide, Mixed Amines, Monoethanolamine, 2-amino-2-methyl-1-propanol

!"#$

L M  g ] v . / e ‚ L M (primary amines)#ƒ‚LM(secondary amines)#„‚LM (tertiary amines v T … @  E † ‡ ˆ L M (sterically hindered amines)5‰ŠLMˆ‹Œ9 Ž6ˆ‘’“5e‚LM”ƒ‚LM4ƒ •–—DE‘’…@˜™‘’šW5›œž‘ ’Ÿjˆ ¡/ carbamate8¢a6£¤¥¦ § ˆ Q R S F ¨ / 0.5(mol-CO2/mol- L M)[1-3]5b„‚LM©E†‡LM4ƒ•–— DE‘’8n‘’šW˜ª8]œ6£¤¥¦§8 ˆQRSF]« 1.0(mol-CO2/mol-LM)[1-3]8 9œ¬Ÿj carbamate8b­n‘’®(enthalpy) ˜¯8°±g²³§8]´¯µF¶·5 *¸¹JKLM/ MEA+AMP89 œ MEA 6–º»¼½¾¿¢¹8…@QR šW#ÀÁÂj*¯#Sò³¢¹TP—Ä –K¡QRW¯ÅƓ8›œÇ@QRSF¯# …ÈɓTüÊËD7 SO2̖ÅÍÎ5b6 „‚LM#E†‡LM7+vÏ AMP89 œ6_ÐLM74ƒ•–—DE‘’+šWÑ =˜86IC/ 28.5Ò§«Ó 681 m3/(kmolÔ s)[4]5

MEA Õe‚LM8AMP ÕE†‡LM8n4

ƒ•–—DE+֑’×Ø[4]:

CO2
2MEA
MEACOOą
MEAHĄ (2-1)

AMP
CO2
H2O
AMPHĄ
HCO3ą (2-2)

*6}
QR~ÙÚ8Û¹xÜÁ݈Þß = T Z [Ntu][Hy] (2-3) n7 ZT =  Ntu = _{1 ( / )} ] ) )( 1 ln[( 2 2 2 1 m m m m m m L mG L mG mx y mx y L mG − + − − − =      HTU m: x2: !"#"$%&'( y1: )*#"$%&'( y2:+, !*#"$%&'( Gm:-*%&./0(kmol/m2 h) Lm:-*%&./0(kmol/m2h) Hy = avg y m a K G         = 12 30 Kya456kmol/m3 hr kPa

àPNtuábâ8eãDgäåæçk8náœè çˆ8bé9êçÖwxy=á8ë]`a Hy á5 ìí8î^ Sherwood Å ïðwxy=+Ð ñz-|[5]ò Kya = bGrmyGsmx (2-4) n7 Gmy4*-.kmol/m2 hr Gmx4*-.kmol/m2 hr b7r 8 s 9: ó*:;QR~}
+Ùôœ NtuáTÖ wxy=ˆ`õ5
 *,-.jö÷ø8ùe÷ø/0123, -8`aZ[,-<=8>?‘’ICTJ”L M(MEA+AMP)újNO5

612378QR~(packed tower) (×ûe ü)ˆýw¸¹ Pyrax þ
jv8. j8 / 20cm8/ 14.3cm +  E8n¡(packing)5¡ˆŸ|/ (Rashing rings)8ýw/8Ù |/8 ¡C/ 15 cm56 @ (redistributor)8v!g E". #8$%&³'3Ž(4DgJK¬£ˆÍÎ5 )@DE#gE¸*+4IC,-.5/ 0‘’.ž12I3¨48nIC3¨5 66 0~70Ò+5*,-¸¹ California Analytic Instruments {78ˆ12|ƒ•–—DE.u 9(ZRH model)8nƒ•–—DEF-ˆBC56 6 0~40%+8:æC6;1%v5 <,-=8 )¹ N24 CO2JKDEt>?@5ƒ•–—+ QRAB(loading)c!¹CçÙD`ð5   4.1JKLMújNOPUVEW+XY ûƒœ6¬FˆJKLMújNOØ801 23+ƒ•–—UVW4GH§ˆGyû(CO2 A3BC 16%;DE3F 2 lpm)h6‰Š,-7. HIrJKLM (MEA/AMP)ÀNOGH§ 6 1 J§KL5 Mûƒ7]Nƒ•–—UVW(MEA/AMP) NáOPbOP8_]Qð MEA æœN AMP @ ˜™ˆ‘’šW5›œR§ˆO8STU ]Qð6 MEAV12Wb AMPX18W¥YØ+U VWµZ˜[8›6 11~15 .\+k]^_ ´8`abWra˜b8‰°±À7 MEA ÷ ø»cd¹i8béeØ AMP ÷øf6g2‘ ’5hi 15 .\k8ƒ•–—UVW‘bœ MEA X6WT AMPV24Wj˜8›nUVW¯ž

40%8‰tkž AMP ‘’šW˜ MEA ªˆo

p8¢ AMP …@˜[[“5 4.2 JKLM4ƒ•–—‘’+ICr– û„œ6¬FˆJKLMújNOØ8‘’ .ICr–4GH§ˆGyû(CO2 A3B C 16%;DE3F 2 lpm)5û7]v&Ž8 ú )…@lFˆmn8ICopqrZÎ8hi 11.\k8skcdØ´5b­‰Š`a)@e

0tu8\ë MEA BCvjnZICëv 8‰tu]vaN8wJKLM7 MEA N v8xðˆyFvq8b Á MEA x ðˆyFž AMP xð+yF8¢a+k ÀPy²³§8 Á MEA zˆyF{ž Á AMP8ó/|}µ~€8JKLM7+ AMPNOvv5 p‚;ƒ78„ƒ•–—UVWbâ8w MEA…18W§86¬FIC؅@¬†UVW5 ìí8„QRSFbâ8c AMP BCvv8 b­ AMP Nv8²³§µ~¶·„v‡8 Èɓ ˆ‰{ ]Š ‹5k _¸¹ F új/ MEA=18W 8 AMP=12WH/k2123,-+ JKLMújNO5 4.3 JKLM4ƒ•–—‘’+QRSF ûœ6¬Fˆ‘’ICØ8QRSF4¬ FˆJKLMújNOˆGyû(CO2 A3BC 16%hDE3F 2 lpm)5¬ƒ‘’6 15Ò#25Ò# 35Ò Ø A  8 Q R S F €  J   £ / (MEA=0%,AMP=30% w/w) > (MEA=6%,AMP=24% w/w) > (MEA=12%,AMP=18% w/w)>(MEA=18%,AMP=12% w/w) > (MEA=24%,AMP=6% w/w) > (MEA=30%,AMP=0% w/w)8ëJKLM7 AMP NOv8QRSF{ v5ìí8Mû78{]v&ŽŒúQRS FICr–ˆŸ5wICM 15Òr–j 25 Ò § 8 (MEA=0%,AMP=30% w/w) 4 (MEA=6%,AMP=24% w/w)‰öúˆQRSFr –Fhi 10%8…@TUˆØ´mn8›nŽŒ ús{´¯ÇŽ‘ªØ´Ž(8QRSFr –F¬hi 4%hbwICM 25Òr–j 35Ò §8ŒúˆQRSFr–F£¬hi 4%8nŽ ‘ªØ´mn5‰°±JKLM7 AMP NOv §86¯I§…@˜ˆQRSF8›wï IC§8nQRSFØ´S™8XYQRSF’ 5k_8w¢¹ AMP À§8z“°nGH IC¬]”8v%QRSFØ´8›z“°ˆ œGHIC•”¯8cƒ•–—UVEW\–´ ¯5 4.4 g/DN+XY û—œJKLM4Á˜¢¹ MEA §8g/D

N4ƒ•–—U VWˆGy û(CO2 A3BC

Ž8wg/DNvJ§8MEA ˜JKLM…@˜ UVW8›Rg/DNOP8öj‹™vJ5 6g/DNV4.08öjš›K8ü_§UVW »môeœá8¬²g/DNOPbOP8• ²ïg/DN8閝žÀ8l¬–ïUV W5ì흍ƒ]N86g/DN/ 1.5 §8JK LM4 MEA +UVW)¬Ó 80%8Ÿœk/n QRSF»mž ”(40123lN˜)8¬µ ²QRƒ•–—8b­À+QRSFg/DN OPbŠ‡5 4.6 Öwxy=#ÖxÜÁÂ=4g/DNGy û¡œJKLM(MEA=18%,AMP=12% w/w) 4 MEA(30% w/w)6¬FgDNPÖwxy=+ GyN˜û(IC 25Òhƒ•–—A3BC 16%h DE3F 10 lpm)5Mû7]N8JKLMg+ Öwxy=(KGa)Rg/DNOPbOP8wg/ DN 1.5 ml/l OPÓ 4.5 ml/l8KGanáM 0.029

(kmol/m3 h kPa)r–Ó 0.113 (kmol/m3 h kPa)5b

Á¢MEA g+Öwxy=(KGa){Rg/DN

OPbOP8wg/DN 1.5 ml/l OPÓ 4.5 ml/l8K_GanáM 0.053 kmol/m3 h kPar–Ó 0.123 kmol/m3 h kPa5¬£œJKLMg©Á¢ MEA g8wg/DNž 4.0 ml/l §8Öwxy=r –F’¤8l­cd¥¦e0œá5ìí86 èçg/DNˆYØ8¢¹Á¢ MEA g˜J KLM@˜ˆÖwxy=8b­öjr–F6 g/DNž 4.0 ml/l §8cd§J5k_86è çˆA3DE3FØ8Ϩ©wˆgE3FšW œS9ˆ8¬s8eª¿OPgE3FšW s«]^]vP™Öwxy=8›œOPÓ¬e 0=ákëcdmže0œá89œ_­²O PgE3FšW8PžÖwxy=b⬲@U Rˆr–8SÃ8jgEÀˆƒ•–—QRS F®¯Ø´8ŸjgEÀˆž8¬]¬°5 4.5 QR~ˆ}
5OvTÖwxy=`õ QR~}
ˆ±*²}ò 1. ÊËD7ƒ•–—ˆBCœ16W5 2. GHIC}/2çIC250³5 3. ²}´µUVW/70W5 4. ¶D3F/10 m3/min at 250³5(¬·¸ SOx#NOx Ź“DE+XY)

5. ²}/ 1 Dº5 *123,-op+UVW4 L/G N ˆGyû(×û»)8]v`aò6 70WˆUVW ØaÓ L/G N}/ 1.858v]vaÓJKLM QRgˆ3F/ 18.5 l/min5 m123,-opAqrFst.u8a ÓÖwxy=+Gy|/ Kya =0.016G1.30myG0.22mx R2 = 0.56 (4-1) ²û¼+ L/G á]`ðÖxÜÁÂ=(Nty) }/ 2.01hHy/ 8.39m8ó(2-3)|]`a}
+~/ 16.8m5   0 1 2 3 , - 7 a N 8 Q R S F  (AMP/MEA)OPbOP8b‘’ICOPbŠ ‡8l­êç123,-7GHIC/ 25Ò8J KLMújNO/ MEA=0.188AMP=0.12561 23,-78QRSFg/DNOPbŠ‡56 g/DNV4.0 §8JKLM4Á˜¢¹ MEA +ƒ •–—UVW8)« 97%vp8s=jQRSF ǘ5 6123ÙÚ8èçˆA3DE3FØ8O PgE3FšWs«]^]vP™Öwxy =8PžÖwxy=b⬲@URˆr–8S Ã8jgEÀˆƒ•–—QRSF®¯Ø´8 ŸjgEÀˆž5wQR~Cèç§8¢ ¹¬FgwHQRÀ89`«Óè爃• –—UVWØ8ÖwxÁÂ=„]¹½ü¬F g+QRµ¾¿À8\ë ÁÂÁ¾J C8_§ÖwxÁÂ=vü ÁÂÁ¾ v5 

1. Pintola, T., Tontiwachwuthikul, P. and Meison, A. ,“Simulation of Pilot plant and Industrial CO₂-MEA Absorbers”, Gas Separation and Purification, Vol.7, No.1, pp.47-52, 1993.

2. Li, M.H. and Chang, B.C., “Solubility of Carbon Dioxide in Water + Monoethanolamine + 2-Amino-2-Methyl-1-Propanol ”, Journal of Chemical and Engineering Data, Vol.39 , No.3, pp.448-452, 1994a.

3. Li, M.H. and Chang, B.C., “Solubility of Hydrogen Sulfide in Water +

Monoethanolamine + 2-Amino-2-Methyl-1-Propanol”, Journal of

Chemical and Engineering Data , Vol.39 . No.2, pp.361-365, 1994b.

4. Saha, A.K., Bandtopadhyay, S.S. and Biswas, A.K., “Kinetics of Absorption of CO₂ into

Aqueous Solutions of 2-Amino-2-Methyl-1-Propanol”, Chemical

Engineering Science, Vol.50, No.22, pp.3587-3598, 1995.

5. Sherwood, T. K., and Holloway, F. A. “Transactions of the America Institute of Chemical Engineers”, 36, p21, 1940.

  
               
  !"#$%&'(! )*+,-./$01
 Ã
2  !"#$%&'(!345, -./$01
                 
6"#$ !789:"#$%&'($01
               
;<=>?@ABCD?=E@ACFGFH =>?<IJCFGFH!"#KG '  LM!)*+'N
  
O<=>?@ABCD?=E@ACFGFH =>?<IJCFGFH!"#K 'P QRS1T'N

UL/G ')*+$01

VL/G 'QSWXYT(Ntu)$01
1 2 3 3 7 7 5 11 8 8 AZ[ \]^ ZLM!_` IZ*a bZcKde` Z2fg hZ78i jZkl3 BZmn3 oZLM!pqr AJZs tu AAZvw AZ:x AIZyK8z` AbZ{|3 AZ}~tu 9 12 10 by pass 15 4 5 12 12 ₁₄ 13  € [














   

  
    !           
   
1 21 31 41 51 61 71 81 91 :1 211 2 2/6 3 3/6 4 4/6 5 5/6
 ,2 ! ǂ9 Ò Ó  NFB 1 21 31 41 51 61 71 81 91 :1 1  21 31
 41 51 61 71 ,2 ! ǂ9 ÒÓ MEA=0%,AMP=30% (w/w) MEA=6%,AMP=24% (w/w) MEA=12%,AMP=18% (w/w) MEA=18%,AMP=12% (w/w) MEA=24%,AMP=6% (w/w) MEA=30%,AMP=0% (w/w) 1/1 6/1 21/1 26/1 31/1 36/1 41/1 46/1 51/1 56/1 1/1 21/1 31/1 41/1 51/1 61/1 71/1

 MEA=0%,AMP=30% (w/w) MEA=6%,AMP=24% (w/w) MEA=12%,AMP=18% (w/w) MEA=18%,AMP=12% (w/w) MEA=24%,AMP=6% (w/w) MEA=30%,AMP=0% (w/w) 1 21 31 41 51 61 71 81 91 :1 211 1 1 /6 2 2/6 3 3/6 4 4 /6 5 5/6 6 L/G ǂ9 % 0 1 2 3 4 5 6 7 8 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 L/G
 (Nty ) 1 1/13 1/15 1/17 1/19 1/2 1/23 1/25 2/1 2/6 3/1 3/6 4/1 4/6 5/1 5/6