TABLE OF CONTENTS
1.1
OVERVI OVERVIEW EW OF FORMIC FORMIC ACID... ACID........ .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... ............. ..........2 ..2
1.2
PHYSICA PHYSICAL L AND AND CHEMIC CHEMICAL AL PROPER PROPERTIES TIES..... .......... .......... .......... .......... .......... .......... ........... .................. ......................3 ..........3
1.3
USES USES AND APPLICA APPLICATIO TION... N........ .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... ............... .................4 .......4
1.4
PRODUCTI PRODUCTION ON OF OF FORMIC FORMIC ACID... ACID........ .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... ............. ...............7 .......7
1.4.1
SODIUM FORMATE............ FORMATE....................................... ...................................................... ....................................................... ............................ 7
1.4.2
HYDROLYSI HYDROLYSIS S OF FORMAMIDE........................ FORMAMIDE................................................... ................................................. ...................... ..7
1.4.3
BUTANE BUTANE LIQUID-PHASE LIQUID-PHASE OXIDATION...... OXIDATION................................. ............................................................7 .................................7
1.4.4
METHYL FORMATE FORMATE HYDROLYSIS HYDROLYSIS.......................... ................................................................. ....................................... .....8 ..... 8
1.
PATENTED TENTED PRODU PRODUCTIO CTION N OF FORMIC FORMIC ACID. ACID...... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... ........8 ...8
1..1 1..1
PRODU PRODUCIN CIN! ! FORMIC FORMIC ACID ACID FROM FROM A CARB CARBOHY OHYDRA DRATE TE-CO -CONT NTA AININ! ININ! MATERIAL...........................................................................................................8
1..2 1..2
MANUF MA NUFA ACTURI CTURIN! N! FORMI FORMIC C ACID ACID BY BY METHY METHYL L FORMA FORMATE TE HYDR HYDROL OLY YSIS... SIS... ..11
1..3 1..3
MANUF MA NUFA ACTURI CTURIN! N! FORMI FORMIC C ACID ACID BY METH METHYL YL FOR FORMA MATE TE HYDR HYDROL OLY YSIS.....13 SIS.....13
1."
PROCESS PROCESS SELECTI SELECTION.. ON....... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... ............ ................... ........................ ...............1" ...1"
1.".1 1.".1 1.7
SCORIN! SCORIN! METHOD... METHOD........ .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... ........... .................17 ...........17
CAT CATALYS ALYST.... T......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... ................. ........................ ................ ....1# 1#
1.7.1 1.7.1
CAT CATALYS ALYST T SELECTI SELECTION.. ON....... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... ............ ................... ....................1# ........1#
1.7.2 1.7.2
CAT CATALYS ALYST T PHAS PHASE... E........ .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... ............... ...................... ...................2$ .......2$
1.8
MODIFIE MODIFIED D FORMI FORMIC C ACID ACID PROCE PROCESS.. SS....... .......... .......... .......... .......... .......... .......... .......... .......... .......... ............. ..................21 ..........21
1.#
PROCESS PROCESS FLOW FLOW DIA!RAM DIA!RAM %PFD&..... %PFD&.......... .......... .......... .......... .......... .......... .......... .......... .............. ..................... ...................22 .......22
1.1$
PROCESS PROCESS DETA DETAILS...... ILS........... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... ............ ................... .............. ..23 23
1.1$.1 1.1$.1
CARBONYL CARBONYLA ATION TION OF CARBON CARBON MONOXID MONOXIDE E AND AND METHANO METHANOL...................23 L...................23
1.1$.2 1.1$.2
SEPAR SEPARA ATION TION OF REACTA REACTANT.. NT....... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... ...............24 ..........24
1.1$.3 1.1$.3
HYDROL HYDROLYS YSIS IS REACTION REACTION OF METHYL METHYL FORMAT FORMATE.... E......... .......... .......... .......... .......... ............. ..........24 ..24
1.1$.4 1.1$.4
SEPAR SEPARA ATION TION OF OF METHA METHANOL. NOL...... .......... .......... .......... .......... .......... .......... .......... .......... .......... .......... ................ ...............2 ....2
REFERENCES....................................................................................................................2"
1
CHAPTER 1
PROCESS BACKGROUND
1.1
OVERVIEW OF FORMIC ACID
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
C H 3 OH + CO ⇌ HCOOC H 3 Methanol 2
Methyl formate
1
HCOOC H 3 + H 2 O ⇌ C H 3 OH + HCOOH Methyl formate
2
Formic acid
B+0 (* +/(*0 1 +* 2> / 5+* 9 0/6;/:/ )+ :(6/5 +5/ /0 ;(5 9, +5/(* (: 5+9(* 6(*(/ /) + +0 ;/5 /* E+/(* 3.
CO + H 2 O ⇌ HCOOH
3 %S(5 !*+0(*> 1##8&
1.2
PHYSICAL AND CHEMICAL PROPERTIES
F(6/5 +5/ /0 +0( =*(* +0 6)+*(/5 +5/> :(6,/5 +5/> ( ),(* 5+9(,/5 +5/> )/5) /0 ) 0/6;0 5+9(,/5 +5/ %P9C)6> 2$1&. I 5(*0/00 (: (* 5+9(* +(6> ( (,* +(60 +* ( ),(* +(60 /) ) 6(5+ :(6+ (:
CH 2 O2
. F(6/5
+5/ /0 + 5+> 5((00 // /) ;** +* //+/* ((. A0 / /0 ) 0/6;0 5+9(,/5 +5/> / /0 6/05/9 /* + /) +0 (: )+ +* :60 /* +/. C+9(,/5 +5/ /0 0+9 +* / 60 9 ;<* :(6 0(* 9+00> 0(* (///* +*0 +* ;( 6+0. I /0 +0( + ),(05(;/5 )/5) /0 ) +9//, ( +0(9 + :(6 /0 0(*/*. T+9 1.1 0)(0 ) ;),0/5+ +* 5)6/5+ ;(;/0 (: :(6/5 +5/.
T+9 1.1 P),0/5+ +* 5)6/5+ ;(;/0 (: :(6/5 +5/. P),0/5+ ;(;/0 F(6+
F(6/5 +5/
R:*50
CH 2 O 2
P, +* !*> 1###
S5 P9C)6> 2$1
3
4".$3
P, +* !*> 1###
M(5+ /) P, +* !*> 1### F(6 +* 5((
C((00 //
S;5/:/5 +,
1.22$ 2$G4
P, +* !*> 1### P, +* !*> 1### M/* ;(/*> C
8." P, +* !*> 1###
B(//* ;(/*> C
1$$.8
P),0/5+ 0+
L//
A<(+( C)6> 1###
P** ((
A<(+( C)6> 1###
434
A<(+( C)6> 1###
"#
A<(+( C)6> 1###
S(* +5/
A<(+( C)6> 1###
M/05/9 /* )> +5(*>
O@N/> 2$$"
O( A(-/*//(* ;(/*> C F+0) ;(/*> C ;H M/05/9//,
), +5+> 6)+*(> )+*(. M/05/9 ;+/+, /* 9**> (*> +* ,*0. W+ 0(9//,
1.3
1$$$$$ 6GL + 2 C
R//5= +.> 1#8
USES AND APPLICATION
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
4
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
T+9 1.2 A;;/5+/(*0 (: :(6/5 +5/ /* /*0/0 %BASF> 2$14&. I*0/0 C+*/* +* 5+/*
A;;/5+/(* D*0 F(( C+* !*+ 0 5+* I*0/+ C+*0
F(( +* B<+
S+*/+, C+*0 A5()(/5 /*=0> B F(( ;(500/*
L/<0(5= 9/*> P0
D/0/*:5+* %:(( ;(500/*& P/0 F+*/* ;/ P/ S( P(, B R6/*+*0 C+:
5
C+ M+*:+5/*
D+/, 5( C)6/5+ M+*:+5/* M+*:+5/* (: 5+*0 M+*:+5/* (: ;0/5/> :// M+*:+5/* (: ;)+6+5/5+0 F/ +* +0 +6* !+0 ;/:/5+/(* W+ ;;++/(* R99 P(500/* T/0 W+ +6*> D/*=/* + I*0/+ M*/5/;+
M/*/*> O/ J !+0
S+ ;(500/* O/ +* +0 +5/(*
T/0 +* L+)
B(/* F/*/0)/* (: /0 B+5)/* %/0& M5/+/(* %/ :/*/0)/*& P+/* %/ :/*/0)/*& L+) 6+*:+5 T+**/*> R+**/*
1.4
PRODUCTION OF FORMIC ACID
B+0 (* R6+** J K/5=+> %2$$&> ) + :( 6)(0 ( ;(5 :(6/5 +5/ )/5) + 1. S(/6 :(6+
6
2. H,(,0/0 (: :(6+6/ 3. B+* //-;)+0 (/+/(* 4. M), :(6+ ),(,0/0
1.4.1
SODIUM FORMATE
P(5/(* (: :(6/5 +5/ :(6 0(/6 :(6+ /0 + +//(*+ +,0. E<* )()> ) 5)*((, /0 ) (0 5)*((, 0 ( ;(5 :(6/5 +5/ 9 / )+< 0(6 /0+<+*+0 05) +0 ;(( (=/* 5(*//(*0 +* 0/(0 ;(/(*. L(* /6> 6+*, /*0/0 +;;, )/0 5)*((, ( ;(5 :(6/5 +5/ 9 *(++,0 ), ;: ( 5)((0 +*() 5)*((, %R6+** J K/5=+> 2$$&.
1.4.2
HYDROLYSIS OF FORMAMIDE
T)/0 6)( ( ;(5 :(6/5 +5/ +0 <(; 9, !6+* BASF C(6;+*,. T) ;(500 ( ;(5 :(6/5 +5/ )+0 ) 0+0. T) :/0 0+ /*<(<0 + 5+9(*,+/(* (: 6)+*( ( ;(5 6), :(6+. T) 05(* 0+ /0 ( ;(5 :(6+6/ )() +66(*(,0/0 (: ), :(6+. A* ) )/ 0+ /0 9, 0/* 0:/5 +5/ ( ),(, :(6+6/ ( :(6/5 +5/ +* +66(*/6 0:+. B +: ,+0 6;(, )/0 6)(> ) 5)*((, 5+/60 )+* )/) 5(0 (: ;(5/(* %R6+** J K/5=+> 2$$&.
1.4.3
BUTANE LIQUID-PHASE OXIDATION
F(6/5 +5/ /0 ;(5 +0 + 9,-;(5 9, +;;,/* ) // ;)+0 (/+/(* (: *-9+*. I* )/0 6)(> 9+* 95(60 + ),(5+9(*. I* ) :/0 0;++/(* ;(500 :(6 (/+/(* ;(5> 9+* )/5) ( *( +5 , /) <(+/ *+ 5(*0/*0 +* + + 0;++ :/0. F(6/5 +5/ /0 ;(5 /* ) * 5(6*. T) ;(00/9//, (: /* ) ;5*+ (: :(6/5 +5/ /0 +9( #$ +* 5+* +0( (9+/* + #8 /* :) 0;++/(* %R6+** J K/5=+> 2$$&.
7
1.4.4
METHYL FORMATE HYDROLYSIS
M), :(6+ ),(,0/0 /0 ) +0 6)( 0 9, 6(0 (: ) /*0/0 /* ) ( ( ;(5 :(6/5 +5/. T) 6)( 0+, 6(/:/ 9, /::* (: 5)*((/0 ;*0 (* /6* (: ) 5(6;+*,. T)/0 5)*((, )+0 9* 0 9, K6/+-L(*+> BASF +* USSR. T)/0 6)( /0 9+0/5+, )+0 ( 0+0. T) :/0 0+ /0 =*(* +0 5+9(*,+/(* ;(500 +* 05(* 0+ + =*(* +0 ),(,0/0 ;(500. F( ) 5+9(*,+/(* ;(500> 6)+*( /0 5+9(*,+ /) 5+9(* 6(*(/. S(6 (: 0+5) :(* ( )(6(*(0 5++,0 0 /* )/0 ;(500 5+* 0; ; ) +5/(*. T)*> ) 6+/* ;(5 :(6 ) 5+9(*,+/(* ;(500 )/5) /0 6), :(6+ /0 ),(, ( :(6/5 +5/. T) ),(,0/0 ;(500 /0 *, :(* ( ( 9 5(*(6/5+, :+0/9 +: ,+0 (: +0+5). T)/0 6)( /0 :(* ( 9 00 )+ 5(*06;/(*> 6(0 +0(*+9 ;(500> +* 00 5(0 5(6;+ ( +*() 6)(. B /* ( ( +5)/< )/) ;/, (: :(6/5 +5/> ) +((; 6+, :(6 9* + +* :(6/5 +5/ ) (( 0;++/(* 5)*/ /0 * %R6+** J K/5=+> 2$$&.
1.
PATENTED PRODUCTION OF FORMIC ACID
I* )/0 09-(;/5> ) /::* ;+* ;(5/(*0 (: :(6/5 +5/ / 9 /0500. I* ( ( *0+* ) :(6/5 +5/ ;(5/(* /* /*0/0 05+> 0,/* /*0/0 ;+* /0 ) 90 +, ( ( 0( ) ) ;(500 /0 6( +/0/5> ;+5/5+> +* /* +/0.
1..1
PRODUCING
FORMIC
ACID FROM
A CARBOHYDRATE-CONTAINING
MATERIAL !F"#$%'"() *#. &+., 212.
B, 0/* +5/ +6*> 5+9(),+ 6(50 /= 5(0 ;(,6> ++5(0> ( 0/6/+ )(* 0+0 5+* 9 ),(, ( 95(6 )(* 6(*(60. F) ),(,0/0 / 0 ( ) :(6+/(* (: :(6/5 +5/ +* </*/5 +5/. E+6; (: 5+9(),+-5(*+/*/* 6+/+0 )+ 5+* 9 0 +0 + 6+/+ (: ) ;(500 + ;+; ;;> ((> :(( +0> 0/5)-+00> +0 ;+; +* 0+. T) + 6+/+ 60 5(*+/*/* 5(0 :( ) ),(,0/0 ;(500 ( ;(5 0+. T) ;(500 /0 5(*0/0/* (: 6/; +5/(*0 ( 0;0 +0 0)(* /* T+9 1.3.
8
T+9 1.3 P(500 0;0 (: :(6/5 +5/ ;(5/(* :(6 + 5+9(),+-5(*+/*/* 6+/+. STEP 10 *
2
3
PROCESS S+ %/*6/+ ),(,0+& /0 ;(5 9, +5/ ),(,0/0 (: ) + 6+/+ )+ 5(*+/*/* 5(0 F) ),(,0/0 (: ) /*6/+ ),(,0+ ( 95(6 * ;(5 5(*+/*/* :(6/5 +5/. S;++/(* ;(500 (: :(6/5 +5/ :(6 ) ),(,0+ ;(5.
T) ,/ (: :(6/5 +5/ 5+* 9 + )+* +* )(/5+, 5+* 9 + )+* 7$. T( /*//+ ) ;(500> +* +5/ /= 0;)/5 +5/> *//5 +5/> ;)(0;)(/5 +5/> ),(5)(/5 +5/> ),(:(/5 +5/> ( ),(9(6/5 +5/ /0 + ( ) + 6+/+ +* ) 6/ 95(6/* +(0 0,. T6;+ +* ;00 (: ) ;(500 5(*//(*0 /0 +0 :( +(/* ) ),(,0/0 ;(500. T+9 1.4 9( 0)(0 ) 066+, (: ) ;(500 )/ F/ 1.1 0)(0 ) ;(500 :( /++6 %PFD& (: ) ;(500.
T+9 1.4 P(500 066+, (: :(6/5 +5/ ;(5 :(6 5+9(),+-5(*+/*/* 6+/+.
PARAMETER Y+ (: ;(500 ;+* R+ 6+/+
PROCESS CHARACTERISTIC 2$12 1. C+9(),+-5(*+/*/* 6+/+ %E+6;> ;+; ;;> ((> :(( +0> 0/5)-+00> +0 ;+; +* 0+& 2. S;)/5 +5/> *//5 +5/> ;)(0;)(/5 +5/> ),(5)(/5 +5/> ),(:(/5 +5/> (
B, ;(5
H/)0 ;(00/9 ;(500 6;+ H/)0 ;(00/9 ;(500 ;00 Y/ ;5*+ C++,0 O;+/* /;6*
1. 2. 3.
1. 2. 3. 4. . ".
9
),(9(6/5 +5/ L</*/5 +5/ C+9(* 6(*(/ +0 W+ 23 C N( 6*/(* N( 0. !/* M/ P6; P :( +5( %PFR& C(*/*(0 0/ +*= +5( %CSTR& F+0) +*=
F/ 1.1 PFD (: :(6/5 +5/ ;(5/(* :(6 + 5+9(),+-5(*+/*/* 6+/+ %F/;+/5= . +.> 2$12&.
1..2
MANUFACTURING FORMIC ACID BY METHYL FORMATE HYDROLYSIS !H/0*(0#$ *# &+., 15.
T)/0 ;(500 /0 /*(5 ( /6;(< ) :(6/5 +5/ ;(5/(* 9, 0/* +5/(,0/0 (: :(6+6/ /) 0:/5 +5/ )/5) )+0 9* 5+/6 ( ;(5 (( 65) (: +66(*/6 0:+ +0 ) 9, ;(5> )/5) /0 *( :+<(+9. T)/0 ;+* /0 +0( 5+/6 ( )+< 9 ;(500 ;(;/0 5(6;+ ( !6+* P+* N(. 2>4$7>17> )/5) /0 ) ;(5/(* (: :(6/5 +5/ 9, 6), :(6+ ),(,0/0. T) ;(500 /0 0+/ ( 9 *+55;+9 ( ) 0+ (: 0;5/+ /0/+/(* ;(500 ( ;00 )/) + (: -0/:/5+/(* 0/* :(6 ) 0+ (: + 5++,0. T) 0;5/+ /0/+/(* ;(500 00 + + +6(* (: 0+6 )/5) /0 06 *5(*(6/5+ 95+0 ) :(6/5 +5/ ;(5 (*, 7 ;/, 9, /) )/5) /0 5(*+0 :(6 )/) ;/, 6+*. H()*05) +.> %1#8$&> )+0 /*(5 ) 9 ;(500 (: :(6/5 +5/ ;(5/(* 9, /6;(* ) 6)( 9, 0/* 6), :(6+
10
),(,0/0. T) ;(500 00 + 6+/+ (: 6), :(6+ /) ;/, (: #7 9, 6( ;5* /) ) 6+/*/* 5(6;(** (: 6)+*(> +> +* + 9+00 )/5) /0 1-%1-*;*,&-/6/+(. T) ;(500 /0 5(*0/0/* (: 6/; +5/(*0 ( 0;0 +0 0)(* /* T+9 1. T+9 1. P(500 0;0 (: :(6/5 +5/ ;(5/(* 9, 6), :(6+ ),(,0/0.
STEP 10
PROCESS M), :(6+> +> +* 1-%1-*-;*,&-/6/+( + /*(5 /*( + 9+ +5(. H,(,0/0 (: 6), :(6+ (550 /* ) +5( +*
*
2
3
;(5/* :(6/5 +5/. T) ( 0+6 (: ) +5( /0 0* ( ) 1 0 ;+5= 5(6* ( 0;++ ) *+5 6), :(6+ +* 5,5 / 9+5= ( ) +5(. T) 0+6 5(*+/*/* :(6/5 +5/> +> +* ) 9+0 /0 0* ( ) 2 * ;+5= 5(6* ( 0;++ + )/5) /0 +0( 9/* 5,5 9+5= ( )
)
4
+5(. T) 6+/*/* 0+6 /0 0* ( ) 3 ;+5= 5(6* ( 0;++ ) 9+0 :(6 ) ;(5> :(6/5 +5/. T) 9+0 /0 5,5 9+5= ( )
)
+5(. T) :(6/5 +5/ /0 :) + /* ) 4 ) ;+5= 5(6* ( ;(5
)/) ;/, (: :(6/5 +5/. T)/0 )( ;(500 /0 +5)/* ## (: :(6/5 +5/ ,/ )/ ) 5(*<0/(* (: 6), :(6+ /0 "4. F( <, (* (: :(6/5 +5/ ;(5> 2.2 (* (: 0+6 //, /0 0 :( ) */ ;(500. T)/0 ;(500 /0 5+/6 ( 9 6( 5(*(6/5+ 5(6;+ ( ) () 6)(0 )+ )+0 9* 6*/(* 9:(. T) 6+/* =, )+ 5(*/9 ( /0 +<+*+(0 ;(500 /0 ) 0+ (: ) 9+0 /* ) 6), :(6+ ),(,0/0. T)/0 /0 95+0 ) 9+0 5+* :(6 + 0+/= 9(* /) :(6/5 +5/ )/5) /0 0::/5/*, 0(* ( /)+ ) ;(5 :(6 ) ),(,0/0 //9/6. T) () +<+*+0 (: ) ;(500 + *( 9,-;(5 ;(5 +* ( *, 5(*06;/(*. T) 066+, (: ) ;(500 5)++5/0/50 /0 0)(* /* T+9 1." 9(.
T+9 1." P(500 066+, (: :(6/5 +5/ ;(5/(* 9, 6), :(6+ ),(,0/0
PARAMETER Y+ (: ;(500 ;+*
PROCESS CHARACTERISTIC 1#8$
11
R+ 6+/+
B, ;(5 H/)0
;(00/9
;(500
6;+ H/)0 ;(00/9 ;(500 ;00 Y/ ;5*+ P/, C++,0 O;+/* /;6*
1..3
1. M), :(6+ 2. 1-%1-*-;*,&-/6/+( 3. W+ N( 9, ;(5 13$ C
1. 2. 3. 4. .
1$ +6 ## N( 6*/(* N( 5++,0 T9+ :( +5( %PFR& 10 ;+5= 5(6* 2* ;+5= 5(6* 3 ;+5= 5(6* 4) ;+5= 5(6*
MANUFACTURING FORMIC ACID BY METHYL FORMATE HYDROLYSIS !H&6 *#. &+., 212
I* )/0 ;+*> :(6/5 +5/ /0 ;(50 9, +5/* 5+9(* 6(*(/ +* 6)+*( 9, 5+9(*,+/(* +5/(* /) + ;0* (: )(*(0 5++,0 ( ;(5 6), :(6+. I* :) +5/(* (: 6), :(6+ /) + 9, ),(,0/0 ;(500 /0 ;(5/* :(6/5 +5/. T) ;(500 5(*0/00 (: " 6+/* 0;0. T+9 1.7 0)(0 ) 6+/* 0;0 (: ) :(6/5 +5/ ;(5/(*.
T+9 1.7 P(500 0; (: :(6/5 +5/ ;(5/(* 9, 6), :(6+ ),(,0/0.
STEP 10
PROCESS C+9(*,+/(* +5/(* (: 6)+*( /) 5+9(* /(/ /* + CSTR /) ) ;0* (: + )(*(0 5++,0. T) +5/(* /0 ;(5/* 6),
*
2 3 )
4
:(6+. T) 6/ (: ) +5( /0 0* ( + :/0 0;++( )/5) /0 + :+0) 5(6*. T) 6/ :(6 ) :/0 0;++( 5(*+/*/* 6), :(6+ /0 0* ( + 05(* 0;++( )/5) /0 + /0/+/(* 5(6*. T) 6/ :(6 ) 05(* 0;++( 5(*+/*/* 6), :(6+ /0 0* ( + +5/< /0/+/(* 5(6* %RDC&. I* ) RDC> + /0 /*(5 +*
)
+50 /) ) 6), :(6+ ( ;(5 :(6/5 +5/ 9, ),(,0/0 +5/(*. T) 6/ :(6 ) DC /0 5(*<, ( + )/ 0;++( )/5) /0 +
12
)
"
/0/+/(* 5(6*. T) 6/ :(6 ) )/ 0;++( 5(*+/*/* :(6/5 +5/ /0 0* ( + :() 0;++( %/0/+/(* 5(6*& ( ;(5 )/) /6;/, (: :(6/5 +5/.
T) ;(500 5(*0/00 (: 6+*, 0;++/(* ;(5000 95+0 :(6/5 +5/ +* + /0 :(6/* +((; 6/. A)() ) ;(500 5(*0/00 (: 6+*, 0;++/(* ;(5000> ) ;/, (: ) ;(5 :(6/5 +5/ /0 <, )/) )/5) /0 ## 9, /) ;5*. T) 066+, (: ) ;(500 5)++5/0/50 /0 0)(* /* T+9 1.8 )/ F/ 1.2 0)(0 ) ;(500 :( /++6 %PFD& (: ) ;(500.
T+9 1.8 P(500 066+, (: :(6/5 +5/ ;(5/(* 9, 6), :(6+ ),(,0/0.
PARAMETER Y+ (: ;(500 ;+* R+ 6+/+
B, ;(5 H/)0
;(00/9
;(500
6;+ H/)0 ;(00/9 ;(500 ;00 Y/ ;5*+ P/, C++,0 O;+/* /;6*
PROCESS CHARACTERISTIC 2$12 1. C+9(* 6(*(/ 2. M)+*( 3. W+ N( 9, ;(5 1$7 C 4$ +6 N( 6*/(* ## %9, /) ;5*& S(/6 6)(/ ( /(*-5)+* 0/* 1. P :( +5( %PFR& ( C(*/*(0 2. 3. 4. . ".
13
0/ +*= +5( %CSTR& F/0 0;++( %F+0) +*=& S5(* 0;++( %/0/+/(* 5(6*& R+5/< /0/+/(* 5(6* T)/ 0;++( %/0/+/(* 5(6*& F() 0;++( %/0/+/(* 5(6*&
F/ 1.2 PFD (: :(6/5 +5/ ;(5/(* 9, 6), :(6+ ),(,0/0 %H+* . +.> 2$12&. .
14
1.7
PROCESS SELECTION
T( 05 ) 90 ;(500 ( 9 +;;/ /* ) :(6/5 +5/ ;(5/(*> 0(6 5)++5/0/50 (: ) ;(500 + 9/* 5(6;+. P++60 )+ * ( 9 5(*0/ /* ) ;(500 05/(* + ,+ (: ) ;(500 ;+*> 5(0 (: + 6+/+0> 0+:,> ;(5 ;/,> 0 (: 5++,0> +* *(*6*+ ::5. T+9 1.# 0)(0 ) +0(*0 (: ), +5) ;++6 0)( 9 5(*0/ /* ;(500 05/(*.
T+9 1.# C(6;+/0(* ;++60 +* /0 0/*/:/5+* /* ;(500 05/(*.
COMPARISON
DESCRIPTION
PARAMETER Y+ (: ;(500 ;+*
Y+ (: ) ;(500 ;+* ;0* )/5) ;(500 /0 ) +0 5)*((, 0 /* ) :(6/5 +5/ ;(5/(*. T) *0 5)*((, /0 :+<(+9 ( ) /6;(<6* )+
C(0 (: + 6+/+0
)+0 9* 6+ 5(6;+ ( ) ( (*. C)+; 5(0 (: + 6+/+ /0 +<+*+(0 0( )+ ) ;(5 5+* 9 0( + ( ;/5 5(6;+ ( ) 0+6 ;(5 /)
S+:,
;*0/< + 6+/+. S+:, /0 /6;(+* ( 6+= 0 ) ;(5/(* /0 *( )+ ( +55/* )+;;* /* ) (=;+5. O* (: ) 5+00 )+ 5+* /*//+ +55/* /0 ) (;+/* 5(*//(*0 (: ) ;(500.
H/) 6;+
+*
;00
(: (;+/*
5(*//(*0 )+0 )/) ;(9+9//, ( 5+0 +* +55/* ( )
+*(0
5(*//(*0.
T):(>
(
(;+/*
6;+ +* ;00 /0 :+<(+9 :( 0+: (=/* P(5 ;/,
5(*//(*. P(5 ;/, /0 +0( ;0*/* ) +/, (: ) ;(5. P(5 /) ( ;/, / 6+= ) 50(6 * ( 5 +//(*+ ;/:/5+/(* ;(500. I: ) /0 ) 0+6 ;(5 /) )/) ;/,> ) 50(6 / 5)((0 ) ;(5 /) )/)
U0 (: 5++,0
;/, ( /0 )/) +/,. U0+ (: 5++,0 +0( ;0*/* ) (;+/* 5(0. R*+/* ( ;+5/* ) 5++,0 / /*5+0 ) (;+/* 5(0 +* /* ) 0+6 /6 /::/5 ( /0;(0 )
15
0 ; 5++,0> ) +//(*+ 5(0 / 9 0;*. E*(*6*+ ::5 (: + ;(500 5+* 9 /*/:/ 9+0 (*
E*(*6*+ ::5
) 6/00/(* (: +0 ;(5> +0 +> ( 9, ;(50. P(500 )+ ;(5 +0> //> ( 0(/ ;(+*0 ( ) *(*6* /0 *( :+<(+9. B0/0> +//(*+ ;(500 /0 / ( + ) ;(+*0 9:( 9/* +0 ( ) *(*6*. T)/0 / 5(0 + ) +6(* (: 6(*,.
1.7.1
SCORING METHOD
O* (: ) 6)(0 )+ 5+* 9 0 ( 5)((0 ) 90 ;(500 /0 9, 0/* 5(*5; 05(/* 6)(. T)/0 /0 + +*/+/< 6)( ) ) 5//+ (: +5) ;(500 + 9/* 05( 9+0 (* /0 :+<(+9//,. T) ;(500 5//+ / 9 05( :(6 +* 1 ( 9+0 (* ) ;(500 ;(;/0 /) / /0 1 B+
2 Q/ 9+
3 !((
4 V, ((
O0+*/*
F( +*, ;(500 )+ )+0 *( /*:(6+/(* (* /0 5//+ / 9 05( +0 9+ ( 1 ( ) /*:(6+/(* /6/+/(* )/5) /0 +006 +0 *:+<(+9 /* ;(500 05/(*. E+5) 5//(* /0 +0( 9/* /) 9+0 (* ) /6;(+*5 (: ) ;++6 ( 9 5(*0/ /* ) ;(500
05/(*.
T(+
∑ Score ×Weightage fraction
05(
(:
+5)
;(500
/
9
5+5+
9,
. T+9 1.1$ 0)(0 ) 5(*5; 05(/* 6)(. T( 6+=
) 5(0 (: + 6+/+ 5+* 9 5(6;+> ) 5(0 (: +5) 6+/+ /0 /*/:/ 9+0 (* /0 5* 6+= <+. T) 5(00 (: ) 6+/+0 + 9/* : :(6 M++,0/+ E*+ T+ D<(;6* C(;(+/(* %MATRADE&> 5; 5(0 (: + )/5) /0 : :(6 ) I*/+ + +/:: :( /*0/+ 0+. B+0 (* ) 0 (: ) 5(*5; 05(/* 6)(> 6+*:+5/* :(6/5 +5/ 9, 6), :(6+ ),(,0/0 /*<* 9, H+* +.> %2$12&> / 9 05 +0 / )+0 ) )/)0 05( (: 2.72.
16
T+9 1.1$ C(*5; 05(/* 6)( :( ;(500 05/(*.
CRITERION
WEIGHT
Y+ (: ;+* C(0 (: + 6+/+0
1$ 14
F/'8"( &("9 %'/9(#"/ :'/8 & (&';/0<9'*-(/#&""6 8*'"&+ !F"#$%'"() *#. &+. CHARACTERISTIC 2$12
C+9(),+5(*+/*/*/* 6+/+ %USD $.G= (: ;+;&
SCORE 4
P(5 ;/, U0 (: 5++,0 E*(*6*+ ::5
T/#&+ (/'* R&)
1
2$ 18
H/)0 (;+/* 6;+ /0 23C )/ ) ;00 /0 *( 6*/(*. $ N( P(5/* 5+9(* 6(*(/ +0> + *)(0 ::5 +0.
CHARACTERISTIC 2$12
SCORE 4
C+9(* 6(*(/ %USD $.$223G=&
S:/5 +5/ %USD $.2#G=& S+:,
F/'8"( &("9 %'/9(#"/ ;< 8*#0<+ :/'8* 0<9'/+<" !H&6 *# &+.
2
1
1
F/'8"( &("9 %'/9(#"/ ;< 8*#0<+ :/'8* 0<9'/+<" !H/0*(0#$ *# &+. CHARACTERISTIC 1#8$
M), :(6+ %USD 1.2G=& 4
2
M)+*( %USD $.28G=&
W+ %USD $.1G63&
W+ %USD $.1G63&
1-%1-*-;*,&-/6/+(
H/)0 (;+/* 6;+ +* ;00 + 1$7C +* 4$ +6> 0;5/<,. ## Y0 R+0 + 06+ +6(* (: 6)+*(> 6), :(6+> +* 5+9(* 6(*(/ )() ; 0+6.
2.3 2
2
2
2
2.=2 1
17
SCORE 1
%USD 2G=& H/)0 (;+/* 6;+ +* ;00 + 13$C +* 1$ +6> 0;5/<,. 7 N( R+0 + 06+ +6(* (: 6)+*(> 6), :(6+> +* :(6/5 +5/ )() ; 0+6.
3
3
2
2.4 3
1.=
CATALYST
B+0 (* ) ;(500 05/(*> :(6/5 +5/ ;(5/(* /*<* 9, H+* +.> %2$12& /0 05. T)/0 ;+* )+0 ;(;(0 0/* 0(/6 6)(/ ( /(* 5)+* 0/* 5++,0 :( ) 5+9(*,+/(* ;(500 (: 6)+*( +* 5+9(* 6(*(/. T):(> + 05/(* (: 5++,0 60 9 6+ /* ( ( /*/:, )/5) 5++,0 /0 ) 90 :( ) ;(500. T) 05/(* / 9 6+ 9+0 (* 0+:, 95+0 )/0 /0 ) 6(0 5(*5* 5//+ :( 5++,0 0+.
1.=.1
CATALYST SELECTION
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
18
:+66+9//,> ;(0/<> +* (/5((, < ) /* () 6+*0> )/0 5++,0 (0 *( )/9/0 )(0 ,;0 (: )++0. T):(> / /0 5(*5 )+ /(* 5)+* 0/* /0 05 ( 9 0 +0 5++,0 /* :(6/5 +5/ ;(5/(* ;(500 ( /0 0+: 0+ 5(6;+ ( 0(/6 6)(/.
1.=.2
CATALYST PHASE
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
C++,0 L// /(* 5)+* 0/*
( ;(5 6), :(6+. H,(,0/0 (: 6), :(6+ /) + (
S(/ /(* 5)+* 0/*
;(5 :(6/5 +5/ +* 6)+*(.
19
1.5
MODIFIED FORMIC ACID PROCESS
B+0 (* ) ;(500 05/(*> ) ;(500 ;+* 9, H+* +.> %2$12& /0 05. T)/0 ;(500 / 9 +;;/ /* )/0 :(6/5 +5/ ;(5/(* 0/* ;(500 /) 0(6 6(/:/5+/(*0. T) + ( 6+( 6(/:/5+/(*0 )+ )+< 9* (* )/5) + ) 6(<+ (: ) :/0 0;++/(* 5 %:+0) 6& +* ) :() 0;++/(* 5 %/0/+/(* 5(6*&. T) +0(* (: /6/*+/* :+0) 6 0+ / 9 /0500 /* 0/6+/(* 5)+; %C)+; 7& * ASPEN PLUS ;(500 0/* 09-(;/5. T) 0/:/5+/(* /0 /0500 * )+ (;/5 95+0 / /0 0(6 0/6+/(* ++ /* ( ( ;+/* ) +0(*. T):(> / / 9 6( +;;(;/+ +* *0+*+9 ( ;+/* ) +0(* /) ) +/ (: 0+6 066+, 0 (: ) 0/6+/(*. T) /6/*+/(* (: ) :() 0;++/(* 5 /0 95+0 (: /::* + ;(5 ;/,. F(6/5 +5/ +* + 6/ )/9/0 +((;/5 6/ ) 6( 0;++/(* 50 + / ( 0;++ ) + :(6 :(6/5 +5/. T( ( 0( H+* +.> %2$12& /0 0/* ( /0/+/(* 5(6*0 ( +5)/< ) / ;(5 ;/,. T) )/ 0;++/(* 5 /0 +9 ( ;(5 8 ;/, (: :(6/5 +5/ +* :) 0;++/(* ;(500 /) ) :() 0;++/(* 5 5+* ;(5 ## ;/, (: :(6/5 +5/. I* )/0 :(6/5 +5/ ;(500 0/*> ) / ;(5 ;/, /0 (*, 8. T)0> ) :() 0;++/(* 5 /0 *( / :( )/0 :(6/5 +5/ ;(500 0/*. T) +0(* (: ;(5/* 8 ;(5 ;/, / 9 /0500 /* 0/6+/(* 5)+; %C)+; 7& * 0;++/(* ;(500 ::/5/*5, 09(;/5. T) :/*+/ +* 6(/:/ ;(500 :( /++6 (: ) :(6/5 +5/ ;(500 /0 ;/5 +0 /* F/ 1.3 +* ) ;(500 +/0 + /0500 /* ) * 09 (;/5.
20
1.
PROCESS FLOW DIAGRAM !PFD
C-1$1 C(6;00(
E-1$1 H+ 5)+*
R-1$1 CSTR
T-1$2 D/0. C(6* 1
T-1$2 R+5/< /0. 5(6*
P-1$1 P6;
M-1$1 M/
C-1$2 C(6;00(
E-1$ H+ 5)+*
T-1$3 D/0. C(6* 2
21
1.1
PROCESS DETAILS
T) 6+/* /;6* 0 /* ) :(6/5 +5/ ;+* /*50 + +5(> :/0 0;++/(* 5> + +5/< /0/+/(* 5> +* 05(* 0;++/(* 5. T) +5+* :( :(6/5 +5/> 6), :(6+ /0 ;(5 /* ) +5( 9, ;:(6/* + 5+9(*,+/(* +5/(* ;(500 (: 5+9(* 6(*(/ +* 6)+*( /) ) ;0* (: /(* 5)+* 0/* 5++,0. T) ;(500 ( ;(5 :(6/5 +5/ /0 (* 9, ),(,/* ) ;(5 6), :(6+ /* 500 + + ) +5/< /0/+/(* 5. T) (< (: ) (<+ ;(500 5+* 9 0* 9( 1. C+9(*,+/(* +5/(* (: 5+9(* 6(*(/ +* 6)+*( ( ;(5 6), :(6+ /* +5(. 2. S;++/(* (: *+5 6)+*( :(6 ) 6/ /* ) :/0 0;++/(* 5. 3. H,(,0/0 +5/(* (: 6), :(6+ +* *+ + ( ;(5 :(6/5 +5/ +* 6)+*( /* ) +5/< /0/+/(* 5(6*. 4. S;++/(* (: 6)+*( :(6 ) 6/ /* ) 05(* 0;++/(* 5 ( ;(5 )/) ;/, (: :(6/5 +5/.
1.1.1
CARBONYLATION OF CARBON MONOXIDE AND METHANOL
T) +5( /0 0 +0 ) 0/ :( 5+9(*,+/(* ;(500. T) +5( 0 /0 + 5(*/*(0 0/ +*= 5 %CSTR&. T) +5( /0 0 + + ;00 (: 2$ $+6 +* + 6;+ (: "$ - 1$0 C. � T) +5+*> 5+9(* 6(*(/ %CO& +* 6)+*( %CH 3OH& + 0;;/ /*( ) +5( :(6 )/ (* (+/* 5)+69. T) :(6+ :( ) 5+9(*,+/(* +5/(* /0
C H 3 OH + CO ⇌ HCOOC H 3
∆ H R ° =−29 kJ / mol
T) +5/(* /0 (* /* ) ;0*5 (: + )(*(0 5++,0. I* )/0 ;+*> ) 5++,0 0 /0 /(*-5)+* 0/*. B+0 (* !*+0(* %1##8&> ) 5(*5*+/(* (: ) 5++,0 60 9 6+/*+/* + 2 (: ) (+ 6+00 /* ) +5(. T) (; (: ) +5( /*50 ) +5/(* ;(5> 6), :(6+> HCOOCH 3 +0 +0 0(6 (: ) *+5 +5+*0> 5+9(* 6(*(/ +* 6)+*(.
22
1.1.2
SEPARATION OF REACTANT
T) (; (: ) +5( /0 )* : ( ) :/0 0;++( */. T) 6+/* :*5/(* (: 6;(,/* )/0 */ /0 ( 0;++ ) *+5 6)+*( :(6 ) 6/ ( 9 5,5 ( ) +5(. T)/0 / :+5//+ ) 5+9(*,+/(* +5/(* ;(500 )0 /*5+0/* ) ;(5/(* +. T) ;00 :( )/0 0;++/(* */ /0 0 + 3 +6. I /*50 + /0/+/(* 5(6*> + 9(/ 5> + 5(**0 5 +* + : 5. T) 9((6 ;(5 :(6 ) /0/+/(* 5(6* /0 : ( ) 9(/ 5. T) (; (: ) 9(/ 5 /0 + 6/ /) )/) 5(** (: 6)+*( )+ )+0 )/) 9(//* ;(/* )+* ) : 0+6 :( ) /0/+/(* 5(6*. T)/0 6/ /0 / /*( ( 0+60 /) (* -*/* ) /0/+/(* 5(6* )/ ) () /0 5,5 ( ) +5( */. T) (; ;(5 :(6 ) /0/+/(* 5(6* /0 : ( ) 5(**0 5 +* )* ( ) : 5. F( 0+:, +0(*0> ) 5(**0 5 /0 0/* ( <+;(/ +*, 6+/*/* 5+9(* 6(*(/ /* ) 0+6. T) (; (: ) : 5 /0 + 6/ (: 6)+*( +* 6), :(6+. I /0 / /*( ( 0+60 /) (* 0+6 : 9+5= ( ) /0/+/(* 5(6* )/ ) () 0+6 /0 : ( ) +5/< /0/+/(* 5(6*.
1.1.3
HYDROLYSIS REACTION OF METHYL FORMATE
T) +5/< /0/+/(* */ /0 0 +0 ) ;(500 */ :( ),(,0/0 ;(500. T) ;00 :( )/0 */ /0 0 + 3 +6. T)/0 */ /*50 + +5/< /0/+/(* 5(6*> + 9(/ 5> + 5(**0 5> +* + : 5. T) +5/< /0/+/(* 5(6* /*50 0<+ +5/< +,0 +* 0/;;/* +,0. T) +5/< +,0 + :/ /) /(*-5)+* 0/*> + )(*(0 5++,0 ( ;;+ :( ) +5/(* ;(500. T) 0/;;/* +,0 + 0/+ 9( ) +5/< +,0 +* + 0 ( 0;++ ) 6/0. T) 5(6* /0 / /*( ( (*0 )/5) + +5/< (*> ) +5/< +,0 0/ +* 0/;;/* (*> /(* )/5) )+0 0/;;/* +,0. I* )/0 */> ) +5/(* (550 + ) +5/< (*. T) +5+*0> 6), :(6+ +* + +5 /* + ),(,0/0 +5/(* ( ;(5 :(6/5 +5/ +* 6)+*(. T) +5/(* :(6+ /0
23
HCOOC H 3 + H 2 O ⇌ C H 3 OH + HCOOH
∆ H g ° =+ 16.3 kJ / mol
W+ :( ) +5/(* /0 ;( :(6 + (+/* 5)+69 /*( ) +5/< +,0. P(0//(* (: ) + /* /0 )/) )+* ) : /* (* ) +5/< /0/+/(* 5(6* ( + )+* + )/) 9(//* ;(/* )+* ) :. T) 6(0 ;: ;(0//(* :( ) + /* /0 + ) )/)0 +5/< +,. W+ 6(<0 (* ) 5(6* )/ 6), :(6+ <+;(/0 ;+0 /* ) ),(,0/0 +5/(*. T) (; ;(5 :(6 ) +5/< /0/+/(* 5(6* /0 : ( ) 5(**0 5 +* )* /*( + : 5. T)/0 0+6 6+/*, 5(*0/00 (: *+5 6), :(6+ +* *0 ( 9 : 9+5= /*( ) 5(6*. H(*(0 5++,0 5+* +0( 9 :/ /* ) : 5 ( 6+/6/ ) 5(*<0/(* +. T) 9((6 ;(5 :(6 ) +5/< /0/+/(* 5(6* /0 : ( ) 9(/ 5. T) (; (: ) 9(/ 5 5(*0/00 6+/*, (: *+5 + +0 +0 :(6/5 +5/ +* 6)+*(. I /0 / /*( ( 0+60 ) (* (: )6 /0 0* 9+5= ( ) +5/< /0/+/(* 5(6*. T) () 0+6 /0 : ( ) 05(* 0;++( */. T)/0 0+6 60 9 5(*( ( 6/*/6/ ) +6(* (: 6), :(6+ :(* /*0/.
1.1.4
SEPARATION OF METHANOL
T) (; (: ) 9(/ 5 /0 : ( ) 05(* 0;++/(* */. T)/0 */ /0 0 ( 5,5 6)+*( 9+5= ( ) +5( ( :+5//+ ) 5+9(*,+/(* +5/(* ;(500 +* /* ) 0+6 /6 ( ;(5 )/) ;/, (: :(6/5 +5/. T) ;00 0 :( )/0 0;++/(* */ /0 3 +6. T)/0 */ /*50 + /0/+/(* 5(6*> + 9(/ 5> + 5(**0 5 +* + : 5. T) (; ;(5 :(6 ) /0/+/(* 5(6* /0 : ( ) 5(**0 5 +* )* ( ) : 5. T) 6/ (* ) ( (: ) : 5 6+/*, 5(*0/00 (: 6)+*(. O* ;+ (: )/0 6/ /0 : 9+5= /*( ) /0/+/(* 5(6* )/ ) () ;+ /0 5,5 ( ) +5( ( 9 0 /* 5+9(*,+/(* +5/(* ;(500. A ;6; /0 6;(, /* ) 5,5 0+6 ( ) ;00 /* ) +5( 9/* )/) )+* ) ;00 /* ) 05(* 0;++/(* */.
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T) 9((6 ;(5 :(6 ) /0/+/(* 5(6* /0 : ( ) 9(/ 5. T) (; (: ) 9(/ 5 5(*0/00 6+/*, (: :(6/5 +5/ +* 500 +. I /0 / /*( ( 0+60 ) (* (: )6 /0 0* 9+5= ( ) /0/+/(* 5(6* )/ ) () /0 +=* +0 ) 0/ ;(5. T) ;(5 0+6 )+0 )/) 9(//* ;(/* )* 5(6;+ ( ) : :( ) )/ 0;++/(* */. T) 5(*5*+/(* (: ) :(6/5 +5/ /* ) ;(5 6/ /0 ;5 ( 9 +9( 8. I* ) (<+ ;(500> ) * +5/(* /0 9* + +* 5+9(* 6(*(/ ( ;(5 :(6/5 +5/. T)/0 /0 :(* )() 5/(* (: ) ( ;(5000 /*<(< 5+9(*,+/(* +* ),(,0/0 ( ;(5 + * 5)6/5+ :(6+ (:
C H 3 OH + CO ⇁ HCOOC H 3
HCOOC H 3 + H 2 O ⇌ C H 3 OH + HCOOH
CO + H 2 O ⇌ HCOOH
F(6 ) (<+ +5/(*> / /0 :(* )+ /* ( ( ;(5 :(6/5 +5/ /) )/) ;/,> ) 6( +/( 9* 5+9(* 6(*(/ +* + 0 /* ) ;(5/(* 0)( 9 11 /* + 5(*0+* /6 ;/(. T)/0 );0 ;<* *+5 +5+*0 :(6 9*/* /) ) ;(5/(* (: :(6/5 +5/ %H+* +.> 2$12&. A (: ) 0/:/5+/(*0 (: /;6* 0*5> 5)(/5 (: /;6*> 0;++/(* ;(500 ::/5/*5,> +* (;+/* ;00 + /0500 /* 0/6+/(* 5)+; %C)+; 7&. I* ) 0+6 5)+;> + 6+/+0 ;/,> /* +* ( ;00G6;+ + +0( /0500.
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REFERENCES
A5/;/+> %2$1&. F(6/5 A5/- U00> B*:/0> +* S/ E::5 (: F(6/5 A5/. A5/;/+ .( T) H(6 (: A5/0. );GG+5/;/+.(G:(6/5+5/G A<(+( C)6> %1###&.
M+/+ S+:, D++ S) (: F(6/5 A5/> );GG+<(+(
.5)6./+0+.GMSDSG:(6/5+5/.)6 BASF> %2$14&. F(6/5 A5/. BASF. );GG;(5-:/*.9+0:.5(6G(;G5(;(+G;(5:/*G*G9+*GFORMICACID F/;+/5=> S. W. %2$12&. P(5/(* (: F(6/5 A5/. US P+* N(. 8>138>371 B2. !*+0(*> H.> %1##8&. I*0/+ !+00 /* P5)6/5+ P(500/*. M+5 D==> I*5. N Y(=> ; 24$.& H()*05)> H.> S5)6/> '. E.> J K/:> H. %1#8$&. P;++/(* (: F(6/5 A5/. US P+* N(. 4>218>"8. H+*> H. P.> L> M. '.> L> H. Y.> J C)*> '. H. %2$12&. F(6/5 A5/ M+*:+5/* S,06 +* M)( (: M+*:+5/* F(6/5 A5/. US P+* N(. 2$12G$12317 A1. K6(+> K.> T.> %1##8&. E::/5/*5/0 /* D/0/+/(* +* R+5/< D/0/+/(*. A5+ P(,5)*/5+ S5+*/*+5+> F/**/0) A5+6, (: T5)*((,. C)6/5+ T5)*((, S/0 N(. 27> 3" ;;. K(=> Q.> A5)0(*> B.> T5(> R.> '+*0> +.> J M++/> !. %2$13&. F/ +* ;(0/(* )++0 + ( ) /*0/+ 0 (: ;(+00/6 +* 0(/6 6)(/0. Journal of Hazardous Materials > 250-251 > 4844#$. );GG(/.(G1$.1$1"G.)+6+.2$13.$1.$7
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Bioresource Technology > 167 > 13313". );GG(/.(G1$.1$1"G.9/(5).2$14.$".$22
ON/> M.'. %2$$"&. T) M5= I* - A* E*5,5(;/+ (: C)6/5+0> D0> +* B/((/5+. W)/)(0 S+/(*> N' M5= +* C(.> I*5.> ;. 727 P,> R.> H.> J !*> D.> W.> %1###&. P,@0 C)6/5+ E*/*0@ H+*9((=. T) M5!+-H/ C(6;+*/0> I*5. P9C)6> %2$1&. N+/(*+ C* :( B/(5)*((, I*:(6+/(*. P9C)6 C(6;(* D++9+0 CID284> );0GG;95)6.*59/.*6.*/).( W.> J K/5=+> H.> %2$$&. F(6/5 A5/. U6+*@0 E*5,5(;/+ (: I*0/+ C)6/0,. 7) E. W/,-VCH V+ !69H J C(. K!+A> W/*)/6. R//5=> '.A.> W.B. B*> S+=+*( T.K. T5)*/0 (: C)6/0, 4) .> V(6 II. O+*/5 S(<*0. N Y(=> NY '()* W/, +* S(*0. 1#8.> ;. 3"$ T)6( F/0) S5/*/:/5> %2$1&. S+:, D++ S). F/0) S5/*/:/5. R/< :(6 );0GG.:/0)05/.5(6G0)(;G600;(,;(5N+6AC2$3$$$$
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