1.
 A Study on Comparison of Liquid-Phase Methanol Synthesis Processes for Coal-Derived Gas
 

      

^†*

  

*   

(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)



$%    Methyl Formate(MF) &'( ) LPMEOH  *+ ,- . /  0 12 34  056 789:. /   ;<=) /  >? @ ABC DEF G# 'DE2 H MF &'(  I7J K,- LMN:. OJ MF &'(  50% %  ! ) 3.7%/  P QR DE6 SF T, LPMEOH# U 30%  ! ) H2/CO P 1 2H 24%/ 

% PQR DE6 S MF &'(  I6 S9:. OJ  012HE 150-180^oC VEW 60X 

XY,- PZ VRJ  01 [F MF &'(  250^oC\] 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: jangsiks@hanmail.net

1.  

   100%     !" #$

%& ' ( )*. +,- ./0 +, 12 3 4  5"   ' ( )*.

467/8 9:; <=>? @A B CDE F GH I JB> KJB> L  )6M, 4N O, P67 Q1R0

 (=7 SA> T U1 VW B CDE &X0 IJB

>  YZ[ $35 \]  &U )*. ^_ KJB

> 4N `> 0a Fischer-Tropsch(FT) ^b c4d eU^

bN f B CDE F GH67, *g" &h ijk FT^b  l0a c4d eU^b mn o ,p )*. q" c4d

 IJ CD7 rs t0 uj, 2vwxyz, MTBE {  D7 =lk )6M, |}~s CD (= &X D7 /€k

 ‚ƒ „" (! …†k )*.

 c4d ‡C` (ˆ‰Š‹ " eU`(]j>4=

(= Œe)E s0a ICIr Lurgir Ž-j>C ‘+\

HWAHAK KONGHAK Vol. 39, No. 2, April, 2001 ’ ‰\ ^b“A67 &Xk )6M, ”•[ ij 0.46-0.5$A

*(‡C` – $0.5-1/million BTU‰—)[1]. ‡C` (

ˆ‰Š‹ R ij? eU` XU H2/CO 3-7˜x lR  4 `> R iU? 4` XU H2/CO 2-0.57 \[

" ~ )*. ICIr Lurgir “A H2/CO l /1 10

˜ 4`E IJ rs0™_ (= XUN o (U` ^b

% CO2& “AN šR› 0œ7 &U ž*. Ÿ  ~¡

¢‰£˜ IGCC(4`>¤e¢) C0a 4`E ]

¥ <" c4d7 90 ¦9 ` 8§’ C=0 G

¨N s0_ &U ‚\ …\?*.
 ¡$67 CŽk

) c4d eU^b ©U eU` ]¥9ª o «*.

¬­® Haldor Topsoer’ Š¢? “A Trickle bed ©(

" ^b‰E rs0a eU` ]¥9ª 92% , scale-up

 hydrodaynamics { ¯& °2k ), 9ªN o‰ ± 0a eU` ²N š ^b²  ³p )’ ´ª U * ' ( )*[2, 3].

Brookhaven National Laboratory’ NaH/RONa/M(OAc)2 ‘+E r s0µ Š¢? “A[4, 5] ‰ heterogeneous ‘+ ¶ ‘+

 Triglyme%  s+ ·y ¸ B\ ^b*.  ^b ¹ O˜ 80-100^oC ^b O 95%\ c4d mnE _’

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= (ˆ‰ & =!k l s “A \¾> ,Ä!˜67 …\?*[7].

B\ c4d eU^b(Liquid-Phase Methanol synthesis, LPMEOH)

Chem systemsr’ Š¢kÅ*[8].  “A ICI“A’ rsk

‘+  lÆ" Ž/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 |Ê67 \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’ Wkœ7 QÓÔ$ ÕÖ9ª  B\’ Wk ‹¶

²  ³p )*.

Methyl Formate(MF) K “A B\’ methyl formateE K

7 0a eU`7/8 c4dN ij0 GH67 ×Øٟ’

SkÅ*[9-11]. B\’ Wk ^bO lÒ$ ’ ]¥

9ª 90% Úµ X¾ t0M,  " o 9ª7 ˜R ‹

= Á? ÛÜ eU`E s' ( ) ,p )*. Ÿ  0.1%

\ % j>4= R ×¼kœ7 Ý " ×¼N ¹Ã' ( ) ‘+ Š¢ t0_ 4` $stU o*.

Þ’ ß CŽ’ 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 >? ‘+ äž? 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 kµ ŽUk )*(Fig. 1). B\ ^biU˜ c4d { condenser  bék ¿‰$67 êë0a `®7­ìŸíî(GC; HP5890, Porapak Q, Carbosieve S column, TCD) å ‹-1‰(Mass Spectroscopy, Balzers)7 1"*. 1¥ ãÏ <= 1¿] =!kœ7 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 t0µ Аk )*.

^b‰ ¿çk Ír4` - å XU bypass lineN  f `¦8 å `®7­ìŸíî7 €€ 1?*. ^b‰E È%"

¦^b` -% ¿ç` -% ~ å € ` XUN òó67 ^b²E j0â*.

3.   (MF)  

B\’ cô2cõE K 7 0a eU`7/8 c4dN i j0 GH c4d ]j>4= ^b0a cô2cõE iU

"[c4d ö÷> ^b; ^b (1)] ƒ cô2cõ (=>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.

 39 2 2001 4

CH₃OH + CO

HCOOCH₃+ 2H₂

2H₂+ CO

 GH q" c4d K  k eU`7/8 cô2c

õE IJ ij' ( )6M[^b (1)ú2 + ^b (2) = ^b (4)], c4 d% cô2cõE }  ij' ( )*.

2H₂+ 2CO

c4d ö÷> ^b wñcûrz ‘+7 w™ü )

[12-14], cô2cõ (=>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% cô2cõ (=>1R ^b }  ]þ*. ^bXÑ 100-180^oC å 40-100 ‰P*.  “A ³ p D` 2Á? j>4=  R ö÷> ^b ‘ +˜ wñcûrz ×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 ž?*. ^b u‰ 250 cc c4d $[- copper chromite(Ba-promoted; Aldrich) KOCH3(Aldrich)E  170^oC, 60

‰P’ 8 K}S copper chromiteE (=7 9 ƒ, -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% cô2cõ D 1N ±" N &0 ^b

‰’ &k 6œ7 ^b‰ °/ ² é$?*. ^b B

 ‰  XU `®7­ìŸíî å ‹-1‰7 10â*.

3-2. 

3-2-1. O

^b (1), (2) ÍL ¢Q^bœ7 O ˆÁ Þ QÓÔ$ Õ Ö9ª Ã="*. ^_ ‘+^b ^bO ˆÁ Þ ^b

² ˆ …\?*. ^bO
> Þ3  ^b²
>

E w‰ ±R 100^oC’ 180^oCV ^bOE
> 6M Ÿ %E Fig. 2 °Å*. Ÿ’  ò  100^oC’  U  *, O ˆÁ Þ  ^b² ˆÁN  â6, 180^oC \ ^bO’ ^b‰°’ s+7 s0

 c4d ˆ¢0 k,  \ B\^b ] *. Ÿ 

œ7 ^b 180^oC 0 O’ (R› "*. 160^oC \ ^ bO’  ^b² ˆ >kÅx  ^bO

ˆ Þ ^b (1) QÓÔ$ ÕÖ †67 },  K ˜ cô2cõ  Ã=Á ‰˜"*. Þ’ ^b <$O

150-180^oCN w ( )*.

3-2-2. j>4= å  ‚

B\  0_ ^b (1) ‘+˜ KOCH3 % ^b0a 2 cõ(HCOOK)E ݁ U ž* w™ü )*[11-13]. ^ bN 0‰  copper chromite KOCH3E c4d% Á ^b

‰ äž0 (=7 copper chromiteE 9 ý %A’  ¢

ik KOCH3E ×¼0 ?*. Þ’ 9 ƒ H2/CO Œe˜ ^ b`E ¿ç0a ^b ò7 k  pž$67 žk

  20 K ƒ A\\ ^b² ¶"*(Fig. 3).

^b u‰ copper chromite 9 R ¢i?  ^b K

% Þ copper chromite (U`^b(Water-Gas Shift; CO + H₂O

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\’ cô2cõ  pp ˆ0 M }  ^b² ˆ0a  20 K ƒ A\\ ^b²

 ¶0 ?*. , copper chromite cô2cõ (=> 1R

^b ‘+  (U`^b å KOCH3 i^b ‘+7

s?*.

^b A\\ ¶" ƒ ˜±$67 ^b‰ N ¿ç0a B\  E 2.5 mol%7 ˆ  %, ^b² Ζy

 ^b  žk !6M, " B\ cô2cõ 

Fig. 2. Change of Methyl Formate(MF) concentration and rate of methanol synthesis at various reaction temperatures(copper chromite 5 g, KOCH₃ 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, 150^oC, 60 atm).

HWAHAK KONGHAK Vol. 39, No. 2, April, 2001 0 kÅ*.  L I# ^b ö÷> ^b žk $67

˜R  ^b Ak‰ "¯*. ­%7 ^b K %Á Þ KOCH3 ik B\’ cô2cõ  pp ˆ

0M }  ^b² ˆ0a  40 K ƒ   A\\

 ^b² kÅ "   0.1 mol%7 ÝÅ*. 

 0.1 mol%(700 ppmv)˜ \[y o ’ ^b ž?* «

 KOCH3 copper chromite R ² i?* «N ¦"*.

 q" \[- KOCH3 lU>? 2cõ \7 ÁN

&"*. Þ’  ·y &? \’  ^bN ž0_ 

g KOCH37  o U ‰?*.

4` \[- j>4= 2Ák ), j>4=E ppm ³±V &0x \[" ls =!kœ7 ' 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 ž

" %E Fig. 3 °Å*. j>4= 1% 2Á?  ^b²

 75% Ã=0, 0.5% 2Á?  52% Ã=kM, " K

˜ cô2cõ  €€ 54% å 45% Ã=0a j>4=

R ö÷> ^b ‘+˜ KOCH3 ×¼N ˜0â*. Ÿ  10,000 ppmv(1%) CO2 2Á? `E rs0 ö÷> ³¼^b

  + ^b žk x ^0a MF K “A 

copper chromite R KOCOOCH3 KOCH37 ik ^b  ' A ž?*(^b 6).

KOCOOCH₃+ 3H₂→KOCH₃+ H₂O + CH₃OH (6)

j>4= 2Ák  eU`E * ,™° ^bN ž

" %, í ^b² 70%V ¥¤k ]/ lÓ$˜ l

U> ]-N w ( )Å*.

3-2-3. eU` ²

¿çk eU` ²
> Þ3 ^b² å 9ª
>E w‰ ±0a 150<sup>o</sup>C’ ^b‰ ¿çk ` ²N
>

 %E Fig. 4 °Å*. Ÿ’ . ( )/ ² ˆ

Þ ^b² ˆ0 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 žkœ7, ²ˆ Þ3 ^b²
> …\0

 %*.  ^b žk \’ 700 ppmv  B\

 )6œ7 (U`^b R ¢ik CO2  ²’ ¦

^b` ² 6œ7 ´%$67 ^b‰’ &k 10‰

"¯67 i€?*.

3-2-4. eU` XU(H2/CO lª)

eU` &X0 GH% D Þ Ÿ XU **. ]^

$67 ï rsk ‡C` (ˆ‰Š‹  H2/COl 3- 7, /1j>(partial oxidation)  1.6-2, Ÿ 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% pž$˜ ^b² ˆE â*.  ^b‰ °/ ] j>4= 1P ˆ Þ3 B\ cô2cõ  ˆ ‰˜"

*(Fig. 5). Ÿ  eU` H2/CO l 0.5˜ , ^b² Î

–y Ã=? ^_ cô2cõ  Ζy ˆkÅ*.   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

 ^b²E a  “A 4` $stU o “A

N r"*.

3-2-5. ,‰K SAU

ß “A \¾>k‰ ±R’ ‘+ , K W lU>

A ’ o UN R› "*. D` H2/CO l 2

˜  100 K W % lU> ² 0-0.4%/]7  

 !*. Ÿ  ß CŽ’ \67 0 4` Ö$˜

XU˜ H2/CO=1’ lU> ] 3.7%/] lU> ²E

˜*. " B  XUN Xr" %, K ˜ cô2cõ 

  Ã=ÁN w ( )Å*(Fig. 6). cô2cõ  Ã=

^b (1) ‘+˜ KOCH3 UN ) «67 R' ( )*. Ÿ 

 £" ò  KOCH3 ^b (2) ‘+˜ copper chromite

R ² ikœ7, ]j>4= 1P o \’ copper chromite pž$˜ ×¼ R KOCH3 i 0 žk

* R' ( )*. ã&7 ^b (2)E copper chromite ‘+\

’ ž' ", ]j>4= Ó$67 copper chromite ‘+E ×

¼0 «67 ? ò )*[13].

Fig. 4. Change of conversion and rate of methanol synthesis at various flow rates of inlet gas(copper chromite 5 g, KOCH₃ 0.833 g in 250 cc methanol, H₂/CO=2, 150^oC, 60 atm).

Fig. 5. Effect of H₂/CO ratio of inlet gas mixture on methanol synthesis rate(copper chromite 5 g, KOCH₃ 0.833 g in 250 cc methanol, 250 cm³/min, 150^oC, 60 atm).

 39 2 2001 4

4. LPMEOH 

LPMEOH “A c4d eU ^b[^b (3)] o ^bQ (∆H₂₉₈^o =

−90.64 KJ/mol)7 ˜" Ž-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_’ ^b0µ 0a ^b`

]¥9ªN 30%V o˜ “A*.

ICIr ‰\ ^b “A% r" X¾XÑ’ Wk LPMEOH

“A ©567
 \s“A’ 6t" ]j>4= lª

 o 4` IJ rs t0M, } A/X¾ { X

¾
 s0, ij? c4d 2Á? (1 ‰ “A(4-20%)  lR $ Ák(1% ¦) c4d A& ls ¹Ãk ,pÝ

 )*. q" X¾  77W ‘+E ² ¿ç' ( )’ C²

$˜ W t0*.

4-1.


^b 300 cc `˜``ô autoclave’ C²¨67 ž?*. ^ b u‰ 150 cc mineral oil(Aldrich) ‘+E  180^oC, 60‰P ’ 10-13 K}S (=7 9 ƒ, -Xæ R XU% -

Xæ? eU` 250^oC7 ? ‘+ Ç E È%"*. ¦^b

` -% ¿ç` -% ~7 ^b²E j0M, ^b6 7 ij? c4d condenser bé?*. ^b B  ‰  X U `®7­ìŸíî å ‹-1‰7 10â*.

^b CuQ 489 \s‘+E rs0â*. Ý ‘+ :_

$(BET, ASAP2010, Micromeriticsr) Table 1 : 0â*.

4-2. 

4-2-1. € ‘+ ^bU

€ \s ‘+ " ^bU ㈠ãÏ %E Fig. 7 °Å*. €

‘+ ^bU ãÏ %, Ÿ’  ò  Cu/ZnOQ A‘

+ ^b² , o, lU ² ,  «67 

LPMEOH “A ㈠‘+7 mn0â*. Ý ‘+ ÍL j>4

= 2Ák  eU`E ,™; % c4d7 9ª 

 0 V<’ j>4= = (!ÁN w ( )Å*. “A ãˆ

‘+7 mn? A‘+ , o :_$ o U% >? )*

 ' ( )6, A‘+ :_$ 1/4N @ C‘+ A‘+ u‰

^b² r0a ‘+ :_$  ‘+ XU { *3 !˜

 ‘+ U ‚N ¦AN š†' ( )*. B7 C‘+ Cu/

ZnO/Al₂O₃ ‘+*.

4-3-2. ^bO

<$ ^bOE Xr0‰ ±0a A‘+ 15 gN äž0 ^b O

E 210^oC’ 275^oCV
> ý_’ c4d eU ãÏN ("

%E Fig. 8 °Å*. Ÿ’ þ ò  O ˆÁ  Þ c4d ^b² ^b` ]¥9ª ˆ0 «N w ( )6M, 210^oC’ 30.0% ]¥9ªN , O ˆ

Á ‘+ U ˆ0a ^bO 250^oC’ 42.7% < ]¥

9ªN FN ( )Å*. 275^oC’ c4d eU² Ã=0â*.

Þ’ ^b <$O 250^oC /467 à»kÅ*.

4-3-3. ^bP5 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, 164 Ncm³/min, H₂/CO=1, 150^oC, 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, 250^oC, 60 atm, CO₂=1.7-5.4%).

Fig. 8. Change of methanol synthesis rate of LPMEOH process and CO_x conversion at various reaction temperatures(catalyst A 15 g in 150 cc mineral oil, 260 Ncm³/min, H₂/CO=2, 60 atm, CO₂=3.2%).

HWAHAK KONGHAK Vol. 39, No. 2, April, 2001

^bP5N 40‰P’ 70‰PV
> N " ^b² ¦º

‚N Fig. 9 °Å*. ^bP5 ˆ0_ c4d eU² ˆ

"*. 40‰P’ 60‰PV ^bP5 10‰P ˆ Þ ^b

² 10%\ ˆE , 60‰P’ 70‰PV ^b²

ˆ 6.3%7 60‰P \ P5ˆ ´sU $N w ( )*.

4-3-4. j>4= ‚

^b‰ äž? 15.0 g A‘+\’ eU` 2Á? CO2

> Þ3 c4d eU²
>E Fig. 10 °Å*. CO2

 0%]  ^b + ] !6M, 3%˜  , o c4d eU²E °Å*.  Klier { & " % ] º"*[18]. CO2 1.0% Á? eU` lR 3% Á? eU

` 1±‰’ 21% UˆE â*. Ÿ  CO2  5%7 ˆ

0_ c4d eU² Ã=0â K - Þ ‘+  U Ã=0 lU> >CkÅ*. , Ž ‘+E rs0

LPMEOH“A 1-3% D 0± CO2 Á? D`

R’ c4d eU tÁN w ( )*.

4-3-5. ^b` ²

A‘+ 6 gN ^b‰ äž0 eU`(H2/CO=2, CO₂=3.7%) 

²N 262 Ncm³/min(GHSV=2620 l/kgEhr)’ 512 Ncm³/min67 ˆ

 ý_’ F %E Fig. 11 °Å*. ² 2Y7 ˆÁ Þ iU²  50% ˆ0 eU` ]¥9ª 35.3%

’ 26.5%7 Ã=0â*. ©" p ² 262 Ncm³/min’ l

U>  Å6 ²N 512 Ncm³/min7 ˆ ý_ ‘+ l

U> ]þ* «*.

4-3-6. ^b` XU å ,‰K SAU `õ

eU` XU(H2/CO)N 2’ 4` :$˜ XU˜ 1

>  %E Fig. 11  °Å*. " lU> ² 24.2%/

]Å*. ‘+ äž-N 15 g67 F eU` XU(H2/CO) 1

˜ eU` ²N 260 Ncm³/min7 ˜  ãÏ %E Fig. 12  °Å6M,   lU>ª 24.4%/]7 lU>
\

 Šm G !*. L HI7 (" \s‘+˜ C‘+ 

 eU` XU(H2/CO) 1% 2 ÍL’ 20%/] Ú o l

U>ªN â*. Þ’ LPMEOH “A 4`E JD7 0

c4d eU rsK  ï g ‘+ =!K «67 …\?*.

5.  

LPMEOH “A% MF K “A ㈠ãÏ %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, 250^oC, 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 cc mineral oil, 260 Ncm³/min, H₂/CO=2, 250^oC, 60 atm).

Fig. 11. Change of methanol synthesis rate at various inlet flow rates over 6.0 g of A catalyst in LPMEOH process(150 cc mineral oil, 250^oC, 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, 260 Ncm³/min, 250^oC, 60 atm, CO₂=3.0%).

 39 2 2001 4

Ò0â*.

“K ²   Ó’ ‘+ ³± 3[ ^b² MF K “A (0*. 4`s c4d eU“A (( Xј

o eU` ]¥9ª _’ MF K “A LPMEOH “A  lR L{y (0*. 4`E D7 rs"  \s> X ј ‘+ SAU_’ MF K “A ‘+ lU>ª

LPMEOH “A lR ’ ^$67 MF K “A 4

`s c4d eU“A67 $e" «67 à»?*. MF K “A

³p˜ =- CO2 " ×¼
\ 0.5% CO2 2Á? eU`

 ^b ž Þ Šm a ) 4` rs t U o*.



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, 95 (1988).

4. Sleigeir, W. A., Sapienza, R., O’Hare, T., Mahajan, D., Foran, M.

and Skaperdas, G.: 9th EPRI Contractors Meeting, Palo Alto, CA, May(1984).

5. Sapienza, R. S., Sleigeir, W. A., O’Hare, T. E. and Mahajan, D.: U.S.

Patent No. 4,619,946(1986).

6. Muhajan, D. and Mattas, L.: Proceedings of the 16th Annual EPRI 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 Cant, 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 2,600 l/kg · hr

24.9 13.9

Maximum conversion per pass 80% 43%

Optimum temperature(^oC) 180 250

Pressure(atm) 60 60

Effect of CO₂ tolerant up to 0.5% Limited to 1-3%

Deactivation rate(H₂/CO)=1 3.7%/day 24%/day