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A Study on Comparison of Liquid-Phase Methanol Synthesis ... · A Study on Comparison of...
Transcript of A Study on Comparison of Liquid-Phase Methanol Synthesis ... · A Study on Comparison of...
HWAHAK KONGHAK Vol. 39, No. 2, April, 2001, pp. 150-156(Journal of the Korean Institute of Chemical Engineers)
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(2000� 9� 26� ��, 2000� 12� 29� ��)
A Study on Comparison of Liquid-Phase Methanol Synthesis Processes for Coal-Derived Gas
Jang-sik Shin, Heon Jung* and Jong-Dae Lee
Dept. of Chem. Eng., Chungbuk National University, Cheongju 360-763, Korea*Energy Conversion Research Team, Korea Institute of Energy Research, Taejon 305-343, Korea
(Received 26 September 2000; accepted 29 December 2000)
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���� ���� � �� �� ��� ���� ��� ���� ��� ���� ���� !�� "#
$% �� �� ��� Methyl Formate(MF) &'( ��) LPMEOH ��� *+ ��,- .��� / ��� ��0
12 34 ��� 056 78�9:. / ��� ��� ;<=) / ��� >? @� ABC ��DEF G# �'DE2
H MF &'( ��� I7J K,- LMN:. OJ MF &'( ��� 50% �%� ���� !�) 3.7%/ � P
Q�R DE6 S�F �T, LPMEOH��# U 30%� ���� !�) H2/CO� P� 1� ����2H 24%/ �
%� PQ�R DE6 S� MF &'( ��� I�6 S9:. OJ �� 012HE 150-180oC� ��VEW 60�X� �
�XY,- PZ� VRJ �� 01� �[F MF &'( ��� 250oC\]� ��VE6 �[F LPMEOH ��S: I
7J K,- LMN:. MF &'( ��� U^,- _`a CO22 bJ cd e%E \ fghi 0.5%� CO26 jk�
F ����2HE ��� a8hiH MF &'( ��� ���� � $% �� ��2 ��J K,- lmhn:.
Abstract − Two liquid-phase methanol synthesis processes, the “Methyl Formate Intermediate” process(MF process) and the
LPMEOH process, were experimentally investigated to find the suitability of the process for the coal-derived syngas. The MF
process showed the superior methanol synthesis rate at the same gas hourly space velocity(GHSV) than LPMEOH process.
The MF process showed more than 50% conversion of syngas per pass and 3.7%/day of deactivation rate which are far better
than 30% conversion per pass and 24%/day deactivation rate of the LPMEOH process. The reaction condition of the MF pro-
cess is milder than that of the LPMEOH process. The weakness of the MF process, which is the severe poisoning by small
amounts of CO2, was able to be overcome from the experimental result that the reaction proceeded even with the syngas with
0.5% CO2. Overall comparison reveals that MF process is more suitable than the LPMEOH process when the coal-derived syn-
gas is to be used for methanol synthesis.
Key words: Methanol Synthesis, Methyl Formate, Liquid-Phase, Coal-Derived Syngas, LPMEOH
†E-mail: [email protected]
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>� ���� YZ[ $35 �\] ��� �&U� )*. ^_ KJB
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D7 =lk� )6M, |}~s CD��� (= &X �D7 /�k
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4� �`>� �R iU? �4�`� XU� H2/CO� 2-0.57 \[
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% CO2 &� �AN ��R� 0�7 �&U� ���*. � � ~¡
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)� c4d eU^b� ©U� eU�`� ]¥�9ª� o� «�*.
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" ^b�E rs0a eU�` ]¥�9ª� 92%� ���, scale-up
�� hydrodaynamics {� ¯&� °2k� )�, �9ªN o�� ±
0a eU�`� �²N ��� ^b²�� �� ³p� )�� ´ª
U� �*� ' ( )*[2, 3].
Brookhaven National Laboratory�� NaH/RONa/M(OAc)2 �+E r
s0�µ �¢? �A[4, 5]� ��� heterogeneous �+� ¶� �+
� Triglyme% �� s+� ·�y ¸� B\ ^b�*. � ^b� ¹
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90%�\� eU�` ]¥�9ªN ���[6], �+� nickel� º»$
� ¼UN �½� nickel carbonylN ij0a X¾\ ¿�E �Àa�
"*. q" eU�`� 2Á? ¦-� �j>4=� \[y ÂÃ" �
+� ©U\ eU�`�� �j>4=� (��� &�� =!k� l
s� �A \¾>� ,Ä!�67 �\?*[7].
B\ c4d eU^b(Liquid-Phase Methanol synthesis, LPMEOH)�
Chem systemsr�� �¢kÅ*[8]. � �A� ICI�A�� rsk�
�+� �� lÆ" ��/j>�C� �+E mineral oil% �� B\�
Ç �>0a eU�`� B\N È%Á67� ^b ¢i0� ^b
Q� ´%$67 1jk� eU�`� ]¥�9ªN o] ( )� �
A�*. 1981É/8 ¦���U� |Ê��67 \s>E �0� )
6M, �� Air Productsr� Eastman Kodakr� 260 Ë/]� ijÌÍ
7 demoÎ ÏÐlE Eastmanr� Kingsport� ÑÐN º� ÏW�
� )*. � �A� ICI�A% lÆ" XÑ� lÒ$ o� O���
W�k�7 QÓÔ$ ÕÖ�9ª� �� B\�� W�k� ���¶
²�� �� ³p� )*.
Methyl Formate(MF) K �A� B\�� methyl formateE K
7 0a eU�`7/8 c4dN ij0� GH67 ×ØÙ���
�SkÅ*[9-11]. B\�� W�k� ^bO�� lÒ$ ��� ]¥�
9ª� 90%� Ú�µ X¾� �t0M, � " o� �9ª7 �R �
=� Á�? ÛÜ eU�`E �s' ( )� ,p� )*. � � 0.1%
�\� �% �j>4=� �R ×¼k�7 �Ý� �" ×¼N ¹Ã'
( )� �+� �¢� �t0_ �4�`� $s�tU� o*.
Þ�� ß C���� LPMEOH �A% MF K �A� �4�
`� $s �tU� o*� à³k�, L �AN �4�`� ©U� á
� ^bXÑ�� lÒÁ67� �4�`s c4d eU �A� $eU
N Xr0â*.
2. ����
ãÏ,º� Ç �>? �+� ä�? �P� Ò^¨ ^b�� �-
�²�(MFC, Model 5850, Brooks)7 H2/CO/CO2 {� lª å �-�
Xæ? Ír�4�`� ¿çk�, ̂ b�E È%" ¦^b �`� con-
denser å ÓP5 XA�(BPR, Tescom)E ÈR �`¦8E �f Yè
k�µ �Uk� )*(Fig. 1). B\ ̂ biU�� c4d {� condenser
� bék� ¿�$67 êë0a �`®7ì�íî(GC; HP5890,
Porapak Q, Carbosieve S column, TCD) å �-1��(Mass Spectroscopy,
Balzers)7 1�"*. 1¥� ãÏ� <= 1¿]� =!k�7 ï� (�
ãÏN ±R 300 cc� 500 ccs-� Autoclave(Autoclave Engineersr)
2�E к0â*. ©y MF�A ãÏ,º�� �P� syringe pump
(Iscor)� ,ðk� ãÏ� � wñ� �+ {� ¿ç� �t0�µ
�k� )*.
^b�� ¿çk� Ír�4�`� �- å XU� bypass lineN �
f �`¦8 å �`®7ì�íî7 �� 1�?*. ̂ b�E È%"
¦^b�`� �-% ¿ç�`� �-%� ~� å � �`� XUN
òó67 ^b²�E �j0â*.
3. �� (MF) ��� ��
B\�� cô2c�õE K 7 0a eU�`7/8 c4dN i
j0� GH� c4d� ]j>4=� ^b0a cô2c�õE iU
"[c4d ö�÷> ^b; ^b (1)] � cô2c�õ� (=>1R7 2
ø� c4d� iUkM[̂ b (2)], ù^b� ]j>4=� (=>7 c
4d� iU[̂ b (3)]k� «�*.
Fig. 1. Schematic diagram of methanol synthesis unit.
HWAHAK KONGHAK Vol. 39, No. 2, April, 2001
152 �����������
CH3OH + CO� HCOOCH3 (1)
HCOOCH3 + 2H2� 2CH3OH (2)
2H2 + CO� CH3OH (3)
� GH� q" c4d� K � k� eU�`7/8 cô2c�
õE IJ ij' (� )6M[̂ b (1)ú2 +^b (2) =^b (4)], c4
d% cô2c�õE }� ij' ( )*.
2H2 + 2CO� HCOOCH3 (4)
c4d� ö�÷> ^b� wñ�cûr�z� �+7 w�ü )�
[12-14], cô2c�õ� (=>1R ^b� copper chromite� ´%
$� �+7 w�ü )*[15-17]. � �A��� ³] ^b�°��
c4d B\� ±� L �+E Ç �>0a eU�`E È%ý_
c4d ö�÷> ^b% cô2c�õ� (=>1R ^b� }�
]�þ*. ^bXÑ� 100-180oC å 40-100 �P�*. � �A� ³
p� �D�`� 2Á? �j>4=� �� �R ö�÷> ^b� �
+� wñ�cûr�z� ×¼67 ^bU� �¹y ¹0?*� «�
*.
� �A� �4�`� $s �tU ÿìE ±R a �A �((O�,
P5, eU�`� H2/CO lª, �², eU�`� �j>4= ��)� ̂
bU� ¦º� ��% ]j>4=� ��� o� �4�`�s� �
²UN Xr0â*.
3-1. ��
^b� 500 cc s-� `���``ô autoclave�� ^¥1¨(semi-
batch)67 ��?*. ^b u�� 250 cc� c4d� $[-� copper
chromite(Ba-promoted; Aldrich)� KOCH3(Aldrich)E �� 170oC, 60
�P�� 8K}S copper chromiteE (=7 9� �, �-Xæ�
(MFC)7 XU% �-� Xæ? eU�`� c4d-�+ Ç �E È%
0_� ^b"*. ̂ b� P5� ÓP5 XA�(BPR)7 Xæk� �9
k� �� eU�`� �`¦87 �-N �A"*. ^b67 ij?
c4d% cô2c�õ� D 1�N ±" �N &�0�� ^b
��� &�k� �6�7 ^b� °/� �² é$?*. ^b B
� � � XU� �`®7ì�íî å �-1��7 1�0â*.
3-2. ��
3-2-1. O�
^b (1), (2) ÍL ¢Q^b��7 O�� ��Á� Þ� QÓÔ$ Õ
Ö�9ª� Ã="*. ̂ _ �+^b� ^bO�� ��Á� Þ� ̂ b
²�� ��� �\?*. ^bO� �>� Þ3 � ^b²�� �>
E w��� ±R 100oC�� 180oCV� ^bO�E �>�6M �
%E Fig. 2� ��°Å*. ���� �� ò� �� 100oC��� �
U� �� �*�, O�� ��Á� Þ� � ^b²�� ��ÁN �
â6�, 180oC �\� ^bO���� ^b�°�� s+7� �s0
� c4d� �¢0� k�, � �\ B\^b� ]��� ��*. �
�7 ^b� 180oC �0� O��� (�R� "*. 160oC �\� ^
bO���� � ^b²�� ��� �>kÅ�x �� ^bO��
��� Þ� ^b (1)� QÓÔ$ ÕÖ� ��67 �}, � K �
cô2c�õ� ��� Ã=Á� ��"*. Þ�� ^b� <$O��
150-180oC�N w ( )*.
3-2-2. �j>4= å �� ��
B\� �� ��0_ ̂ b (1)� �+� KOCH3� �% ̂ b0a 2
c�õ(HCOOK)E �Ý� �U� ���*� w�ü )*[11-13]. ̂
bN �0� �� copper chromite� KOCH3E c4d% Á� ^b
�� ä�0� (=7 copper chromiteE 9�ý� %A�� �� ¢
ik� KOCH3E ׼0� ?*. �� 9� � H2/CO �e�� ^
b�`E ¿ç0a� ^b� �ò7 �k� �� p�$67 ��k
� � 20K �� A\\�� ^b²�� �¶"*(Fig. 3).
^b u�� copper chromite� 9�� �R ¢i? �� ^bK�
�%�� � copper chromite� (U�`^b(Water-Gas Shift; CO +
H2O� CO2 + H2)� �+7� �s0a �N �j>4=7 �90�
�j>4=� ¦^b�`� Á� ^b��� Yè?*. �� ��� Ã
=0_� HCOOK q" copper chromite� �R KOCH37 �i?*.
Copper Chromite
HCOOK + 2H2→KOCH3 + H2O (5)
KOCH3� �i� Þ� B\��� cô2c�õ ��� pp ��0
M }� ^b²�� ��0a � 20K �� A\\�� ^b²�
� �¶0� ?*. �, copper chromite� cô2c�õ� (=> 1R
^b� �+ ��� (U�`^b å KOCH3� �i^b� �+7�
�s?*.
^b� A\\�� �¶" �� �±$67 ^b�� �N ¿ç0a
B\� �� ��E 2.5 mol%7 ��� %, ̂ b²�� Î�y
� ^b� �� ��k� �!6M, �" B\� cô2c�õ ���
Fig. 2. Change of Methyl Formate(MF) concentration and rate of methanolsynthesis at various reaction temperatures(copper chromite 5 g,KOCH 3 0.833 g in 250 cc methanol, 260 Ncm3/min, H2/CO=2,60 atm).
Fig. 3. Effect of CO2 in inlet mixture gas(copper chromite 5 g, KOCH3
0.833 g in 250 cc methanol, 260 Ncm3/min, H2/CO=2, 150oC, 60 atm).
���� �39� �2� 2001� 4�
������� � �� � �� �� �� 153
0� kÅ*. �� L I# ^b ö�÷> ^b� ��k� �$67
�R � ^b� A�k� "¯�*. %��7 ^bK� �%Á�
Þ� KOCH3� �ik� B\��� cô2c�õ ��� pp ��
0M }� ^b²�� ��0a � 40K �� �� �� A\\�
� ^b²�� kÅ� �"� �� ��� 0.1 mol%7 �ÝÅ*. �
� 0.1 mol%(700 ppmv)� \[y o� ���� ^b� ��?*� «
� KOCH3� copper chromite� �R �² �i?*� «N �¦"*.
�� q" \[-� KOCH3� l�U>? 2c�õ \�7 ��ÁN
&"*. Þ�� �� ·�y &�? \��� � ^bN ��0_ ��
g� KOCH37 � o� �U� �?*.
�4�`�� \[-� �j>4=� 2Ák� )�, �j>4=E
ppm ³±V� &�0�x� \[" ls� =!k�7 �' A�� �
j>4=E 2Á" �4�`� c4d7� �9� (!0*. ö�÷>
^b� �+� KOCH3� �j>4=� ^b0a KOCOOCH37 �9
k� �UN )� ?*[14]. ^b� A\\�� �¶0âN ", ^b�
� ¿çk� �`� �j>4=E 1% å 0.5%7 *�� ^bN ��
" %E Fig. 3� ��°Å*. �j>4=� 1% 2Á? �� ^b²
�� 75% Ã=0�, 0.5%� 2Á? �� 52% Ã=kM, �" K
� cô2c�õ� ��� �� 54% å 45% Ã=0a �j>4=�
�R ö�÷> ^b� �+� KOCH3� ×¼�N ��0â*. � �
10,000 ppmv(1%)� CO2� 2Á? �`E rs0� ö�÷> ³¼^b
� �� �+ ^b� ��k� ��x ^0a MF K �A� ��
copper chromite� �R KOCOOCH3� KOCH37 �ik� ^b� �
' A� ��?*(̂ b 6).
KOCOOCH3 + 3H2 → KOCH3 + H2O + CH3OH (6)
�j>4=� 2Ák� �� eU�`E * ,��°� ^bN �
�" %, �í ^b²�� 70%V�� ¥¤k� ]/ l�Ó$� l
�U>� ]�-N w ( )Å*.
3-2-3. eU�`� �²
¿çk� eU�`� �² �>� Þ3 ̂ b²� å �9ª� �>E
w��� ±0a 150oC�� ^b�� ¿çk� �`� �²N �>
� %E Fig. 4� ��°Å*. ���� . ( )/� �²� ���
Þ� ^b²�� ��0� eU�`� ]¥ �9ª� Ã="*. ©y
¿çk� �`� 50 Ncm3/min� �� �²��� 80% �\� +� o
� �9ªN ��*.
ß ãÏ��� ^b�� Ò^ ²�� 1,000 rpm67 +� o�� �
/ ���¶²� &"(external mass transfer limitation)� �� 0±�
� ^b� ��k�7, �²��� Þ3 ^b²�� �>� �\0�
�� %�*. �� ^b� ��k� \��� 700 ppmv� �� B\
� )6�7 (U�`^b� �R ¢ik� CO2� �� �²��� ¦
^b�`� �²� �6�7 ´%$67 ^b��� &�k� 10�
"¯67 i�?*.
3-2-4. eU�`� XU(H2/CO lª)
eU�`� &X0� GH% �D� Þ� � XU� *�*. ]^
$67 ï� rsk� �C�`� (����� �� H2/COl� 3-
7��, /1j>(partial oxidation)� ��� 1.6-2, ��� �4� �
`>� ��� 0.5-2�*. *g" XU� eU�`� �s �tUN
w��� ±R ^b� � eU�`� XUN �>� %E Fig. 5
� ��°Å*. eU�`� H2/CO lE 4�� 17 Ã=2 ��, �
77%� p�$� ^b²�� ��E �â*. �� ^b� °/� ]
j>4= 1P ��� Þ3 B\ cô2c�õ� �� ��� ��"
*(Fig. 5). � � eU�`� H2/CO l� 0.5� ��, ^b²�� Î
�y Ã=? ^_ cô2c�õ� ��� Î�y ��kÅ*. �� �
3 o� ]j>4=� 1P� �" copper chromite� ×¼% �3
�� (= 1P67 �0a ^b (2)� (=>1R ²�� ¹0kÅ
*� R�' ( )*. ©y �4�`� XU� H2/CO=1 /4�� o
� ^b²�E �a � �A� �4�`� $s�tU� o� �A�
N r"*.
3-2-5. ,�K SAU
ß �A� \¾>k� ±R�� �+�� ,K W��� l�U>
A�� ��� o� �UN ��R� "*. �D�`� H2/CO l� 2
� �� 100K� W� % l�U> ²�� 0-0.4%/]7 �� ��
�� �!*. � � ß C��� \67 0� �4�`� �Ö$�
XU� H2/CO=1��� l�U>� ]�� 3.7%/]� l�U> ²�E
��*. �" B � XUN Xr" %, K � cô2c�õ� �
�� �� Ã=ÁN w ( )Å*(Fig. 6). cô2c�õ� �� Ã=�
^b (1)� �+� KOCH3� �UN )� «67 R�' ( )*. �
� �£" ò� �� KOCH3� ^b (2)� �+� copper chromite�
�R �² �ik�7, ]j>4=� 1P� o� \��� copper
chromite� p�$� ׼� �R KOCH3� �i� ��0� ��k�
��*�� R�' ( )*. ã&7 ^b (2)E copper chromite �+\
�� ��' ", ]j>4=� �Ó$67 copper chromite �+E ×
¼0� «67 ��? ò )*[13].
Fig. 4. Change of conversion and rate of methanol synthesis at variousflow rates of inlet gas(copper chromite 5 g, KOCH3 0.833 g in250 cc methanol, H2/CO=2, 150oC, 60 atm).
Fig. 5. Effect of H2/CO ratio of inlet gas mixture on methanol synthesisrate(copper chromite 5 g, KOCH3 0.833 g in 250 cc methanol,250 cm3/min, 150oC, 60 atm).
HWAHAK KONGHAK Vol. 39, No. 2, April, 2001
154 �����������
4. LPMEOH ��
LPMEOH �A� c4d eU ̂ b[̂ b (3)]� o� ̂ bQ (∆H298o =
−90.64 KJ/mol)7 �" ��-j>�C� �+� = N �� ±0a 10-
12%7 &"k� eU�`� ]¥�9ªN o�� ±0a ^bQN ´
%$67 1j &�' ( )� mineral oil% �� B\� �+E Ç
�>0a eU�`� B\N È%0_� ^b0�µ 0a ^b�`�
]¥�9ªN 30%V� o� �A�*.
ICIr� �\ ^b �A% �r" X¾XÑ�� W�k� LPMEOH
�A� ©567 ��� \s�A��� 6�t" ]j>4=� lª
� o� �4�`� IJ rs� �t0M, �} A�/�X¾ {� X
¾��� s�0�, ij? c4d� 2Á? (1� �� �A(4-20%)
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Fig. 6. Long-term change of methanol synthesis rate and methyl for-mate concentration during the reaction with simulated coal gas(copper chromite 5 g, KOCH3 0.833 g in 250 cc methanol, 164Ncm3/min, H2/CO=1, 150oC, 60 atm).
Table 1. BET surface areas of commercial catalysts tested
Catalyst A B C D
Surface area[m2/g] 67.79 72.27 15.97 49.26
Fig. 7. Change of initial rate of methanol synthesis of LPMEOH pro-cess over various commercial catalysts(2.68 g in 150 mineral oil,260 Ncm3/min, 250oC, 60 atm, CO2=1.7-5.4%).
Fig. 8. Change of methanol synthesis rate of LPMEOH process andCOx conversion at various reaction temperatures(catalyst A 15 gin 150 cc mineral oil, 260 Ncm3/min, H2/CO=2, 60 atm, CO2=3.2%).
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o� c4d eU²�E ��°Å*. �� Klier {� &" %� ]
º"*[18]. CO2� 1.0% Á�? eU�`� lR 3%� Á�? eU�
` 1±��� 21%� �U��E �â*. � � CO2 ��� 5%7 �
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� 26.5%7 Ã=0â*. ©�" p� �²� 262 Ncm3/min��� l
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�U>� ]�þ*� «�*.
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>� %E Fig. 11� �� ��°Å*. �" l�U> ²�� 24.2%/
]�Å*. �+� ä�-N 15 g67 F�� eU�` XU(H2/CO)� 1
� eU�`� �²N 260 Ncm3/min7 � ��� ãÏ %E Fig. 12
� ��°Å6M, � ���� l�U>ª� 24.4%/]7 l�U> �\
� �m� �G��� �!*. L HI7 �(" \s�+� C�+� �
�� eU�`� XU(H2/CO)� 1% 2 ÍL�� 20%/]� Ú� o� l
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c4d eU� rsK �� ï� g� �+� =!K «67 �\?*.
5. � �
LPMEOH �A% MF K �A� ã� ãÏ %E Table 2� l
Fig. 9. Change of methanol synthesis rate of LPMEOH process at var-ious reaction pressures(catalyst A 15.0 g in 150 cc mineral oil,260 Ncm3/min, 250oC, CO2=3.2%).
Fig. 10. Change of methanol synthesis rate at various CO2 concentra-tion of syngas with 15.0 g A catalyst in LPMEOH process(150 ccmineral oil, 260 Ncm3/min, H2/CO=2, 250oC, 60 atm).
Fig. 11. Change of methanol synthesis rate at various inlet flow ratesover 6.0 g of A catalyst in LPMEOH process(150 cc mineral oil,250oC, 60 atm, CO2=3.7).
Fig. 12. Deactivation behavior of A catalyst when simulated coal gas(H2/CO=1) was fed(15 g A catalyst in 150 cc mineral oil, 260Ncm3/min, 250oC, 60 atm, CO2=3.0%).
HWAHAK KONGHAK Vol. 39, No. 2, April, 2001
156 �����������
95
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����
1. Brown, D. P., Brown, D. M., Jones, W. C. and Kornosky, R. M.: “The
Liquid Phase Methanol(LPMEOH) Process Demonstration at King-
sport,” presented at Fifth Annual DOE Clean Coal Technology Con-
ference, Tampa, Florida(1997).
2. Westerturp, K. R. and Kuczinski, M.: Hydrocarbon Processing, 65(11),
80(1986).
3. Wainwright, M. S.: in “Methane Conversion,” ed. by D. M. Bibby, C. D.
Chang, R. F. Howe and S. Yurchak, Elsevior, B. V., Amsterdam,
(1988).
4. Sleigeir, W. A., Sapienza, R., O’Hare, T., Mahajan, D., Foran,
and Skaperdas, G.: 9th EPRI Contractors Meeting, Palo Alto, C
May(1984).
5. Sapienza, R. S., Sleigeir, W. A., O’Hare, T. E. and Mahajan, D.: U
Patent No. 4,619,946(1986).
6. Muhajan, D. and Mattas, L.: Proceedings of the 16th Annual EP
Conference on Fuel Science, Palo Alto, CA, April(1992).
7. Trimm, D. L. and Wainwright, M. S.: Catal. Today, 6, 261(1990).
8. Sherwin, M. S. and Frank, M. E.: Hydrocarbon Processing, 55(11),
122(1976).
9. Chemical Week, October 25, 41(1995).
10. Liu, Z., Tierney, J. W., Shah, Y. T. and Wender, I.: Fuel Processing
Technol., 23, 149(1989).
11. Palekar, V. M., Jung, H., Tierney, J. W. and Wender, I.: Appl. Catal. A,
102, 14(1993).
12. Tonner, S. P., Trimm, D. L., Wainwright, M. S. and Cant, N. W.: J. Mol.
Catal., 18, 215(1983).
13. Liu, Z., Tierney, J. W., Shah, Y. T. and Wender, I.: Fuel Processing
Technol., 18, 185(1988).
14. Choi, S. J., Lee, J. S. and Kim, Y. G.: HWAHAK KONGHAK, 32, 317
(1994).
15. Evans, J. W., Casey, P. S., Wainwright, M. S., Trimm, D. L. and Ca
N. W.: Appl. Catal., 7, 31(1983).
16. Monti, D. M., Kohler, M. A., Wainwright, M. S., Trimm, D. L. and
Cant, N. W.: Appl. Catal., 22, 123(1986).
17. Kim, Y. G., Lee, J. S., Kim, J. C., Lee, S. H., Kim, K. M.: HWAHAK
KONGHAK, 27, 396(1989).
18. Klier, K., Chatikavanij, V., Herman, R. G. and Simmons, G. W.: J.
Catal., 74, 343(1982).
Table 2. Results of reaction for LPMEOH & MF process
MF process LPMEOH process
Synthesis rate(mole/kg · hr) at GHSV of 2,600l/kg · hr
24.9 13.9
Maximum conversion per pass 80% 43%Optimum temperature(oC) 180 250Pressure(atm) 60 60Effect of CO2 tolerant up to 0.5% Limited to 1-3%Deactivation rate(H2/CO)=1 3.7%/day 24%/day
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