Production of methanol from biomass 1

Carlo N. Hamelinck (currently working with Ecofys b.v. the Netherlands, $trecht the Netherlands%

anaalweg 1!"#,

&ndr' P.C. (aai) ($trecht $niversity * Co+ernicus ,nstitute of -ustainable .evelo+ment and ,nnovation, Heidelberglaan /, $trecht the Netherlands%

This chapter is broadly based on Hamelinck CN and Faaij APC, 2002, Future prospects or production o methanol and hydro!en rom biomass, "ournal o Po#er $ources 111%1&'1(22)

1 ,ntroduction.........................................................................................................................0 / 1echnology...........................................................................................................................2 /.1 3verview..................................................................................................................2 /./ Pre"treatment...........................................................................................................2 /.0 #asification...............................................................................................................2 *+T !asi ier -C. !asi ier 01y!en supply , / /

/.2 #as cleaning and contaminant limits.........................................................................4 2a# !as 3ersus system re4uirements Tar remo3al 7et !as cleanin! 8ry 9 hot !as cleanin! 5 6 10 11

/.5 #as conditioning.....................................................................................................1/ 2e ormin! 7ater !as shi t C02 remo3al 12 1: 1;

/.! 6ethanol synthesis.................................................................................................15 Fi1ed bed technolo!y .i4uid phase methanol production 1/ 1/

0 3+tions for synergy............................................................................................................17 0.1 Electricity co"generation by combined cycle............................................................17 0./ Natural gas co"firing * co"feeding...........................................................................18 0.0 9lack li:uor gasification..........................................................................................18 0.2 3ther biofuels via gasification.................................................................................18 Hydro!en Fischer(Tropsch %FT& diesel <ethanol to diesel <ethanol to !asoline 8imethyl ether %8<=& 16 20 20 20 20

2 1echno"economic +erformance...........................................................................................// 2.1 -election of conce+ts..............................................................................................// 2./ 6odelling mass and energy balances....................................................................../0 2.0 Costing method......................................................................................................./2 2.2 ;esults..................................................................................................................../4 5 Conclusions........................................................................................................................01 ! <iterature...........................................................................................................................0/

1 ,n t r o d uc t i o n

Methanol (CH3OH), also known as methyl alcohol or wood alcohol, is the simplest alcohol. It can be sed as a ! el, either as blend with "asoline in internal comb stion en"ines 2 or in ! el cell #ehicles3. $lso, Methanol has a #ersatile ! nction in the chemical ind stry as startin" point !or many chemicals. Methanol is prod ced nat rally in the anaerobic metabolism o! many #arieties o! bacteria and in some #e"etation. % re methanol was !irst isolated in 1&&1 by 'obert (oyle, by distillation o! bo)wood. In 1*3+, the ,rench chemists - mas and %eli"ot determined its elemental composition. In 1.22 ($/, de#eloped a process to con#ert synthesis "as (a mi)t re o! carbon mono)ide and hydro"en) into methanol. 0his process sed a 1inc o)ide 2 chromi m o)ide catalyst, and re3 ired e)tremely #i"oro s conditions4 press res ran"in" !rom 35561555 bar, and temperat res o! abo t +55 7C. Modern methanol prod ction has been made more e!!icient thro "h the se o! catalysts capable o! operatin" at lower press res. $lso the synthesis "as is at present mostly prod ced !rom nat ral "as rather than !rom coal. 0oday (2558) the "lobal methanol prod ction capacity is abo t +5 Mtonne2year, the act al prod ction or demand is abo t 32 Mtonne (Methanol Instit te 2558). /ince the early 1.*5s, lar"er plants sin" new e!!icient low6press re technolo"ies are replacin" less6e!!icient small !acilities. In 1.*+, more than three 3 arters o! world methanol capacity was located in the traditional markets o! 9orth $merica, : rope and ;apan, with less than 15 percent located in <distant6!rom 6market< de#elopin" re"ions s ch as /a di $rabia. ( t !rom that time most new methanol plants ha#e been erected in de#elopin" re"ions while hi"her cost !acilities in more de#eloped re"ions were bein" sh t down. 0he c rrent standard capacities o! con#entional plants ran"e between 2,555 and 3,555 tonne methanol per day. Howe#er, the newest plants tend to be m ch lar"er, with sin"le trains o! 8555 tonne2day in %oint =isas, 0rinidad (start6 p in 255+), 8555 tonne2day in -ayyer, Iran (start6 p in 255&), and 8555 tonne2day in =ab an, Malaysia (start constr ction in 255&). Methanol prod ced !rom biomass and employed in the a tomoti#e sector can address se#eral o! the problems associated with the c rrent se o! mineral oil deri#ed ! els, s ch as ener"y sec rity and "reenho se "as emissions. 0his chapter disc sses the technolo"y !or the prod ction o! methanol !rom biomass. ,or a selection o! concepts, e!!iciencies and prod ction costs ha#e been calc lated.

*n =urope methanol may be blended in re!ular !asoline up to , > by 3olume #ithout notice to the consumer) Hi!her blends are possible like <?, %?, > methanol #ith 1, > !asoline& but #ould re4uire adaptations in cars or specially de3eloped cars) <oreo3er, blends hi!her than , > re4uire adaptations in the distribution o uels to !as stations and at the !as stations themsel3es) Pure methanol is sometimes used as racin! uel, such as in the *ndianapolis ,00) <ethanol can be the source or hydro!en 3ia on board re ormin!) 8irect methanol uel cells are under de3elopment that can directly process methanol %3an den Hoed 200;&)

/ 1e c h n o l o g y

/.1

3verview

Methanol is prod ced by a catalytic reaction o! carbon mono)ide (CO), carbon dio)ide (CO 2) and hydro"en (H2). 0hese "asses, to"ether called synthesis gas, are "enerally prod ced !rom nat ral "as. One can also prod ce synthesis "as !rom other or"anic s bstances, s ch as biomass. $ train o! processes to con#ert biomass to re3 ired "as speci!ications precedes the methanol reactor. 0hese processes incl de pre6treatment, "asi!ication, "as cleanin", "as conditionin" and methanol synthesis, as is depicted in ,i" re 1 and disc ssed in /ections 2.2 6 2.&4

Biomass

Pre-treatment section

Gasifier

Gas cleaning section

Reformer

Shift reactor

Methanol reactor

Methanol

Fi!ure 1)

@ey components in the con3ersion o

bio mass t o met hano l)

/./

Pre"treatment

Chippin" or commin tion is "enerally the !irst step in biomass preparation. 0he ! el si1e necessary !or !l idised bed "asi!ication is between 5 and 85 mm (%ierik et al. 1..8). 0otal ener"y re3 irements !or chippin" woody biomass are appro)imately 155 k;e2k" o! wet biomass (>ato!sky 1..3) down to 2+5 k?e !or 28 @ 85 tonne2h to 3)3 cm in a hammermill, which "i#es 1A @ 38 k;e2k" wet biomass (%ierik et al. 1..8). 0he ! el sho ld be dried to 15 @ 18 B dependin" on the type o! "asi!ier. 0his cons mes ro "hly 15 B o! the ener"y content o! the !eedstock. -ryin" can be done by means o! hot !l e "as (in a rotary dr m dryer) or steam (direct2indirect), a choice that amon" others depends on other steam demands within the process, and the e)tent o! electricity co6prod ction. ,l e "as dryin" "i#es a hi"her !le)ibility towards "asi!ication o! a lar"e #ariety o! ! els. In the case o! electricity "eneration !rom biomass, the inte"ration in the total system is simpler than that o! steam dryin", res ltin" in lower total in#estment costs. 0he net electrical system e!!iciency can be somewhat hi"her (#an 'ee et al. 1..8). On the other hand, !l e "as dryin" holds the risk o! spontaneo s comb stion and corrosion (Consonni et al. 1..+). ,or methanol prod ction, steam is re3 ired thro "ho t the entire process, th s re3 irin" a elaborate steam cycle anyway. It is not a priori clear whether !l e "as or steam dryin" is a better option in methanol prod ction. $ !l e "as dryer !or dryin" !rom 85 B moist re content to 18 or 15 B wo ld ha#e a speci!ic ener"y se o! 2.+ @ 3.5 M;2tonne water e#aporated (twe) and a speci!ic electricity cons mption o! +5 @ 155 k?h e2twe (%ierik et al. 1..8). $ steam dryer cons mes 12 bar, 255 7C (process) steamC the speci!ic heat cons mption is 2.* M;2twe. :lectricity se is +5 k?h e2twe (%ierik et al. 1..8).

/.0

#asification

0hro "h "asi!ication solid biomass is con#erted into synthesis "as. 0he ! ndamentals ha#e e)tensi#ely been described by amon" others >ato!sky (1..3). (asically, biomass is con#erted to a mi)t re o! CO, CO 2, H2O, H2, and li"ht hydrocarbons, the m t al ratios dependin" on the type o! biomass, the "asi!ier type, temperat re and press re, and the se o! air, o)y"en and steam.

Many "asi!ication methods are a#ailable !or synthesis "as prod ction. (ased on thro "hp t, cost, comple)ity, and e!!iciency iss es, only circ lated !l idised bed "asi!iers are s itable !or lar"e6scale synthesis "as prod ction. -irect "asi!ication with air res lts in nitro"en dil tion, which in t rn stron"ly increases downstream e3 ipment si1e. 0his eliminates the 0%/ (0ermiska %rocesser $() and :n#iropower "asi!iers, which are both direct air blown. 0he M0CI (Man !act rin" and 0echnolo"y Con#ersion International, a!!iliate o! 0hermochem Inc.) "asi!ier is indirectly !ired, b t prod ces a #ery wet "as and the net carbon con#ersion is low. 0wo "asi!iers are selected !or the present analysis4 the ID0 (Instit te o! Das 0echnolo"y) press rised direct o)y"en !ired "asi!ier, and the (C= ((attelle Col mb s) atmospheric indirectly !ired "asi!ier. 0he ID0 "asi!ier can also be operated in a maximum hydrogen mode, by increasin" the steam inp t. (oth "asi!iers prod ce medi m calori!ic "as, ndil ted by atmospheric nitro"en, and represent a #ery broad ran"e !or the H24CO ratio o! the raw synthesis "as.
IGT gasifier

0he ID0 "asi!ier (,i" re 2) is directly heated, this implies that some char and2or biomass are b rned to pro#ide the necessary heat !or "asi!ication. -irect heatin" is also the basic principle applied in press rised reactors !or "asi!yin" coal. 0he hi"her reacti#ity o! biomass compared to coal permits the se o! air instead o! p re o)y"en. 0his co ld be !ort ito s at modest scales beca se o)y"en is relati#ely costly (Consonni and =arson 1..+a). Howe#er, !or the prod ction o! methanol !rom biomass, the se o! air increases the #ol me o! inert (9 2) "as that wo ld ha#e to be carried thro "h all the downstream reactors. 0here!ore, the se o! o)y"en th s impro#es the economics o! synthesis "as processin". $ir6!ired, directly heated "asi!iers are considered not to be s itable be!ore methanol prod ction.
Product gas

Biomass

Ash

Steam + oxygen
Fi!ure 2) The directly heated, bubblin! luidised bed !asi ier o *+T %@ato sky 166:&)

0his "asi!ier prod ces a CO2 rich "as. 0he CH+ !raction co ld be re!ormed to hydro"en, or be sed in a "as t rbine. 0he H24CO ratio (1.+ 4 1) is attracti#e to prod ce methanol, altho "h the lar"e CO 2 content lowers the o#erall yield o! methanol. 0he press rised "asi!ication allows a lar"e thro "hp t per reactor #ol me and diminishes the need !or press risation downstream, so less o#erall power is needed. 0he bed is in !l idised state by inEection o! steam and o)y"en !rom below, allowin" a hi"h de"ree o! mi)in". 9ear the o)idant entrance is a comb stion 1one with a hi"her operation temperat re, b t "asi!ication reactions take place o#er the whole bed, and the temperat re in the bed is relati#ely ni!orm (*55 @ 1555 7C). 0he "as e)its essentially at bed temperat re. $sh, nreacted char and partic lates are entrained within the prod ct "as and are lar"ely remo#ed sin" a cyclone. $n important characteristic o! the ID0 synthesis "as is the relati#ely lar"e CO 2 and CH+ !ractions. 0he hi"h methane content is a res lt o! the non6e3 ilibri m nat re o! biomass "asi!ication and o! press rised operation. 'elati#ely lar"e amo nts o! CO2 are prod ced by the direct heatin", hi"h press re, and the hi"h o#erall O4C ratio (241). ?ith con#entional "as processin" technolo"y, a lar"e CO 2 content wo ld mean that o#erall yields o! !l id ! els wo ld be 8

relati#ely low. 0he synthesis "as has an attracti#e H24CO ratio !or methanol prod ction, which red ces the need !or a shi!t reactor. /ince "asi!ication takes place nder press re, less downstream compression is needed. ?hen operated with hi"her steam inp t the ID0 "asi!ier prod ces a prod ct "as with hi"her a hydro"en content. 0his maximum hydrogen mode is especially se! l i! hydro"en wo ld be the desired prod ct, b t the H 24CO ratio is also better !or methanol prod ction. Howe#er, the "asi!ier e!!iciency is lower and m ch more steam is needed.
BCL gasifier

0he (C= "asi!ier is indirectly heated by a heat trans!er mechanism with as shown in ,i" re 3. $sh, char and sand are entrained in the prod ct "as, separated sin" a cyclone, and sent to a second bed where the char or additional biomass is b rned in air to reheat the sand. 0he heat is trans!erred between the two beds by circ latin" the hot sand back to the "asi!ication bed. 0his allows one to pro#ide heat by b rnin" some o! the !eed, b t witho t the need to se o)y"en, beca se comb stion and "asi!ication occ r in separate #essels.
Offgas Product gas

Biomass

Steam
Fi!ure :)

Air
-C. %@ato sky 166:&)

The indirectly heated, t#in bed !asi ier o

(eca se o! the atmospheric press re, the (C= "asi!ier prod ces a "as with a low CO 2 content, b t conse3 ently containin" more hea#ier hydrocarbons. 0here!ore, tar crackin" and re!ormin" are lo"ical s bse3 ent steps in order to ma)imise CO and H2 prod ction. 0he reactor is !ast !l idised allowin" thro "hp ts e3 al to the b bblin" !l idised ID0, despite the atmospheric operation. 0he atmospheric operation decreases cost at smaller scale, and the (C= has some commercial e)perience (demo in ( rlin"ton F/$, (%aisley et al. 1..*)). (eca se biomass "asi!ication temperat res are relati#ely low, si"ni!icant depart res !rom e3 ilibri m are !o nd in the prod ct "as. 0here!ore, kinetic "asi!ier modellin" is comple) and di!!erent !or each reactor type (Consonni et al. 1..+C =i et al. 2551). 0he main per!ormance characteristics o! both "asi!iers are "i#en in 0able 1.
Oxygen supply

Dasi!iers demand o)y"en, pro#ided as air, p re o)y"en or anythin" in between. 0he se o! p re o)y"en red ces the #ol me !lows thro "h the ID0 "asi!ier and thro "h downstream e3 ipment which red ces in#estment costs. $lso the $ tothermal 'e!ormer (see later) is, !or the same reason, pre!erably !ired by o)y"en. $s the prod ction o! o)y"en is e)pensi#e, there will likely be an economical optim m in o)y"en p rity. O)y"en enriched air co ld be a compromise between a cheaper o)y"en s pply and a red ced downstream e3 ipment si1e. Cryo"enic air separation is commonly applied when lar"e amo nts o! O 2 (o#er 1555 9m 32h) are re3 ired. /ince air is !reely a#ailable, the costs !or o)y"en prod ction are directly related to the costs !or air compression and re!ri"erationC &

Table 1)

Characteristics o

!asi iers, taken IGT ! (u((ling fluidised (ed

rom 7illiams et al) %166,&) IGT max "#$! (u((ling fluidised (ed '/*1 *45#' **546 # 5# tonne,hr ""2 6#'56 , &"2 /$45-5' 6 -5/' 4##1 *#*1! 4 '-56' +-! -5#6 +-56 #! -5**1 +-5##*! -5* +-5/-'! -5--1 +-5--4! * +*! /54""2 /-4 , &"2 #/* B%&'! Indirectly heated fast fluidised (ed '/**456 *#5-$ //5- tonne,hr ""2 6/#56 , &"2 /'/5# -5-*4 *51# #5' / *5# 615' / 6 -5*44 +-! -5* $ +-5#-'! -5/$* +-56 /! -5-'4 +-5***! -5*# +-5*1$! -5-6# +-5-1#! -5-+-5--$6! * +*! *#5$ ""2 /6' , &"2 /*

Biomass in)ut dry (asis*! +tonne,hr! Initial moisture content +.! 0ry moisture content +.! ""2dry (iomass +G3,tonne! &"27et (iomass#! +G3,tonne! Steam demand drier/! +tonne,hr! Thermal Biomass in)ut +M8! Steam +9g,9g dry feed! Steam6! +tonne,hr! Oxygen +9g,9g dry feed! Air +9g,9g dry feed!

'/*1 *45#' **546 # 5# ""2 6#'56 , &"2 /$45-5/ #6 -5/ -

Product tem)erature +:%! 4'# ;xit )ressure +(ar! /651 Gas yield +9mol,dry tonne! '#58et gas out)ut 9mol,hour 1 %om)osition< mole fraction on 7et (asis +on dry (asis! "# O -5/*' +-! "# -5#-' +-5/-1! %O -5*1 +-5##! %O# -5#/4 +-5/1! %"6 -5-'*4 +-5*#! %# "6 -5--/* +-5--1! %# " O# =# > * +*! &"27et synthesis gas +M3,=m/! 5$Thermal flo7 +M8! ""2 /1# ,&"2 #4
1& 2&

:&

;& ,& /& 5& ?&

/;0 ktonne dry #ood annual, load is ?000 h) Calculated rom .HA#et B HHAdry %1 ( 7& ( = # %7 C H#et mH20&D #ith =# the ener!y needed or #ater e3aporation %2)2/ <"9k!&, H#et the hydro!en content on #et basis % or #ood Hdry B 0)0/2& and mH20 the amount o #ater created rom hydro!en %?)6; k!9k!&) 7et biomass' ?090)5 B 11; tonne9hr to dry biomass ?090)?, B 6;)1 tonne9hr or *+T e3aporate #ater 20)2 tonne9hr at 1): ts9t#e in Niro %indirect& steam dryer) Calculation or -C. is alike) The steam has a pressure o 12 bar and a temperature o minimally 200 EC +Pieri9 et al5 *441!) Pressure is :;),, 2, or 1)2 bar, temperature is minimally 2,0, 2;0 or 120 EC) Calculated rom the total mass stream, 1??), tonne9hr) Fuoted rom 0PPA +*44-! by 7illiams et al) +*441!) @ni!ht +*44'!) Compiled by 7illiams et al) +*441!)

the main nit operations in an air separation plant. $s a conse3 ence, the o)y"en price is mainly determined by the ener"y costs and plant in#estment costs (#an -iEk et al. 1..8C #an 'ee 1..2). 0he con#entional air separation nit is both capital and ener"y intensi#e. $ potential !or cost red ction is the de#elopment o! air separation nits based on cond cti#e ionic trans!er membranes (I0M) that operate on the partial press re di!!erential o! o)y"en to passi#ely prod ce p re o)y"en. 'esearch and de#elopment o! the I0M are in demonstration phase (-e=allo et al. 2555). $lternati#e options are membrane air separation, sorption technolo"ies and water decomposition, b t these are less s itable !or lar"e scale application (#an 'ee 1..2).

/.2

#as cleaning and contaminant limits

Raw gas versus system requirements

0he raw synthesis "as prod ced by "asi!ication contains imp rities. 0he most typical imp rities are or"anic imp rities like condensable tars and (0G (ben1ene, tol ene, and )ylenes), inor"anic imp rities (9H 3, HC9, H2/, CO/, and HCl), and ! rthermore #olatile metals, d st, and soot (0iEmensen 2555C #an 'ee et al. 1..8). 0hese contaminants can A

lower catalyst acti#ity in re!ormer, shi!t and methanol reactor, and ca se corrosion in compressors, heat e)chan"ers and the (optional) "as t rbine. 0he estimated ma)imal acceptable contaminant concentrations are s mmarised in 0able 2, to"ether with the e!!ecti#eness o! wet and dry "as cleanin", as described below. 0he "as can be cleaned sin" a#ailable con#entional technolo"y, by applyin" "as coolin", low temperat re !iltration, and water scr bbin" at 155 @ 285 7C. $lternati#ely, hot "as cleanin" can be considered, sin" ceramic !ilters and rea"ents at 385 @ *55 7C. 0hese technolo"ies ha#e been described thoro "hly by se#eral a thors (Consonni et al. 1..+C > rkela 1..&C 0iEmensen 2555C #an -iEk et al. 1..8C #an 'ee et al. 1..8). 0he considered press re ran"e is no problem !or either o! the technolo"ies. Hot "as cleanin" is ad#anta"eo s !or the o#erall ener"y balance when a re!ormer or a ceramic membrane is applied directly a!ter the cleanin" section, beca se these processes re3 ire a hi"h inlet temperat re. Howe#er, not all elements o! hot "as cleanin" are yet pro#en technolo"y, while there is little ncertainty abo t the cleanin" e!!ecti#eness o! low temperat re "as cleanin". (oth cleanin" concepts are depicted in ,i" re +.

Table 2)

=stimated contaminant speci icat ion s or e ecti3eness o #et and dry !as clean in !) Gas phase Specification - ))( Existing technologies

<ethanol

synt hesis 1& ,

and

cleanin!

Contaminant Soot +dust? char? ash! Al9aline +halide! metals Tar

Treatment method & remarks Dry gas cleaning3)

BTX Halide compounds "%l +"Br? "D!

%yclones? metal filters? mo@ing (eds? candle filters? (ag filters? s)ecial soot scru((er S)ecifications are met5 A *- ))( Acti@e coal (ed meets s)ecification#! Sor(ents Bnder de@elo)ment Belo7 de7 )oint All tar and BTC< All tar and BTC< Thermal tar crac9er? %atalytic tar crac9er? %atalyst )oisoning Oil scru((er6!? other catalytic o)erations5 com)ounds A S)ecifications are met Bnder de@elo)ment5 * ))m2 Belo7 de7 )oint A *- ))( Remo@ed (y aEueous scru((er Acti@e coal (ed meets s)ecification A(sor(ed (y dolomite in tar crac9er +if a))lica(le! In-(ed sor(ents or in-stream sor(ents A * ))m Guard(eds necessary All nitrogen< catalytic decom)osition? Remo@ed (y aEueous scru((er com(ined remo@al of Remo@ed to s)ecification ="/,"#S Acti@e coal (ed Selecti@e oxidation )ossi(ly )receded (y hydrolysis to ="/ Bnder de@elo)ment S)ecifications are met All sul)hur< In-(ed %alcium sor(ents FnO guard (ed in case of high sul)hur loads a s)ecial remo@al Metal oxide sor(ents A #- ))m ste)? e.g5 %laus unit acti@e coal (ed )ossi(ly )receded (y hydrolysis to "#S S)ecifications are met

Nitrogen compounds ="/ "%= Sulphur compounds "# S %OS

Total = A* ))m2

Total S A* ))m2#!

1&

2&

:&

;&

<ost numbers are 4uoted rom Fischer(Tropsch synthesis o3er a cobalt catalyst %-echtel 166/D -oerri!ter et al) 200:D Tijmensen 2000&) +as turbine speci ications are met #hen FT speci ications are) Cleanin! re4uirements or <e0H synthesis are 0)1 %3an 8ijk et al) 166,& to 0)2, ppm H2$ %@ato sky 166:&) Total sulphur G1 ppmA %-oerri!ter et al) 200:&) For Fischer(Tropsch synthesis re4uirements are e3en more se3ere' 10 ppb %Tijmensen 2000&) Hot !as cleanin! #as practiced in the AHrnamo 8emonstration plant, $#eden %@#ant 2001&) All data on dry !as cleanin! here is based on the e1tensi3e research into hi!h temperature !as cleanin! by <itchell %<itchell 1665D <itchell 166?&) -er!man et al) %-er!man et al) 200:&)

Tar removal

:specially in atmospheric "asi!ication lar"er hydrocarbons are !ormed, "enerally cate"orised as HtarsI. ?hen condensin", they !o l downstream e3 ipment, coat s r!aces and enter pores in !ilters and sorbents. 0o a#oid this, their concentration thro "ho t the process m st be below the condensation point. On the other hand, they contain a lot o! potential CO and H2. 0hey sho ld th s pre!erably be cracked into smaller hydrocarbons. ,l idised beds prod ce tar at abo t 15 "2m 90%3 or 1 @ 8 wtB o! the biomass !eed ((oerri"ter et al. 2553C Milne et al. 1..*C 0iEmensen 2555). (0G, acco ntin" !or 5.8 #ol me B o! the synthesis "as, ha#e to be remo#ed prior to the acti#e carbon !ilters, which otherwise sorb the (0G completely and 3 ickly "et !illed p ((oerri"ter et al. 2553). 0hree methods may be considered !or tar remo#al2crackin"4 thermal crackin", catalytic crackin", and scr bbin". $t temperat res abo#e 1555 @ 1255 7C, tars are destroyed witho t a catalyst, s ally by addition o! steam and o)y"en, which acts as a selecti#e o)idant (Milne et al. 1..*). -rawbacks are the need !or e)pensi#e materials, the soot prod ction and the low thermal e!!iciency. Catalytic crackin" (dolomite or 9i based) is best applied in a secondary bed, and a#oids the mentioned problems o! thermal crackin". Howe#er, the technolo"y is not yet ! lly pro#en (Milne et al. 1..*). It is not clear to what e)tent tars are remo#ed (0iEmensen 2555) and the catalyst cons mption and costs are matters o! concern. %er k" dry wood (18 B moist re), 5.52&* k" dolomite. %art o! the H 2/ and HCl present adsorb on dolomite (#an 'ee et al. 1..8). 0he tar crackers can be inte"rated with the "asi!ier. .

"ydrolysis

AEueous scru((ing Remo@es ="/? "%l? metals? )art "%=? "#S

Gasifier '1- G%

Tar crac9er */-- G%

%yclones

Gas cooling *-- G%

0ust remo@al

Residual contaminants 7et cleaning

%onditioning

Guard (eds

Methanol reactor

"P steam Tar+oil

Gasifier '1- G%

%yclones

Gas cooling 6-- G%

Oil scru((er *-- G%

Residual contaminants 7et cleaning

%onditioning

Guard (eds

Methanol reactor

"P steam

Gasifier '1- G%

Tar crac9er */-- G%

%yclones

Gas cooling 6-- G%

%andle filters

Residual contaminants dry cleaning

Gas cooling #- G%

%onditioning

Guard (eds

Methanol reactor

"P steam

(ase a(sor)tion Remo@es ="/

acid a(sor)tion Remo@es "%l? "%=

Sul)hur a(sor)tion Remo@es "#S and %OS

Acti@e car(on + FnO guard(eds Remo@es traces "%=? "#S? ="/? %OS

Fi!ure ;)

Three possible !as cleanin ! t rain s) To p' tar crackin ! an d con 3en t io nal #e! !as cleanin!D middle' tar scrubbin ! an d con 3en t io nal #et !as clean in !D an d bottom' tar crackin! and dry !as clean in !)

0ars can also be remo#ed at low temperat re by ad#anced scr bbin" with an oil based medi m ((er"man et al. 2553C (oerri"ter et al. 2553). 0he tar is s bse3 ently stripped !rom the oil and reb rned in the "asi!ier. $t atmospheric press res (0G are only partially remo#ed, !rom abo t & bar (0G are ! lly remo#ed. 0he "as enters the scr bber at abo t +55 7C, which allows hi"h temperat re heat e)chan"e be!ore the scr bber.
Wet gas cleaning

?hen the tars and (0G are remo#ed, the other imp rities can be remo#ed by standard wet "as cleanin" technolo"ies or ad#anced dry "as cleanin" technolo"ies. ?et low temperat re synthesis "as cleanin" is the pre!erred method on the short term (#an 'ee et al. 1..8). 0his method will ha#e some ener"y penalty and re3 ires additional waste water treatment, b t on the short term it is more certain to be e!!ecti#e than hot dry "as cleanin". $ cyclone separator remo#es most o! the solid imp rities, down to si1es o! appro)imately 8 m (>ato!sky 1..3). 9ew "eneration ba" !ilters made !rom "lass and synthetic !ibres ha#e an pper temperat re limit o! 2&5 7C (%erry et al. 1.*A). $t this temperat re partic lates and alkali, which condense on partic lates, can s ccess! lly be remo#ed ($lderliesten 1..5C Consonni et al. 1..+C 0iEmensen 2555C #an 'ee et al. 1..8). (e!ore enterin" the ba" !ilter, the synthesis "as is cooled to E st abo#e the water dew point. $!ter the !ilter nit, the synthesis "as is scr bbed down to +5 7C below the water dew point, by means o! water. 'esid al partic lates, #apo r phase chemical species ( nreacted tars, or"anic "as condensates, trace elements), red ced halo"en "ases and red ced nitro"en compo nds are remo#ed to a lar"e e)tend. 0he scr bber can consist o! a ca stic part where the b lk o! H2/ is remo#ed sin" a 9aOH sol tion (#an 'ee et al. 1..8) and an acid part !or ammonia2cyanide remo#al. $lkali remo#al in a scr bber is essentially complete (Consonni et al. 1..+). ?ith less than 35 ppm H2/ in the biomass deri#ed synthesis "as a JnO bed may be s !!icient to lower the s lph r concentration below 5.1 ppm. JnO beds can be operated between 85 and +55 7C, the hi"h6end temperat re !a#o rs e!!icient tilisation. $t low temperat res and press res less s lph r is absorbed, there!ore m ltiple beds will be sed in series. 0he JnO bed ser#es one year and is not re"enerated (>ato!sky 1..3C #an -iEk et al. 1..8). ( lk remo#al o! 15

s lph r is th s not re3 ired, b t i! CO 2 remo#al is demanded as well (see /ection 2.8), a sol#ent absorption process like 'ectisol or / l!inol co ld be placed downstream, which also remo#es s lph r. H2/ and CO/ are red ced to less than 5.1 ppm and all or part o! the CO2 is separated (Hydrocarbon %rocessin" 1..*).
Dry !ot gas cleaning

In dry 2 hot "as cleanin", resid al contaminations are remo#ed by chemical absorbents at ele#ated temperat re. In the methanol process, hot "as cleanin" has little energy ad#anta"es as the methanol reactor operates at 255 @ 355 7C, especially when precedin" additional compression is re3 ired (e!!icient compression re3 ires a cold inlet "as). Howe#er, dry 2 hot "as cleanin" may ha#e lower operational costs than wet "as cleanin" (Mitchell 1..*). ?ithin ten years hot "as cleanin" may become commercially a#ailable !or (ID2CC applications (Mitchell 1..*). Howe#er, re3 irements !or methanol prod ction, especially !or catalyst operation, are e)pected to be more se#ere (0iEmensen 2555). It is not entirely clear to what e)tent hot "as cleanin" will be s itable in the prod ction o! methanol. 0ars and oils are not e)pected to be remo#ed d rin" the hot "as cleanin" since they do not condense at hi"h temperat res. 0here!ore, they m st be remo#ed prior to the rest o! the "as cleanin" as disc ssed abo#e. ,or particle remo#al at temperat res abo#e +55 7C, slidin" "ran lar bed !ilters are sed instead o! cyclones. ,inal d st cleanin" is done sin" ceramic candle !ilters (>lein 0eeselink et al. 1..5C ?illiams 1..*) or sintered6metal barriers operatin" at temperat res p to A25 7CC collection e!!iciencies "reater that ...* B !or 2 @ A m particles ha#e been reported (>ato!sky 1..3). /till better ceramic !ilters !or sim ltaneo s /O ), 9O) and partic late remo#al are nder de#elopment (?hite et al. 1..2). %rocesses !or alkali remo#al in the A85 @ .55 7C ran"e are nder de#elopment and e)pected to be commercialised within !ew years. =ead and 1inc are not remo#ed at this temperat re ($lderliesten 1..5). Hi"h temperat re alkali remo#al by passin" the "as stream thro "h a !i)ed bed o! sorbent or "etter material that pre!erentially adsorbs alkali #ia physical adsorption or chemisorption was disc ssed by 0 rn et al. (1..*). (elow &55 7C alkali metals condense onto partic lates and can more easily be remo#ed with !ilters (>ato!sky 1..3). 9ickel6based catalysts ha#e pro#ed to be #ery e!!icient in decomposin" tar, ammonia and methane in biomass "asi!ication "as mi)t res at abo t .55 7C. Howe#er, s lph r can poison these catalysts (Hepola et al. 1..AC 0iEmensen 2555). It is nclear i! the nitro"eno s component HC9 is remo#ed. It will probably !orm 9O ) in a "as t rbine (Kerschoor et al. 1..1). Halo"ens are remo#ed by sodi m and calci m6based powdered absorbents. 0hese are inEected in the "as stream and remo#ed in the ded stin" sta"e (Kerschoor et al. 1..1). Hot "as des lph risation is done by chemical absorption to 1inc titanate or iron o)ide6on6silica. 0he process works optimally at abo t &55 7C or 385 7C, respecti#ely. - rin" re"eneration o! the sorbents, /O 2 is liberated and has to be processed to H2/O+ or elemental s lph r (;ansen 1..5C ;othim r "esan et al. 1..&). JnO beds operate best close to +55 7C (#an -iEk et al. 1..8). :arly compression wo ld red ce the si1e o! "as cleanin" e3 ipment. Howe#er, s lph r and chloride compo nds condense when compressed and they may corrode the compressor. 0here!ore, intermediate compression to & bar takes place only a!ter b lk remo#al and &5 bar compression E st be!ore the " ardbed.

11

/.5

#as conditioning

Reforming

0he synthesis "as can contain a considerable amo nt o! methane and other li"ht hydrocarbons, representin" a si"ni!icant part o! the heatin" #al e o! the "as. /team re!ormin" (/M') con#erts these compo nds to CO and H 2 dri#en by steam addition o#er a catalyst ( s ally nickel) at hi"h temperat res (>ato!sky 1..3). $ tothermal re!ormin" ($0') combines partial o)idation in the !irst part o! the reactor with steam re!ormin" in the second part, thereby optimally inte"ratin" the heat !lows. It has been s ""ested that $0', d e to a simpler concept co ld become cheaper than /M' (>ato!sky 1..3), altho "h others "i#e m ch hi"her prices (Oonk et al. 1..A). 0here is disp te on whether the /M' can deal with the hi"h CO and CL content o! the biomass synthesis "as. ?here >ato!sky writes that no additional steam is needed to pre#ent cokin" or carbon deposition in /M', 0iEmensen (2555) poses that this problem does occ r in /M' and that $0' is the only technolo"y able to pre#ent cokin". /team re!ormin" is the most common method o! prod cin" a synthesis "as !rom nat ral "as or "asi!ier "as. 0he hi"hly endothermic process takes place o#er a nickel6based catalyst4 C H + L H 2 O C O L 3H 2 C 2 H + L 2H 2 O 2C O L +H 2 C 2 H & L 2H 2 O 2C O L 8H 2
=4uation 1 =4uation 2 =4uation :

Conc rently, the water "as shi!t reaction (see below) takes place, and brin"s the re!ormer prod ct to chemical e3 ilibri m (>ato!sky 1..3). 'e!ormin" is !a#o red at lower press res, b t ele#ated press res bene!it economically (smaller e3 ipment). 'e!ormers typically operate at 1 @ 3.8 M%a. 0ypical re!ormer temperat re is between *35 7C and 1555 7C. Hi"h temperat res do not lead to a better prod ct mi) !or methanol prod ction (>ato!sky 1..3). 0he inlet stream is heated by the o tlet stream p to nearby the re!ormer temperat re to match re!ormer heat demand and s pply. In this case less synthesis "as has to be b rned compared to a colder "as inp t, this e#ent ally !a#o rs a hi"her methanol prod ction. $ltho "h less steam can be raised !rom the heat at the re!ormer o tlet, the o#erall e!!iciency is hi"her. /M' ses steam as the con#ersion reactant and to pre#ent carbon !ormation d rin" operation. 0 be dama"e or e#en r pt re can occ r when the steam to carbon ratio drops below acceptable limits. 0he speci!ic type o! re!ormin" catalyst sed, and the operatin" temperat re and press re are !actors that determine the proper steam to carbon ratio !or a sa!e, reliable operation. 0ypical steam to hydrocarbon6carbon ratios ran"e !rom 241 !or nat ral "as !eeds with CO 2 recycle, to 341 !or nat ral "as !eeds witho t CO 2 recycle, propane, naphtha and b tane !eeds (>in" et al. 2555). Fs ally ! ll con#ersion o! hi"her hydrocarbons in the !eedstock takes place in an adiabatic pre6re!ormer. 0his makes it possible to operate the t b lar re!ormer at a steam to carbon ratio o! 2.8. ?hen hi"her hydrocarbons are still present, the steam to carbon ratio sho ld be hi"her4 3.8. In older plants, where there is only one steam re!ormer, the steam to carbon ratio was typically 8.8. $ hi"her steam4carbon ratio !a#o rs a hi"her H 24CO ratio and th s hi"her methanol prod ction. Howe#er, more steam m st be raised and heated to the reaction temperat reC this decreases the process e!!iciency. 9either is additional steam necessary to pre#ent cokin" (>ato!sky 1..3). %re6heatin" the hydrocarbon !eedstock with hot !l e "as in the /M' con#ection section, be!ore steam addition, sho ld be a#oided. -ry !eed "as m st not be heated abo#e its crackin" temperat re. Otherwise, carbon may be !ormed, thereby, decreasin" catalyst acti#ities, increasin" press re drop and limitin" plant thro "hp t. In the absence o! steam, crackin" o! nat ral "as occ rs at temperat res abo#e +85 7C, while the !l e "as e)itin" /M's is typically abo#e 1555 7C (>in" et al. 2555). 9ickel catalysts are a!!ected by s lph r at concentrations as low as 5.28 ppm. $n alternati#e wo ld be to se catalysts that are resistant to s lph r, s ch as s lphided cobalt2molybdate. Howe#er, since other catalysts downstream o! the 12

re!ormer are also sensiti#e to s lph r, it makes the most sense to remo#e any s lph r be!ore conditionin" the synthesis "as (>ato!sky 1..3). 0he li!etime o! catalysts ran"es !rom 3 years (#an -iEk et al. 1..8) to A years (>in" et al. 2555). 0he reason !or chan"e o t are typically catalyst acti#ity loss and increasin" press re drop o#er the t bes. $ tothermal re!ormin" ($0') combines steam re!ormin" with partial o)idation. In $0', only part o! the !eed is o)idised, eno "h to s pply the necessary heat to steam re!orm the remainin" !eedstock. 0he re!ormer prod ces a synthesis "as with a lower H24CO ratio than con#entional steam methane re!ormin" (>ato!sky 1..3C %ieterman 2551). $n $ tothermal 'e!ormer consists o! two sections. In the b rner section, some o! the preheated !eed2steam mi)t re is b rned stoichiometrically with o)y"en to prod ce CO2 and H2O. 0he prod ct and the remainin" !eed are then !ed to the re!ormin" section that contains the nickel6based catalyst (>ato!sky 1..3). ?ith $0' considerably less synthesis "as is prod ced, b t also considerably less steam is re3 ired d e to the hi"her temperat re. Increasin" steam addition hardly in!l ences the H 24CO ratio in the prod ct, while it does dil te the prod ct with H2O (>ato!sky 1..3). 0ypical $0' temperat re is between .55 7C and 1555 7C. /ince a tothermal re!ormin" does not re3 ire e)pensi#e re!ormer t bes or a separate ! rnace, capital costs are typically 85 @ &5 B less than con#entional steam re!ormin", especially at lar"er scales (-ybkEaer et al. 1..AC 3 oted by %ieterman 2551). 0his e)cl des the cost o! o)y"en separation. $0' co ld there!ore be attracti#e !or !acilities that already re3 ire o)y"en !or biomass "asi!ication (>ato!sky 1..3). 0he maEor so rce o! H2 in oil re!ineries, catalytic re!ormin", is decreasin". 0he lar"est 3 antities o! H 2 are c rrently prod ced !rom synthesis "as by steam6re!ormin" o! methane, b t this approach is both ener"y and capital intensi#e. %artial o)idation o! methane with air as the o)y"en so rce is a potential alternati#e to the steam6re!ormin" processes. In methanol synthesis startin" !rom C1 to C3, it o!!ers special ad#anta"es. 0he amo nt o! methanol prod ced per kmol hydrocarbon may be 15 to 25 B lar"er than in a con#entional process sin" a steam re!ormer (de =atho der 1.*2). Howe#er, the lar"e dil tion o! prod ct "ases by 9 2 makes this path neconomical, and, alternati#ely, se o! p re o)y"en re3 ires e)pensi#e cryo"enic separation (Maiya et al. 2555). 'e!ormin" is still s bEect to inno#ation and optimisation. % re o)y"en can be introd ced in a partial o)idation reactor by means o! a ceramic membrane, at *85 @ .55 7C, in order to prod ce a p rer synthesis "as. =ower temperat re and lower steam to CO ratio in the shi!t reactor leads to a hi"her thermodynamic e!!iciency while ma)imisin" H 2 prod ction (Maiya et al. 2555).
Water gas s!ift

0he synthesis "as prod ced by the (C= and ID0 "asi!iers has a low H24CO ratio. 0he water "as shi!t (?D/) reaction (:3 ation +) is a common process operation to shi!t the ener"y #al e o! the carbon mono)ide to the hydro"en, which can then be separated sin" press re swin" adsorption. I! the stoichiometric ratio o! H 2, CO and CO2 is n!a#o rable !or methanol prod ction, the water "as shi!t can be sed in combination with a CO 2 remo#al step. 0he e3 ilibri m constant !or the ?D/ increases as temperat re decreases. Hence, to increase the prod ction to H 2 !rom CO, it is desirable to cond ct the reaction at lower temperat res, which is also pre!erred in #iew o! steam economy. Howe#er, to achie#e the necessary reaction kinetics, hi"her temperat res are re3 ired ($rmor 1..*C Maiya et al. 2555). C O L H2 O C O 2 L H2
=4uation ;

0he water "as shi!t reaction is e)othermic and proceeds nearly to completion at low temperat res. Modern catalysts are acti#e at as low as 255 7C (>ato!sky 1..3) or +55 7C (Maiya et al. 2555). - e to hi"h catalyst selecti#ity, all "ases e)cept those in#ol#ed in the water6"as shi!t reaction are inert. 0he reaction is independent o! press re. Con#entionally, the shi!t is realised in a s ccessi#e hi"h temperat re (3&5 7C) and low temperat re (1.5 7C) reactor. 9owadays, the shi!t section is o!ten simpli!ied by installin" only one CO6shi!t con#erter operatin" at medi m 13

temperat re (215 7C) (Haldor0opsoe 1..1). ,or methanol synthesis, the "as can be shi!ted partially to a s itable H24CO ratio, there!ore Hless than oneI reactor is applied. 0he temperat re may be hi"her beca se the reaction needs not to be complete and this way less process heat is lost. 0heoretically the steam4carbon mono)ide ratio co ld be 241. On lab scale "ood res lts are achie#ed with this ratio (Maiya et al. 2555). In practice e)tra steam is added to pre#ent cokin" (0iEmensen 2555).
CO" removal

0he synthesis "as !rom the "asi!ier contains a considerable amo nt o! CO 2. $!ter re!ormin" or shi!tin", this amo nt increases. 0o "et the ratio (H26CO2)2(CO LCO2) to the #al e desired !or methanol synthesis, part o! the carbon dio)ide co ld be remo#ed. ,or this p rpose, di!!erent physical and chemical processes are a#ailable. Chemical absorption sin" amines is the most con#entional and commercially best6pro#en option. %hysical absorption, sin" /ele)ol, has been de#eloped since the se#enties and is an economically more attracti#e technolo"y !or "as streams containin" hi"her concentrations o! CO2. $s a res lt o! technolo"ical de#elopment, the choice !or one technolo"y or another co ld chan"e in time, e.". membrane technolo"y or still better amine combinations co ld play an important role in ! t re. Chemical absorption sin" amines is especially s itable when CO 2 partial press res are low, aro nd 5.1 bar. It is a technolo"y that makes se o! chemical e3 ilibria, shi!tin" with temperat re rise or decline. (asically, CO 2 binds chemically to the absorbent at lower temperat res and is later stripped o!! by hot steam. Commonly sed absorbents are alkanolamines applied as sol tions in water. $lkanolamines can be di#ided into three classes4 primary, secondary and tertiary amines. Most literat re is !oc sed on primary amines, especially monoethanolamine (M:$), which is considered the most e!!ecti#e in reco#erin" CO 2 (,arla et al. 1..8C ?ilson et al. 1..2), altho "h it mi"ht well be that other a"ents are also s itable as absorbents (Hendriks 1..+). 0he Fnion Carbide M,l e D ardN process and the ,l or -aniel :conamine ,D process (!ormerly known as the -ow Chemical Das2/pec ,061 process) se M:$, combined with inhibitors to red ce amine de"radation and corrosion. 0he cost o! amine based capt re are determined by the cost o! the installation, the ann al se o! amines, the steam re3 ired !or scr bbin" and the electric power. 0here is in!l ence o! scale and a stron" dependence on the CO 2 concentration (Hendriks 1..+). 0he in#estment costs are in#ersely proportional to the CO2 concentration in the !eed "as when these ran"e !rom + to * B. M:$ is partly entrained in the "as phase, this res lts in chemical cons mption o! 5.8 @ 2 k" per tonne CO 2 reco#ered (,arla et al. 1..8C / da et al. 1..2). 0he presence o! /O2 leads to an increased sol#ent cons mption (Hendriks 1..+). ?hen the CO2 content makes p an appreciable !raction o! the total "as stream, the cost o! remo#in" it by heat re"enerable reacti#e sol#ents may be o t o! proportion to the #al e o! the CO 2. 0o o#ercome the economic disad#anta"es o! heat re"enerable processes, physical absorption processes ha#e been de#eloped which are based on the se o! essentially anhydro s or"anic sol#ents which dissol#e the acid "ases and can be stripped by red cin" the acid6"as partial press re witho t the application o! heat. %hysical absorption re3 ires a hi"h partial press re o! CO 2 in the !eed "as to be p ri!ied, ..8 bar is "i#en as an e)ample by Hendriks (1..+). Most physical absorption processes !o nd in literat re are /ele)ol, which is licensed by Fnion Carbide, and = r"iIs 'ectisol (Hendriks 1..+C Hydrocarbon %rocessin" 1..*C 'iesen!eld et al. 1.A+). 0hese processes are commercially a#ailable and !re3 ently sed in the chemical ind stry. In a co nter c rrent !low absorption col mn, the "as comes into contact with the sol#ent, a .8 B sol tion o! the dimethyl ether o! polyethylene "lycol in water. 0he CO 2 rich sol#ent passes a recycle !lash dr m to reco#er co6absorbed CO and H2. 0he CO2 is reco#ered by red cin" the press re thro "h e)panders. 0his reco#ery is accomplished in serially connected dr ms. 0he CO 2 is released partly at atmospheric press re. $!ter the desorption sta"es, the /ele)ol still contains 28 6 38 B o! the ori"inally dissol#ed CO 2. 0his CO2 is ro ted back to the absorber and is reco#ered in a later cycle. 0he CO 2 reco#ery rate !rom the "as stream will be appro)imately .* to .. B when all losses are taken into acco nt. Hal! o! the CO 2 is released at 1 bar and hal! at ele#ated press re4 + bar. Minor "as 1+

imp rities s ch as carbonyl s lphide, carbon dis lphide and mercaptans are remo#ed to a lar"e e)tent, to"ether with the acid "ases. $lso hydrocarbons abo#e b tane are lar"ely remo#ed. Complete acid6"as remo#al, i.e. to ppm le#el, is possible with physical absorption only, b t is o!ten achie#ed in combination with a chemical absorption process. /ele)ol can also remo#e H2/, i! this was not done in the "as6cleanin" step. It has been s ""ested by -e =atho der (1.*2) to scr b CO2 sin" cr de methanol !rom the synthesis reactor that has not yet been e)panded. 0he press re needed !or the CO 2 absorption into the methanol is similar tot the methanol press re directly a!ter synthesis. 0his way only a limited amo nt o! CO 2 is remo#ed, and the re3 ired CO2 partial press re is hi"h, b t the desired ' can be reached i! conditions are well chosen. 0he ad#anta"e o! this method is that no separate re"eneration step is re3 ired and that it is not necessary to apply e)tra coolin" o! the "as stream be!ore the scr bbin" operation. 0he CO2 loaded cr de methanol can be e)panded to abo t atmospheric press re, so that the carbon dio)ide is a"ain released, a!ter which the methanol is p ri!ied as wo ld normally be the case. %hysical adsorption systems are based on the ability o! poro s materials (e.". 1eolites) to selecti#ely adsorb speci!ic molec les at hi"h press re and low temperat re and desorb them at low press re and hi"h temperat re. 0hese processes are already commercially applied in hydro"en prod ction, besides a hi"hly p re hydro"en stream a p re carbon dio)ide stream is co6prod ced. %hysical adsorption technolo"ies are not yet s itable !or the separation o! CO 2 only, d e to the hi"h ener"y cons mption (Ishibashi et al. 1..*C >ato!sky 1..3).

/.!

6ethanol synthesis

Methanol is prod ced by the hydro"enation o! carbon o)ides o#er a s itable (copper o)ide, 1inc o)ide, or chromi m o)ide6based) catalyst4 C O L 2H 2 CH 3 OH C O 2 L 3H 2 CH 3 OH L H 2 O
=4uation , =4uation /

0he !irst reaction is the primary methanol synthesis reaction, a small amo nt o! CO 2 in the !eed (2615B) acts as a promoter o! this primary reaction and helps maintain catalyst acti#ity. 0he stoichiometry o! both reactions is satis!ied when ' in the !ollowin" relation is 2.53 minimally (>ato!sky 1..3). H2 b ilds p in the recycle loop, this leads to an act al ' #al e o! the combined synthesis !eed (make p pl s recycle !eed) o! 3 to + typically.

R=

H 2 CO2 CO + CO2

=4uation 5

0he reactions are e)othermic and "i#e a net decrease in molar #ol me. 0here!ore, the e3 ilibri m is !a#o red by hi"h press re and low temperat re. - rin" prod ction, heat is released and has to be remo#ed to keep optim m catalyst li!e and reaction rate. 5.3 B o! the prod ced methanol reacts ! rther to !orm side prod cts as dimethyl ether, !ormaldehyde or hi"her alcohols (#an -iEk et al. 1..8). 0he catalyst deacti#ates primarily beca se o! loss o! acti#e copper d e to physical blocka"e o! the acti#e sites by lar"e by6prod ct molec lesC poisonin" by halo"ens or s lph r in the synthesis "as, which irre#ersibly !orm inacti#e copper saltsC and sinterin" o! the copper crystallites into lar"er crystals, which then ha#e a lower s r!ace to #ol me ratio. Con#entionally, methanol is prod ced in two6phase systems4 the reactants and prod cts !ormin" the "as phase and the catalyst bein" the solid phase. 0he prod ction o! methanol !rom synthesis "as was !irst de#eloped at ($/, in 1.22 Dermany. 0his process sed a 1inc o)ide 2 chromi m o)ide catalyst with poor selecti#ity, and re3 ired e)tremely #i"oro s conditionsOpress res ran"in" !rom 355@1555 bar, and temperat res o! abo t +55 7C. In the 1.&5s and A5s the more acti#e C 2Jn2$l catalyst was de#eloped allowin" more ener"y6e!!icient and cost6e!!ecti#e plants, and lar"er scales. %rocesses nder de#elopment at present !oc s on shi!tin" the e3 ilibri m to the prod ct side to achie#e hi"her con#ersion per pass. :)amples are the "as2solid2solid trickle !low reactor, with a !ine adsorbent powder !lowin" down 18

a catalyst bed and pickin" p the prod ced methanolC and li3 id phase methanol processes where reactants, prod ct, and catalyst are s spended in a li3 id. , ndamentally di!!erent co ld be the direct con#ersion o! methane to methanol, b t despite a cent ry o! research this method has not yet pro#ed its ad#anta"es.
#ixe$ %e$ tec!nology

0wo reactor types predominate in plants b ilt a!ter 1.A5 (Cyb lski 1..+C >irk6Othmer 1..8). 0he ICI low6press re process is an adiabatic reactor with cold nreacted "as inEected between the catalyst beds (,i" re 8, le!t). 0he s bse3 ent heatin" and coolin" leads to an inherent ine!!iciency, b t the reactor is #ery reliable and there!ore still predominant. 0he = r"i system (,i" re 8, ri"ht), with the catalyst loaded into t bes and a coolin" medi m circ latin" on the o tside o! the t bes, allows near6isothermal operation. Con#ersion to methanol is limited by e3 ilibri m considerations and the hi"h temperat re sensiti#ity o! the catalyst. 0emperat re moderation is achie#ed by recyclin" lar"e amo nts o! hydro"en rich "as, tilisin" the hi"her heat capacity o! H 2 "as and the hi"her "as #elocities to enhance the heat trans!er. 0ypically a "as phase reactor is limited to abo t 1& B CO "as in the inlet to the reactor, in order to limit the con#ersion per pass to a#oid e)cess heatin".

"ot synthesis gas

Methanol

%ool synthesis gas

%atalyst (eds

Steam

8ater

Methanol

"ot synthesis gas

Fi!ure ,)

<ethanol %ri!ht&)

reactor

types'

adiabatic

4uench

%le t&

and

isot hermal

steam

r a is i n !

0he methanol synthesis temperat re is typically between 235 and 2A5 7C. 0he press re is between 85 and 185 bar. Hi"her press res "i#e an economic bene!it, since the e3 ilibri m then !a#o rs methanol. Only a part o! the CO in the !eed "as is con#erted to methanol in one pass thro "h the reactor, d e to the low temperat re at which the catalyst operates. 0he nreacted "as is recycled at a ratio typically between 2.3 and &. 0he copper catalyst is poisoned by both s lph r and chlorine, b t the presence o! !ree 1inc o)ides does help pre#ent poisonin".
Liqui$ p!ase met!anol pro$uction

In li3 id phase processes (Cyb lski 1..+C F/-O: 1...), the heat trans!er between the solid catalyst and the li3 id phase is hi"hly e!!icient, and there!ore the process temperat re is #ery ni!orm and steady. $ "as phase deli#ers reactants to the !inely di#ided catalyst and remo#es the prod cts swi!tly. 0his allows hi"h con#ersions to be obtained witho t loss o! catalyst acti#ity. 0he hi"her con#ersion per pass (compared to !i)ed bed technolo"y) eliminates the need !or a recycle loop, which implies less a )iliary e3 ipment, less ener"y re3 irements, smaller #ol metric !low thro "h the reactor (>ato!sky 1..3). $n additional ad#anta"e is the ability to withdraw spent catalyst and add !resh catalyst witho t interr ptin" the process. 1&

Methanol + unreacted gas Gas (u((les

"# %O

%"/O"

Synthesis gas

Slurry 7ith catalyst

Fi!ure /)

. i4uid phase methano l synt hesis #ith th ree ph ases' slu rry, !as an d solid)

-i!!erent reactor types are possible !or li3 id phase methanol prod ction, s ch as a !l idised beds and monolithic reactors. $ir %rod cts and Chemicals, Inc. in#ented a sl rry b bble col mn reactor in the late 1.A5s, which was ! rther de#eloped and demonstrated in the 1.*5s and 1..5s. ,rom 1..A tot 2553, a 355 tonne2day demonstration !acility at :astman Chemical Company in >in"sport 09 prod ced abo t +55 million litres methanol !rom coal #ia "asi!ication (Heydorn et al. 2553). In the sl rry b bble col mn reactor (,i" re &), reactants !rom the "as b bbles dissol#e in the li3 id and di!! se to the catalyst s r!ace, where they react. %rod cts then di!! se thro "h the li3 id back to the "as phase. Heat is remo#ed by "eneratin" steam in an internal t b lar heat e)chan"er. Commercial C 2Jn2$l catalysts de#eloped !or the two6phase process are sed !or the three6phase process. 0he powdered catalyst particles typically meas re 1 to 15 m and are densely s spended in a thermostable oil, chemically resistant to components o! the reaction mi)t re at process conditions, s ally para!!in. Catalyst deacti#ation d e to e)pos re to trace contaminants is a point o! concern (Cyb lski 1..+). Con#ersion per pass depends on reaction conditions, catalyst, sol#ent and space #elocity. :)perimental res lts show 18 @ +5 B con#ersion !or CO rich "ases and +5 @ A5 B CO !or balanced and H2 rich "ases. Comp tation models predict ! t re CO con#ersions o! o#er .5 B, p to .A B respecti#ely (Cyb lski 1..+C Ha"ihara et al. 1..8). 'esearchers at the (rookha#en 9ational =aboratory ha#e de#eloped a low temperat re (acti#e as low as 155 7C) li3 id phase catalyst that can con#ert .5 B o! the CO in one pass (>ato!sky 1..3). ?ith steam addition the reaction mi)t re becomes balanced thro "h the water "as shi!t reaction. F/-O: claims that the initial hydro"en to carbon mono)ide ratio is allowed to #ary !rom 5.+ to 8.& witho t a ne"ati#e e!!ect on per!ormance (F/-O: 1...). 0he in#estment costs !or the li3 id phase methanol process are e)pected to be 8 @ 23 B less than !or a "as phase process o! the same methanol capacity. Operatin" costs are 2 @ 3 B lowerC this is mainly d e to a !o r times lower electricity cons mption (F/-O: 1...).

1A

0 3+ t i o n s f o r sy n e r g y

0.1

Electricity co"generation by combined cycle

Fncon#erted synthesis "as that remains a!ter the methanol prod ction section can still contain a si"ni!icant amo nt o! chemical ener"y. 0hese "as streams may be comb sted in a "as t rbine, altho "h they "enerally ha#e a m ch lower heatin" #al e (+ @ 15 M;2m 390%) than nat ral "as or distillate ! el (38 @ +5 M;2m 390%) !or which most "as t rbine comb stors ha#e been desi"ned. ?hen considerin" commercially a#ailable "as t rbines !or low calori!ic "as !irin", the !ollowin" items deser#e special attention (Consonni et al. 1..+C 'odri" es de /o 1a et al. 2555C #an 'ee et al. 1..8)4 0he comb stion stability, the press re loss thro "h the ! el inEection system, and the limits to the increasin" mass !low thro "h the t rbine. -i!!erent ind strial and aeroderi#ati#e "as t rbines ha#e been operated s ccess! lly with low =HK "as, b t on the condition that the hydro"en concentration in the "as is hi"h eno "h to stabilise the !lame. Fp to 25 B H 2 is re3 ired at 2.. M;2m390%. Hydro"en has a hi"h !lame propa"ation speed and th s decreases the risk o! e)tin" ishin" the !lame (Consonni et al. 1..+). InEectin" a lar"er ! el #ol me into the comb stor thro "h a no11le ori"inally desi"ned !or a ! el with m ch hi"her ener"y density can lead to press re losses, and th s to a decreased o#erall cycle e!!iciency. Minor modi!ications are s !!icient !or most e)istin" t rbines. In the lon"er term, new t rbines optimised !or low heatin" #al e "as mi"ht incl de a complete no11le comb stor re6desi"n (Consonni et al. 1..+). 0he lar"er ! el !low rate also implies an increase in mass !low thro "h the t rbine e)pander, relati#e to nat ral "as !irin". 0his can be accommodated partly by increasin" the t rbine inlet press re, b t this is limited by the compressor power a#ailable. $t a certain moment the compressor cannot match this increased press re any more and "oes into stall4 the compressor blocks. 0o pre#ent stall, decreasin" the comb stion temperat re is necessaryC this is called deratin". 0his will lower the e!!iciency o! the t rbine, tho "h (Consonni et al. 1..+C #an 'ee et al. 1..8). Hi"her t rbine capacity wo ld normally "i#e a hi"her e!!iciency, b t as the deratin" penalty is also stron"er the e!!iciency "ain is small ('odri" es de /o 1a et al. 2555). - e to the set6 p o! the en"ine the compressor deli#ers a speci!ic amo nt o! air. Howe#er, to b rn one m 390% o! ! el "as less compressed air is needed compared to !irin" nat ral "as. 0he s rpl s air can be bled !rom the compressor at di!!erent press res and sed elsewhere in the plant, e.". !or o)y"en prod ction (#an 'ee et al. 1..8). I! not, e!!iciency losses occ r. $ll the possible problems mentioned !or the c rrently a#ailable "as t rbines, can be o#ercome when desi"nin" ! t re D0s. On"oin" de#elopments in "as t rbine technolo"y increase e!!iciency and lower the costs per installed k? o#er time (#an 'ee et al. 1..8). Cooled intersta"es at the compressor will lower compressor work and prod ce heat, which can be sed elsewhere in the system. $lso "as t rbine and steam t rbine co ld be p t on one a)is, which sa#es o t one "enerator and "i#es a somewhat hi"her e!!iciency. 0 rbines set limits to the "as 3 ality. 0he "as cleanin" system needs to match particles and alkali re3 irements o! the D0s. ?hen these standards are e)ceeded wearin" becomes more se#ere and li!etime and e!!iciency will drop (#an 'ee et al. 1..8). Howe#er, the synthesis "as that passed #ario s catalysts prior to the "as t rbine has to meet stricter demands. It is there!ore e)pected that contaminants are not a real problem in "as t rbines r nnin" on !l e "as !rom methanol prod ction. 1*

0./

Natural gas co"firing * co"feeding

I! the caloric #al e o! the ncon#erted synthesis "as is too low !or (direct) comb stion in a "as t rbine, this co ld be compensated !or by co6!irin" nat ral "as. (esides raisin" the heatin" #al e o! the "as, the application o! nat ral "as can also increase the scale, thermal e!!iciency, and economics o! the "as t rbines. 9at ral "as can also be applied as co6!eedin" in the entire process. Or, #ice #ersa, the lar"e scale o! e)istin" methanol prod ction nits co ld be tilised by pl ""in"6in a biomass "asi!ier and "as make6 p section. 0he prod ct can be considered partially o! biomass ori"in.

0.0

9lack li:uor gasification

% lp and paper mills prod ce h "e amo nts o! black li3 or as a resid e. 0hey are the most important so rce o! biomass ener"y in co ntries s ch as /weden and ,inland, representin" a potential ener"y so rce o! 285 @ 855 M? per mill. $s modern kra!t p lp mills ha#e a s rpl s o! ener"y, they co ld become key s ppliers o! renewable ! els in the ! t re ener"y system, i! the primary ener"y in the black li3 or co ld be con#erted to an ener"y carrier o! hi"h #al e. :kbom et al. (2553) ha#e e#al ated the prod ction o! methanol and -M: (see later) !rom black li3 or "asi!ication (BLGMF process). 0his scheme co ld be realised a"ainst reasonable costs, i! heat reco#ery boilers which economic li!e has ended are replaced by (=DM,. Fsin" black li3 or as a raw material !or methanol2-M: prod ction wo ld ha#e the !ollowin" ad#anta"es4 (iomass lo"istics are e)tremely simpli!ied as the raw material !or ! el makin" is handled within the ordinary operations o! the p lp P paper plant 0he process is easily press rised, which enhances ! el prod ction e!!iciency 0he prod ced syn"as has a low methane content, which optimises ! el yield % lp mill economics becomes less sensiti#e to p lp prices as the economics are di#ersi!ied with another prod ct Dasi!ication capital cost is shared between reco#ery o! inor"anic chemicals, steam prod ction and syn"as prod ction.

0.2

3ther biofuels via gasification

Dasi!ication, "as cleanin" and make6 p are important parts o! the process to make methanol !rom biomass. 0hese parts are also key to the prod ction o! hydro"en and ,ischer60ropsch li3 ids !rom biomass. -e#elopment o! methanol !rom biomass th s o!!ers syner"y with de#elopment o! hydro"en and ,ischer60ropsch li3 ids. Methanol can also be an intermediate in the prod ction o! other renewable ! els s ch as synthetic diesel, "asoline and dimethyl ether.
&y$rogen

0he prod ction o! hydro"en !rom synthesis "as is somewhat simpler and cheaper than the prod ction o! methanol. 0he "asi!ication step sho ld aim at ma)imisin" the hydro"en yield, which can be ! rther increased by re!ormin" any methane le!t and a water6"as6shi!t reaction. Hydro"en separation takes place by press re swin" adsorption or (in ! t re) membranes. Hydro"en is already prod ced at lar"e scale in chemical and oil ind stry. It is o!ten seen as the ! t re ! el !or the transportation sector and ho seholds.

1.

#isc!er'Tropsc! (#T) $iesel

$ broad ran"e o! hydrocarbons, ran"in" !rom methane to wa)es o! hi"h molec lar wei"ht can be prod ced !rom synthesis "as sin" an iron or cobalt catalyst. 0hese are called ,ischer60ropsch (,0) li3 ids or Das6to6=i3 ids (D0=). (y crackin" the lon"er hydrocarbons and re!inin", a diesel is prod ced that can be blended into standard diesel. ,0 diesel has #ery low le#els o! s lph r and aromatic compo nds compared to ordinary diesel and, when processed in an internal comb stion en"ine, emit less 9O) and partic lates than diesel ! els. 0he ,0 process was !irst de#eloped at commercial scale !or the prod ction o! synthetic oil in Dermany d rin" /econd ?orld ?ar and was ! rther de#eloped by /asol in /o th $!rica. /asol remains today the only prod cer o! ,0 prod cts !rom low "rade coals. 0he risin" oil price, a#ailability o! lar"e amo nts o! Mstranded "asN, and decreasin" in#estment costs ha#e increased the interest in ,0 li3 ids. Qatar seems to be the dri#er o! ,0 de#elopment, with planned proEects totalin" to *55,555 bbl2day or abo t 11+ ktonne2day ((ensaRd 255+). In 1... when the world had a considerable s rpl s o! methanol prod ction capacity, se#eral companies proposed to retro!it methanol plants to prod ce alternati#e prod cts, e.". ,ischer60ropsch li3 ids or hydro"en ((rown 1...C Sakobson 1...). 0he demonstration nit o! Choren in ,reiber" Dermany, has prod ced both ,0 li3 ids and methanol.
*et!anol to $iesel

= r"i claims to de#elop a cheaper way to make ltra6clean diesel ! el !rom syn"as #ia methanol. 0he process !irst con#erts methanol into propylene, this is !ollowed by ole!in oli"omeri1ation (con#ersion to distillates), then prod ct separation6pl s6hydro"enation. 0he intermediate methanol6to6propylene step so !ar is only pro#en at demonstration scale. 0he process wo ld yield mostly kerosene and diesel, alon" with a small yield o! "asoline and li"ht ends. 0he near61ero s lph r 2 polyaromatics diesel ! el res ltin" !rom this process wo ld di!!er !rom more con#entional ,ischer60ropsch diesel only in cetane n mbe (T82 #ia MMethanol6to6/yn! elN #ers s TA5 cetane !or ,0 diesel). 0he incidental "asoline stream not only wo ld be near61ero s l! r, b t also ha#e commercial octane ratin"s (.2 'O9, *5 MO9) and ma)imally 11 B aromatics (%eckham 2553).
*et!anol to gasoline

In the 1.A5s, Mobil de#eloped and commercialised a methanol to "asoline (M0D) process. $ plant was b ild in Mont n i 2 9ew Jealand in 1.*8 and sold to Methane). It prod ced "asoline ntil 1..A when the plant was permanently idled. I! the "asoline is to be sold witho t additional blendin", then ! rther treatin" is necessary to red ce the amo nt o! ben1enes.
Dimet!yl et!er (D*+)

-imethyl ether (CH3OCH3) is "enerally prod ced by dehydration o! methanol. $t lar"e scale, the methanol prod ction and dehydration processes are combined in one reactor, s ch that -M: is prod ced directly !rom synthesis "as sli"htly more e!!icient than methanol. 0he pre#io sly mentioned sl rry b bble col mn reactor o! :astman Chemical Company in >in"sport 09 has been demonstrated to be able to prod ce -M: as well. 0he =%-M:U %rocess ses a physical mi)t re o! a commercial methanol catalyst and a commercial dehydration catalyst in a sin"le sl rry reactor (Heydorn et al. 2553). =ike methanol, -M: has promisin" !eat res as ! el candidate with both the Otto and the diesel en"ine. ?ith small adaptations to en"ine and ! el system, -M: can be sed in blends with diesel (15 @ 25 B), leadin" to hi"her ! el e!!iciency and lower emissions. In otto en"ines, -M: can be sed with =%D (any B) and neat. /ince -M: is as easily 25

re!ormed as methanol, it has a bi" potential as ! el o! ! el cell #ehicles (#an ?alwiEk et al. 1..&). -M: can be easily press rised and handled as a li3 id (:kbom et al. 2553).

21

2 1e c h n o" e c on o m ic + er f o r m a n c e

,ollowin" the train o! components o! ,i" re 1 and "i#en the potential options !or "asi!ication, "as cleanin" and conditionin", synthesis and separation, many ro tes to prod ce methanol !rom biomass can be ima"ined. 0he a thors ha#e pre#io sly analysed the techno6economic per!ormance o! methanol !rom wood thro "h & concepts which will be recapit lated here. $t the end o! the section, res lts will be placed into broader perspecti#e with other literat re and with !ossil "asoline and diesel.

2.1

-election of conce+ts

/ome concepts chosen resemble con#entional prod ction o! methanol !rom nat ral "as, makin" se o! wet "as cleanin", steam re!ormin", shi!t, and a solid bed methanol reactor. /imilar concepts ha#e pre#io sly been analysed by >ato!sky (1..3). $d#anced components co ld o!!er direct or indirect ener"y bene!its (li3 id phase methanol synthesis, hot "as cleanin"), or economic bene!its (a tothermal re!ormin"). $#ailable process nits are lo"ically combined so the s pplied "as composition o! a nit matches the demands o! the s bse3 ent nit, and heat leaps are restricted i! possible. 0he !ollowin" considerations play a role in selectin" concepts4 0he ID0 direct o)y"en !ired press rised "asi!ier, in the normal and ma)imised H 2 option, and the (attelle indirect atmospheric "asi!ier are considered !or synthesis "as prod ction, beca se they deli#er a medi m calori!ic nitro"en ndil ted "as stream and co#er a broad ran"e o! "as compositions. Hot "as cleanin" is only sensible i! !ollowed by hot process nits like re!ormin" or (intermediate temperat re) shi!tin". Hot "as cleanin" is not applied a!ter atmospheric "asi!ication since the s bse3 ent press risation o! the synthesis "as necessitates coolin" anyway. ,or re!ormin" ! el "as prod ced #ia an ID0 "asi!ier, an a tothermal re!ormer is chosen, beca se o! the hi"her e!!iciency, and lower costs. 0he hi"h hydro"en yield, possible with steam re!ormin" is less important here since the H24CO ratio o! the "as is already hi"h. 0he (C= "asi!ier, howe#er, is !ollowed by steam re!ormin" to yield more hydro"en. %recedin" li3 id phase methanol synthesis, shi!tin" the synthesis "as composition is not necessary since the reaction is !le)ible towards the "as composition. ?hen steam is added, a shi!t reaction takes place in the reactor itsel!. (e!ore "as phase methanol prod ction the composition is partially shi!ted and beca se the reactor is sensible to CO2 e)cess, part o! the CO2 is remo#ed. $!ter the methanol once thro "h options, the "as still contains a lar"e part o! the ener"y and is e)pected to s it "as t rbine speci!ications. 0he same holds !or nre!ormed (C= and ID0 "ases, which contain ener"y in the !orm o! C2L !ractions. ?hen the heatin" #al e o! the "as stream does not allow stable comb stion in a "as t rbine, it is !ired in a boiler to raise process steam. 0he chemical ener"y o! ID0L "as is entirely in hydro"en and carbon mono)ide. $!ter once thro "h methanol prod ction the "as still contains eno "h chemical ener"y !or comb stion in a "as t rbine. Heat s pply and demand within plants are to be matched to optimise the o#erall plant e!!iciency.

22

Table :) Gasifier * # / 6 1 IGTmax"# IGT IGT B%& IGT B%&

$ e l e c t e d m e t h a n o l p r o d u c t io n c o n c e p t s ) Gas cleaning 8et "ot +11- :%! 8et 8et "ot +11- :%! 8et Reforming ATR SMR ATR SMR Shift Partial Partial Methanol reactor &iEuid )hase &iEuid )hase? 7ith steam addition &iEuid )hase? 7ith steam addition &iEuid )hase? 7ith steam addition and recycle Solid (ed? 7ith recycle Solid (ed? 7ith recycle o!er generation %om(ined cycle %om(ined cycle %om(ined cycle Steam cycle Steam cycle Steam cycle

O)y"en is sed as o)idant !or the ID0 "asi!ier and the a tothermal re!ormer. 0he se o! air wo ld enlar"e downstream e3 ipment si1e by a !actor +. $lternati#ely, o)y"en enriched air co ld be sed. 0his wo ld probably "i#e an optim m between small e3 ipment and low air separation in#estment costs.

0hese considerations led to a selection o! & con#ersion concepts (see 0able 3). 0he si) concepts selected potentially ha#e low cost and2or hi"h ener"y e!!iciency. 0he concepts are composed makin" se o! both e)istin" commercially a#ailable technolo"ies, as well as (promisin") new technolo"ies.

2./

6odelling mass and energy balances

0he selected systems were modelled in $spen %l s, a widely sed process sim lation pro"ram. In this !lowsheetin" pro"ram, chemical reactors, p mps, t rbines, heat e)chan"in" apparat s, etc are #irt ally connected by pipes. :#ery component can be speci!ied in detail4 reactions takin" place, e!!iciencies, dimensions o! heatin" s r!aces and so on. ,or "i#en inp ts, prod ct streams can be calc lated, or one can e#al ate the in!l ence o! apparat s adE stments on electrical o tp t. 0he plant e!!iciency can be optimised by matchin" the heat s pply and demand. 0he res ltin" dimensions o! streams and nits and the ener"y balances can s bse3 ently be sed !or economic analyses. 0he pre6treatment and "asi!ication sections are not modelled, their ener"y se and con#ersion e!!iciencies are incl ded in the ener"y balances, tho "h. 0he models start with the synthesis "as composition !rom the "asi!iers as "i#en in 0able 1. 0he heat s pply and demand within the plant is care! lly matched, aimed at ma)imi1in" the prod ction o! s perheated steam !or the steam t rbine. 0he intention was to keep the inte"ration simple by placin" !ew heat e)chan"ers per "as2water2steam stream. O! co rse, concepts with more process nits demandin" more temperat re alterin" are more comple) than concepts consistin" o! !ew nits. ,irst, an in#entory o! heat s pply and demand was made. /treams matchin" in temperat re ran"e and heat demand2s pply were combined4 e.". heatin" be!ore the re!ormer by sin" the coolin" a!ter the re!ormer. ?hen the heat demand is met, steam can be raised !or power "eneration. -ependin" on the amo nt and ratio o! hi"h and low heat, process steam is raised in heat e)chan"ers, or drawn !rom the steam t rbine4 I! there is eno "h ener"y in the plant to raise steam o! 355 7C, b t barely s perheatin" capacity, then process steam o! 355 7C is raised directly in the plant. I! there is more s perheatin" than steam raisin" capacity, then process steam is drawn !rom the steam cycle. /team !or "asi!ication and dryin" is almost always drawn !rom the steam cycle, nless a per!ect match is possible with a heat6s pplyin" stream. 0he steam enterin" the steam t rbine is set at *& bar and 815 7C. 0able + s mmarises the o tcomes o! the !lowsheet models. In some concepts still si"ni!icant #ariations can be made. In concept +, the re!ormer needs "as !or !irin". 0he re!ormer can either be entirely !ired by p r"e "as (th s restrictin" the recycle #ol me) or by part o! the "asi!ier "as. 0he !irst option "i#es a somewhat hi"her methanol prod ction and o#erall plant e!!iciency. In concept 8, one can choose between a lar"er recycle, and more steam prod ction in the boiler. $ recycle o! !i#e times the !eed #ol me, instead o! !o r, "i#es a m ch hi"her methanol prod ction and plant e!!iciency. %er concept, only the most e!!icient #ariation is reported in 0able +. 23

Table ;)

2esults o the Aspen Plus per ormance calcu lat ion s, or ;:0 <7 th in pu t HHA systems %e4ui3alent to :?0 <7 th .HA or biomass #ith :0> mo istu re& o the methanol pro ductio n co ncepts co nsidered) ""# $%tp%t &M') )%el *et electricity+) Efficiency() 1- . 11 . 1* . 1$ . 11 . 11 .

* # / 6 1

IGT H max "#? Scru((er? &iEuid Phase Methanol Reactor? %om(ined %ycle IGT? "ot Gas %leaning? Autothermal Reformer? &iEuid Phase Methanol Reactor 7ith Steam addition? %om(ined %ycle IGT? Scru((er? &iEuid Phase Methanol Reactor 7ith Steam addition? %om(ined %ycle B%&? Scru((er? Steam Reformer? &iEuid Phase Methanol Reactor 7ith Steam Addition and Recycle? Steam %ycle IGT? "ot Gas %leaning? Autothermal Reformer? Partial Shift? %on@entional Methanol Reactor 7ith Recycle? Steam Tur(ine B%&? Scru((er? Steam Reforming? Partial Shift? %on@entional Methanol Reactor 7ith Recycle? Steam Tur(ine

* * *$/ **/ #6 ##* #11

1/ # *-1 *1 -*$

1&

2&

Net electrical output is !ross output minus internal use) +ross electricity is produced by !as turbine and9or steam turbine) The internal electricity use stems rom pumps, compressors, o1y!en separator, etc) The o3erall ener!y e iciency is e1pressed as the net overall fuel + electricity efficiency on HHA basis) This de inition !i3es a distorted 3ie#, since the 4uality o ener!y in uel and electricity is considered e4ual, #hile in reality it is not) Alternati3ely, one could calculate a fuel only efficiency, assumin! that the electricity part could be produced rom biomass at e)!) ;, > HHA in an ad3anced -*+9CC %Faaij et al) 166?&, this de inition #ould compensate or the ine4uality o electricity and uel in the most justi ied #ay, but the re erenced electric e iciency is o decisi3e importance) Another 4uali ication or the per ormance o the system could use e1er!y' the amount o #ork that could be deli3ered by the material streams)

(ased on e)periences with low calori!ic comb stion elsewhere (Consonni et al. 1..+C #an 'ee et al. 1..8), the "as !lows in the con!i" rations presented here are e)pected to "i#e stable comb stion in a "as t rbine. 0able + only incl des the ad#anced t rbines. $d#anced t rbine con!i" rations, with set hi"h compressor and t rbine e!!iciencies and no dimension restrictions, "i#e "as t rbine e!!iciencies o! +1 @ 82 B and 1 @ 2 B point hi"her o#erall plant e!!iciency than con#entional con!i" rations. (ased on the o#erall plant e!!iciency, the methanol concepts lie in a close ran"e o! 85 @ 8A B. =i3 id phase methanol prod ction preceded by re!ormin" (concepts 2 and +) res lts in somewhat hi"her o#erall e!!iciencies. $!ter the press rised ID0 "asi!ier hot "as cleanin" leads to hi"her e!!iciencies than wet "as cleanin", altho "h not better than concepts with wet "as cleanin" a!ter a (C= "asi!ier. /e#eral nits may be realised with hi"her e!!iciencies than considered here. ,or e)ample, new catalysts and carrier li3 ids co ld impro#e li3 id phase methanol sin"le pass e!!iciency p to .8 B (Ha"ihara et al. 1..8). 0he electrical e!!iciency o! "as t rbines will increase by 2 @ 3 B points when "oin" to lar"er scale (Das 0 rbine ?orld 1..A).

2.0

Costing method

$n economic e#al ation has been carried o t !or the concepts considered. %lant si1es o! *5, +55, 1555 and 2555 M? th HHK are e#al ated, +55 M?th bein" the base scale. 0he scale o! the con#ersion system is e)pected to be an important !actor in the o#erall economic per!ormance. 0his iss e has been st died !or (ID2CC systems (,aaiE et al. 1..*C =arson et al. 1..A), showin" that the economies o! scale o! s ch nits can o!!set the increased costs o! biomass transport p to capacities o! se#eral h ndreds o! M? th. 0he same reasonin" holds !or the methanol prod ction concepts described here. It sho ld, howe#er, be realised that prod ction !acilities o! 1555 @ 2555 M? th re3 ire #ery lar"e #ol mes o! !eedstock4 255 @ +55 dry tonne2ho r, or 1.& @ 3.2 dry Mtonne per year. (iomass a#ailability will be a limitation !or most locations !or s ch lar"e6scale prod ction !acilities, especially in the shorter term. In the lon"er term (2515 @ 2535), i! biomass prod ction systems become more commonplace, this can chan"e. Kery lar"e scale biomass con#ersion is not witho t precedent4 #ario s lar"e6scale s "ar2ethanol plants in (ra1il ha#e a biomass thro "hp t o! 1 @ 3 Mtonne o! s "arcane per year, while the prod ction season co#ers less than hal! a year. $lso, lar"e paper and p lp

2+

comple)es ha#e comparable capacities. 0he base scale chosen is comparable to the si1e order st died by ?illiams et al. (1..8) and >ato!sky (1..3), 3A5 @ 3*8 M?th. 0he methanol prod ction costs are calc lated by di#idin" the total ann al costs o! a system by the prod ced amo nt o! methanol. 0he total ann al costs consist o!4 $nn al in#estments Operatin" and Maintenance (iomass !eedstock :lectricity s pply 2 demand (!i)ed power price)

0he total ann al in#estment is calc lated by a !actored estimation (%eters et al. 1.*5), based on knowled"e o! maEor items o! e3 ipment as !o nd in literat re or "i#en by e)perts. 0he ncertainty ran"e o! s ch estimates is p to 35 B. 0he installed in#estment costs !or the separate nits are added p. 0he nit in#estments depend on the si1e o! the components (which !ollow !rom the $spen %l s modellin"), by scalin" !rom known scales in literat re (see 0able 8), sin" :3 ation *4

Costb Costa
with

Sizeb = Size a
'

=4uation ?

V /calin" !actor

Kario s system components ha#e a ma)im m si1e, abo#e which m ltiple nits will be placed in parallel. Hence the in!l ence o! economies o! scale on the total system costs decreases. 0his aspect is dealt with by ass min" that the base in#estment costs o! m ltiple nits are proportional to the cost o! the ma)im m si1e4 the base in#estment cost per si1e becomes constant. 0he ma)im m si1e o! the ID0 "asi!ier is s bEect to disc ssion, as the press rised "asi!ier wo ld lo"ically ha#e a lar"er potential thro "hp t than the atmospheric (C=. 0he total in#estment costs incl de a )iliary e3 ipment and installation labo r, en"ineerin" and contin"encies. I! only e3 ipment costs, e)cl din" installation, are a#ailable, those costs are increased by applyin" an o#erall installation !actor o! 1.*&. 0his #al e is based on 33 B added in#estment to hardware costs (instr mentation and control 8B, b ildin"s 1.8B "rid connections 8 B, site preparation 5.8 B, ci#il works 15 B, electronics A B, and pipin" + B) and +5 B added installation costs to in#estment (en"ineerin" 8 B, b ildin" interest 15 B, proEect contin"ency 15 B, !ees2o#erheads2pro!its 15 B, start6 p costs 8 B) (,aaiE et al. 1..*). 0he ann al in#estment takes into acco nt the technical and economic li!etime o! the installation. 0he interest rate is 15 B. Operational costs (maintenance, labo r, cons mables, resid al streams disposal) are taken as a sin"le o#erall percenta"e (+ B) o! the total installed in#estment (,aaiE et al. 1..*C =arson et al. 1..*). -i!!erences between con#ersion concepts are not anticipated. It was ass med that eno "h biomass will be a#ailable at 2 F/W2D; (HHK), this is a reasonable price !or =atin and 9orth $merican conditions. Costs o! c lti#ated ener"y crops in the 9etherlands amo nt appro)imately + F/W2D; and thinnin"s 3 F/W2D; (,aaiE 1..A), and biomass imported !rom /weden on a lar"e scale is e)pected to cost A F/W2D; (1..*). On the other hand biomass "rown on (ra1ilian plantations co ld be deli#ered to local con#ersion !acilities at 1.& @ 1.A F/W2D; (Hall et al. 1..2C ?illiams et al. 1..8). It has been shown elsewhere that international transport o! biomass and bioener"y is !easible a"ainst modest costs. :lectricity s pplied to or demanded !rom the "rid costs 5.53 F/W2k?h. 0he ann al load is *555 ho rs.

28

Table ,) Bnit

Costs o

system components in <I$J 20011&) Base In@estment %ost +fo(! -5/1 -56* *5$5 -5/$ -56* * 5/ /'5* 665# /5* #5 544 *5 #5 /**5* 456 65$ / 54 165* $ /51 *15* *'54 15* 65/ Scale Dactor Base Scale O@erall installation factor
##!

Maximum SiIe #/! ************'/ $1 1# *'6 6 -

Pre-treatment #! %on@eyers /! Grinding /! Storage /! 0ryer /! Iron remo@al /! Deeding system /?6! Gasification System B%& 1! IGT ! Oxygen Plant +installed! $! Gas Cleaning Tar %rac9er /! %yclones /! "igh-tem)erature heat exchanger '! Baghouse filter /! %ondensing Scru((er /! "ot Gas %leaning 4! Synthesis gas Processing %om)ressor *-! Steam Reformer **! Autothermal Reformer *#! Shift Reactor +installed! */! Selexol %O# remo@al +installed! *6! Methanol Production Gas Phase Methanol *1! &iEuid Phase Methanol * ! Refining *$! Po er !sle *'! Gas Tur(ine + "RSG /?*4! Steam Tur(ine + steam system /?#-! ;x)ansion Tur(ine #*!
1&

-5' -5 -5 1 -5' -5$ * -5 1 -5$ -5'1 -5$ -5$ -5 -5 1 -5$ *5-5'1 -5 -5 -5'1 -5$ -5 -5$# -5$ -5$ -5$ -5$

//51 7et tonne,hour //51 7et tonne,hour //51 7et tonne,hour //51 7et tonne,hour //51 7et tonne,hour //51 7et tonne,hour '5' dry tonne,hour '5' dry tonne,hour 6*5$ tonne O#,hour /65# m/ gas,s /65# m/ gas,s /45# 9g steam,s *#5* m/ gas,s *#5* m/ gas,s $65* m/ gas,s */5# M8 e */4- 9mol total,hour */4- 9mol total,hour *15 Mmol %O+"#,hour 44-4 9mol %O#,hour '$51 tonne MeO",hour '$51 tonne MeO",hour '$51 tonne MeO",hour # 5/ M8 e *-5/ M8 e *-5/ M8 e

*5' *5' *5' *5' *5' *5' *5 4 *5 4 *

+@! +@! +@! +@! +@! +@!

*5' +@! *5' +@! *5'6 +@! *5' +@! *5' +@! *5$# +@! *5$# +@! #5/ +@! #5/ +@! * * #5* +@! #5* +@! #5* +@! *5' +@! *5' +@! *5' +@!

2&

:&

;& ,&

/&

5&

?&

6&

10&

Annual +8P de lation up to 166; is determined rom 0=C8 %166/& numbers) A3era!e annual +8P de lation a ter 166; is assumed to be 2), > or the I$, :)0 > or the =I) Cost numbers o 8utch ori!in are assumed to be dependent on the =I market, there ore =I +8P de lators are used) 1 K2001 B 0)6; I$J2001 B 2)20; 8 l2001) Total pre(treatment appro1imately sums up to a base cost o ?)1, <I$J 2001 at a base scale o ::), tonne #et9hour #ith an 2 actor o 0)56) -ased on irst !eneration -*+9CC installations) Faaij et al) %166,& e3aluated a 26 <7 e -*+9CC installation %input 6):0 k! dry #ood9s, produces 10),, Nm : uel !as9s& usin! 3endor 4uotes) 7hen a ran!e is !i3en, the hi!her 3alues are used %Faaij et al) 166?&) The scale actors stem rom Faaij et al) %166?&) T#o double scre# eeders #ith rotary 3al3es %Faaij et al) 166,&) 12)52 <I$J1661 %already includes added in3estment to hard#are& or a 1/,0 dry tonne per day input -C. !asi ier, eedin! not included, 2 is 0)5 %7illiams et al) 166,&) $tron!er e ects o scale or atmospheric !asi iers %0)/& #ere su!!ested by Faaij et al) %166?&) Technical director <r) Paisley o -attelle Columbus, 4uoted by Tijmensen %2000& estimates the ma1imum capacity o a sin!le -C. !asi ier train at 2000 dry tonnes9day) 26)5; <I$J1661 %includes already added in3estment to hard#are& or a 1/,0 dry tonne9day input *+T !asi ier, 2 B 0)5 %7illiams et al) 166,&) <a1imum input is ;00 <7th HHA %Tijmensen 2000&) Air $eparation Init' Plant in3estment costs are !i3en by Aan 8ijk %3an 8ijk et al) 166,&' * B 0)10/6LC0)?,0? in <I$J166, installed, C B Capacity in tonne 0 29day) The relation is 3alid or 100 to 2000 tonne 0 29day) 7illiams et al) %166,& assume hi!her costs or small installations, but #ith a stron!er e ect o scale' * B 0)2/0LC 0)512 in <I$J1661 ob plus an o3erall installation actor o 1)5, %2, and ;0>&) .arson et al) %166?& assume lo#er costs than Aan 8ijk, but #ith an e3en stron!er scalin! actor than 7illiams' 25 <I$J 1665 installed or an 1100 tonne 02 per day plant and 2B0)/) 7e ha3e applied the irst ormula %by Aan 8ijk& here) The production o 66),> pure 02 usin! an air separation unit re4uires 2,0 M :,0 k7h per tonne 0 2 %3an 8ijk et al) 166,D 3an 2ee 1662&) Hi!h temperature heat e1chan!ers ollo#in! the !asi ier and %in some concepts& at other locations are modelled as H2$+Ns, raisin! steam o 60 bar9,20 EC) A :6)2 k! steam9s unit costs /):: <I$J 1665 ob, o3erall installation actor is 1)?; %.arson et al) 166?&) Tijmensen %2000& assumes the ob price or Hot +as Cleanin! e4uipment to be :0 <I$J 2000 or a ;00 <7th HHA input) This e4uals 5;)1 m:9s rom a -C. !asi ier %TB?/:EC, 1)2 bar&) There is no e ect o scalin!) @ato sky %166:& assumes compressors to cost 500 I$J 166: per re4uired k7mech, #ith an installation actor o 2)1) The relation used here stems rom the compressor manu acturer $ulOer 4uoted by %2000&) At the indicated base(scale, total installed costs are about 1, > hi!her than assumed by @ato sky) <ultiple compressors, or synthesis !as, recycle streams, or hydro!en, are considered as separate units) 03erall installation actor is taken 1)52 because the base unit matches a ;00 <7 th plant rather than a 50 <7th plant)

2&

11&

12&

1:&

1;&

1,&

1/&

15&

1?&

16& 20&

21& 22&

2:&

*n3estments or steam re ormer 3ary rom 1/)6 <I$J 166:, or a throu!hput o ,?00 kmol methane9hour #ith an o3erall installation actor o 2)1 %@ato sky 166:& to 5?/5 kJ166, or a /)2 k! methane9s %1:60 kmol9hour&, o3erall installation actor is 2): %3an 8ijk et al) 166,&) These 3alues su!!est a stron! e ect o scalin! 2B0),1, #hile @ato sky uses a modest 2B0)5) Here, #e use the 3alues o Aan 8ijk in combination #ith an 2 actor o 0)/) The total amount o moles determines the 3olume and thus the price o the reactor) Autothermal 2e ormin! could be ,0 > cheaper than steam re ormin! %@ato sky 166:&, althou!h hi!her costs are ound as #ell %0onk et al) 1665&) *n3estment or shi t reactors 3ary rom 6)02 <IJ166, or an ??16 kmol C0CH29hr reactor, and an o3erall installation actor is 1)?1 %7illiams et al) 166,& to :0 <I$J166; installed or a :,0000 Nm:9hr C0CH29hr %1,/2, kmol9hr& reactor %Hendriks 166;&) 7illiams assumes an 2B0)/,, but comparison o the 3alues su!!est only a #eak in luence o scale %2B0)6;&) Here, #e use the the 3alues rom Hendriks , #ith 2 is set 0)?,) A dual shi t is costed as a shi t o t#ice the capacity) Costs or C02 remo3al throu!h $ele1ol amounts 1;): <I$J 166: ob %o3erall installation actor is 1)?5& or an ?10 kmol C029hr unit, 2 B 0)5 %@ato sky 166:& up to ;; <I$J166; installed or a 6606 kmol C029hour unit %Hendriks 166;&) The 3alue rom Hendriks is assumed to be ri!ht, since his research into C0 2 remo3al is comprehensi3e) Aan 8ijk et al) %166,& estimate that a <ethanol 2eactor or a 2)1 ktonne methanol per day plant costs ;;:: kI$J166, % ob& or 6,2/ kI$J166, installed %o3erall installation actor is 2)1&) The total plant in3estment in their study is 1:? <I$J166,, or 1,0 <I$J2001) @ato sky %166:& estimates the costs or a 10,/ tonne methanol9day plant to be ,0 <I$J 166, ob, this e1cludes the !eneration and alterin! o synthesis !as, but includes make(up and recycle compression and re inin! to#er) A 1000 tpd plant costs about 1/0 <I$J 2001, and a 2000 tpd plant 200 <I$J2001, #hich su!!ests a total plant scale actor o 0): %Hamelinck et al) 2001&) These 3alues come near the ones mentioned by @ato sky) This implies that the 3alues !i3en by Aan 8ijk are too optimistic and should be altered by a actor 1)::) *t is there ore assumed that the base in3estment or the methanol reactor only is 5 <I$J2001, the installation actor is 2)1) The in luence o scale on reactor price is assumed to be not as stron! as or the complete plant' 0)/) *nstalled costs or a ;,/ tonne per day .i4uid Phase <ethanol unit, are 26 <IJ1665, e1cludin! !eneration and alterin! o synthesis !as, but includin! make(up and recycle compression, and re inin! to#er) 2 B 0)52 %Tijm et al) 1665&) Corrected or scale and in lation this 3alue is about hal the cost o the con3entional unit by @ato sky and the corrected costs o Aan 8ijk) *t is there ore assumed that the price o a .i4uid Phase <ethanol reactor is :), <I$J2001 or a 2)1 ktonne per day plant, installation actor is 2)1) Cost number or methanol separation and re inin! is taken rom Aan 8ijk, increased #ith :: > as described in note 1,) For indication' A complete Combined Cycle amounts about ?:0 I$J 1665 per installed k7e) Fuoted rom %$olantausta et al) 166/& by %0onk et al) 1665&) $caled on +as Turbine siOe) $team system consists o #ater and steam system, steam turbine, condenser and coolin!) $caled on $team Turbine siOe) =1pansion turbine costs are assumed to be the same as steam turbine costs %#ithout steam system&) 03erall installation actor) *ncludes au1iliary e4uipment and installation labour, en!ineerin! and contin!encies) Inless other 3alues are !i3en by literature, the o3erall installation actor is set 1)?/ or a 50 <7 th scale %Faaij et al) 166?&) This 3alue is based on ::> added in3estment to hard#are costs %instrumentation and control ,>, buildin!s 1),> !rid connections ,>, site preparation 0),>, ci3il #orks 10>, electronics 5>, and pipin! ;>& and ;0 > added installation costs to in3estment %en!ineerin! ,>, buildin! interest 10>, project contin!ency 10>, ees9o3erheads9pro its 10>, start(up costs ,>&) For lar!er scales, the added in3estments to hard#are decreases sli!htly) <a1imum siOes rom Tijmensen %2000&)

2.2

;esults

'es lts o! the economic analysis are "i#en in ,i" re A. 0he +55 M?th con#ersion !acilities deli#er methanol at *.& 6 12 F/W2D;. Considerin" the 35 B ncertainty ran"e one sho ld be care! l in rankin" the concepts. Methanol + and & per!orm somewhat better than the other concepts d e to an ad#anta"eo s combination o! lower in#estment costs and hi"her e!!iciency. 0he lowest methanol prod ction price is !o nd !or concepts sin" the (C= "asi!ier, ha#in" lower in#estment costs. 0he combination o! an e)pensi#e o)y"en !ired ID0 "asi!ier with a combined cycle seems "enerally n!a#o rable, since the e!!iciency "ain is small compared to the hi"h in#estment. In#estment redemption acco nts !or +2 @ A& B o! the ann al costs and is in!l enced by the nit in#estment costs, the interest rate and the plant scale. 0he b ild6 p o! the total in#estment !or all concepts is depicted in ,i" re *. It can be seen that the costs !or the "asi!ication system (incl din" o)y"en prod ction), synthesis "as processin" and power "eneration "enerally make p the lar"er part o! the in#estment. ,or a tothermal re!ormin" hi"her in#estment costs (Oonk et al. 1..A), wo ld increase the methanol price !rom considered concepts by abo t 1.8 F/W2D;. -e#elopments in "asi!ication and re!ormin" technolo"y are important to decrease the in#estments. On the lon"er term capital costs may red ce d e to technolo"ical learnin"4 a combination o! lower speci!ic component costs and o#erall learnin". $ third plant b ild may be 18 B cheaper leadin" to an * @ 18 B prod ct cost red ction. 2A

#1

#-

)%el price &,S-.G/)

*1

*-

%once)t *
Fi!ure 5)

<ethano l price or ;00 <7 th in put concepts, #it h :0 > un cert ain t y on in 3estment and 0P< %because 0P< is linear unction o in3estment&)

0he interest rate has a lar"e in!l ence on the methanol prod ction costs. $t a rate o! 8 B methanol prod ction costs decrease with abo t 25 B to A.2 @ ..5 F/W2D;. $t a hi"h interest rate (18 B) methanol prod ction costs become ... @ 1+ F/W2D;, Doin" to 1555 and 2555 M? th scales the methanol prod ction costs reach cost le#els as low as A.1 @ ..8 F/W2D;. ,eedstock costs acco nt !or 3& @ &2 B o! the !inal prod ct costs !or the mentioned technolo"ies. I! a biomass price o! 1.A F/W2D; co ld be realised (a realistic price !or e.". (ra1il), methanol prod ction costs wo ld become *.5 @ 11 F/W2D; !or +55 M?th concepts. On the other hand, when biomass costs increase to 3 F/W2D; (short term ?estern : rope) the prod ction cost o! methanol will increase to 15 @ 1& F/W2D;. I! the electricity can be sold as "reen power, incl din" a carbon neutral premi m, the ! el prod ction costs !or power co6prod cin" concepts drops, where the "reen premi m essentially pays a lar"e part o! the ! el prod ction costs. $ power price o! 5.5* F/W2D; wo ld decrease methanol costs to 65.& @ ..8 F/W2D;. O! co rse the decrease is the stron"est !or concepts prod cin" more electricity. $ "reen electricity scenario, howe#er, may be a typical western : ropean scenario. $s s ch it is nlikely that it can be realised conc rrent with biomass a#ailable at 1.A F/W2D;. On the lon" term di!!erent cost red ctions are possible conc rrently (0iEmensen 2555). (iomass co ld be widely a#ailable at 1.A F/W2D;, capital costs !or a third plant b ilt are 18 B lower, and the lar"e (2555 M? th) plants pro!it !rom economies o! scale. 0hese red ctions are depicted in ,i" re .4 methanol concepts prod ce a"ainst &.1 @ A.+ F/W2D;. 0he in!l ence o! capital redemption on the ann al costs has stron"ly red ced and the ! el costs o! the di!!erent concepts lie closer to"ether. %re#io s analyses on short term methanol prod ction, by >ato!sky (>ato!sky 1..3) and ?illiams et al. (3A2 M?HHK, 3.+ F/W2D;HHK !eedstock, 5.5A F/W2k?he (?illiams 1..8C ?illiams et al. 1..8)) yielded similar ener"y e!!iciencies (8+ @ &1 B by HHK), b t si"ni!icantly hi"her methanol prod ction costs4 1+ @ 1A F/W2D; HHK. 0he lar"est di!!erence is in the hi"her capital costs4 hi"her 0CI and hi"her ann ity "i#e 28 @ 85 B hi"her ann al capital costs. 0he 2*

/-Po7er Generation

#1Methanol Production

0n1estment &M,S-)

#-Syngas Processing

*1Gas %leaning

*-Gasification system

1Total Pre-treatment

%once)t *
Fi!ure ?) -reakdo#n o

/
in3estment costs

or ;00 <7 th concepts)

$-=2D$K: st dy ($rth r -. =ittle 1...) reports 13 F/W2D; methanol (!eed 2 F/W2D;, +33 M? inp t) lar"ely sin" inp t parameters !rom >ato!sky. >omiyama et al (2551) instead "i#e m ch lower costs than presented here4 8 F/W2D;HHK !or methanol at 835 M? HHK biomass inp t. Howe#er, in that st dy, process e!!iciencies and biomass cost are not "i#en, and a si"ni!icant amo nt o! ener"y is added as =%D. In these lon"6term scenarios, methanol prod ced !rom biomass costs considerably less than methanol at the c rrent market, which is priced abo t 15 F/W2D; (Methane) 2551). ,or application as a tomoti#e ! el, comparison with "asoline and diesel is rele#ant. 0heir prod ction costs #ary stron"ly dependin" on cr de oil prices, b t !or an indication4 2553 "asoline market prices were abo t A F/W2D; at oil prices o! 28 @ 35 F/W2bbl ((% 255+). -O:2:I$ proEects the world oil price in 2513 to amo nt between 1A and 3+ F/W, cr de oil prices may decline as new deepwater oil !ields are bro "ht into prod ction in the D l! o! Me)ico and ?est $!rica, new oil sands prod ction is initiated in Canada, and O%:C and ' ssia e)pand prod ction capacity (-O:2:I$ 2558). In 255+ the a#era"e oil price was some 38 F/W2bbl, and c rrently e#en hi"her prices o! abo t 85 F/W2bbl are paid.

2.

#1 Base case Bltimate case #)%el price &,S-.G/)

*1
*

*-

# /

Fi!ure 6)

%once)t *

0ptimistic 3ie# scenario ) 8i eren t cost redu ct io ns are o reseeable' %1& bio mass costs 1)5 I $J9+" instead o 2 I $J9+", %2& tech no lo !ical learn in ! reduces capital i n 3 e s t m e n t b y 1 , > a n d % : & a p p l i c a t i o n o l a r ! e s c a l e % 2 0 0 0 < 7 t h & r e d u c e s u n it in3estment costs)

35

5 C o nc l u s i o n s

Methanol can be prod ced !rom wood #ia "asi!ication. 0echnically, all necessary reactors e)ist and the !easibility o! the process has been pro#en in practice. Many con!i" rations are possible, o! which se#eral ha#e been disc ssed in this chapter. 0he con!i" rations incorporated impro#ed or new technolo"ies !or "as processin" and synthesis and were selected on potential low cost or hi"h ener"y e!!iciency. /ome con!i" rations e)plicitly co6prod ced power to e)ploit the hi"h e!!iciencies o! once6thro "h con#ersion. 0he o#erall HHK ener"y e!!iciencies remain aro nd 88 B. $cco ntin" !or the lower ener"y 3 ality o! ! el compared to electricity, once6thro "h concepts per!orm better than the concepts aimin" at ! el only prod ction. $lso hot "as cleanin" "enerally shows a better per!ormance. /ome o! the technolo"ies considered in this chapter are not yet ! lly pro#en2commercially a#ailable. /e#eral nits may be realised with hi"her e!!iciencies than considered here. :.". new catalysts and carrier li3 ids co ld impro#e li3 id phase methanol sin"le pass e!!iciency. $t lar"er scales, con#ersion and power systems (especially the combined cycle) may ha#e hi"her e!!iciencies, b t this has not been researched in depth. 0he methanol prod ction costs are calc lated by di#idin" the total ann al costs o! a system by the prod ced amo nt o! methanol. Fnit si1es, res ltin" !rom the plant modellin", are sed to calc late the total installed capital o! methanol plantsC lar"er nits bene!it !rom cost ad#anta"es. $ss min" biomass is a#ailable at 2 F/W2D;, a +55 M? th inp t system can prod ce methanol at . @ 12 F/W2D;, sli"htly abo#e the c rrent prod ction !rom nat ral "as prices. 0he o tcomes !or the #ario s system types are rather comparable, altho "h concepts !oc ssin" on optimised ! el prod ction with little or no electricity co6prod ction per!orm somewhat better. 0he methanol prod ction cost consists !or abo t 85 B o! capital redemption, o! which the b lk is in the "asi!ication and o)y"en system, synthesis "as processin" and power "eneration nits. , rther work sho ld "i#e more insi"ht in in#estment costs !or these nits and their dependence to scale. 0he ma)im m possible scale o! partic larly the press rised "asi!ier "i#es rise to disc ssion. 0he operation and maintenance costs are taken as a percenta"e o! the total in#estment, b t may depend on plant comple)ity as well. =on" term (2525) cost red ctions mainly reside in sli"htly lower biomass costs, technolo"ical learnin", and application o! lar"e scales (2555 M? th). 0his co ld brin" the methanol prod ction costs to abo t A F/W2D;, which is in the ran"e o! "asoline2diesel. Methanol !rom biomass co ld become a maEor alternati#e !or the transport sector in a world constrained by "reenho se "as emission limits and hi"h oil prices.

31

! <iterature

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O:C- 9ational accounts ! Main aggregates$ 2dition -33/4 %aris, 1..&, 1A5 pp. Oonk, H.C Kis, ;.C ?orrell, :.C ,aaiE, $.C (ode, ;.6?. 7he MethaHydro!proces ! preliminary design and cost e+aluationC 09O4 0he Ha" e, 1..A. O%%$ 'ssesment o0 costs and bene0its 0o 0lexible and alternati+e 0uel use in the ?S transportaion sector$ 7echnical Report :" Costs o0 methanol production 0rom biomass C F/ -O:4 ?ashin"ton -C, F/$, 1..5. %aisley, M.$.C ,arris, M.C.C (lack, ;.C Ir#in", ;.M.C O#erend, '.%. Commercial demonstration o! the (attelle2,:'CO (iomass "asi!ication process4 start p and initial operatin" e)perience. In Fourth Biomass Con0erence o0 the 'mericasC O#erend, '.%.C Chornet, :. (:ds.)C :lse#ier /cience, O)!ord, F>4 Oakland, F/$, 1..*C pp 15&1615&&. %eckham, ;. = r"i4 cheaper "tl diesel ro te thro "h methanol, www.world! els.com. Das6to6=i3 ids news 2003, @(11). %erry, '.H.C Dreen, -.?.C Maloney, ;.O. #erry>s chemical engineers> handboo($ sixth edition C McDraw6Hill (ook Co4 /in"apore, 1.*A. %eters, M./.C 0immerha s, >.-. #lant design and economics 0or chemical engineers$ 7hird edition C McDraw6Hill (ook Company4 9ew Sork 9S F/$, 1.*5, .A3 pp. %ierik, ;.0.D.C C r#ers, $.%.?.M. Logistics and pretreatment o0 biomass 0uels 0or gasi0ication and combustionC :ner"y research Center o! the 9etherlands :C94 %etten the 9etherlands, 1..8. %ieterman, M. 7he historical de+elopment o0 inno+ati+e and energy!e00icient synthesis gas production technologies )MSc thesis,C Ftrecht Fni#ersity2-epartment o! /cience, 0echnolo"y and /ociety4 Ftrecht the 9etherlands, 2551. 'iesen!eld, ,.C.C >ohl, $.=. Gas #uri0icationC D l! % blishin" Company4 Ho ston, 1.A+, A&1 pp. 'odri" es de /o 1a, M.C ?alter, $.C ,aaiE, $. $n analysis o! scale e!!ects on co6!ired (ID6CC system (biomass L nat ral "as) in the state o! /Zo %a lo2(ra1il. In -st <orld con0erence on biomass 0or 2nergy and 8ndustryC >yritsis, /.C (eenackers, $.$.C.M.C Helm, %.C Drassi, $.C Chiaramonti, -. (:ds.)C ;ames P ;ames, =ondon4 /e#illa, 2555C pp *136*1&. /olanta sta, S.C (rid"ewater, 0.C (eckman, -. 2lectricity production by ad+anced biomass po;er systems C 0echnical 'esearch Centre o! ,inland (K00)4 :spoo ,inland, 1..&. / da, 0.C , Eii, M.C Soshida, >.C IiEima, M.C /eto, 0.C Mits oka, /. -e#elopment o! !l e "as carbon dio)ide reco#ery technolo"y. In First 8nternational Con0erence on Carbon *ioxide Remo+al C (lok, >.C 0 rkenb r", ?.C.C Hendriks, C.$.C /teinber", M. (:ds.)C %er"amon %ress4 $msterdam the 9etherlands, 1..2 0iEm, %.;.$.C (rown, ?.'.C Heydorn, :.C.C Moore, '.(. 'd+ances in LiAuid #hase 7echnology ! #resentation at 'merican Chemical Society Meeting$ 'pril -&!-/ 4 /an ,rancisco C$ F/$, 1..A. 0iEmensen, M.;.$. 7he production o0 Fischer 7ropsch liAuids and po;er through biomass gasi0ication )MSc thesis,C Ftrecht Fni#ersity2-epartment o! /cience, 0echnolo"y and /ociety4 Ftrecht the 9etherlands, 2555. 0 rn, /.Q.C >inoshita, C.M.C Ishim ra, -.M.C Jho , ;.C Hiraki, 0.0.C Mas tani, /.M. $ re#iew o! sorbent materials !or !i)ed bed alkali "etter systems in biomass "as!ier combined cycle power "eneration applications. ;o rnal o! the Instit te o! :ner"y 1998, /-, 1&361AA. F/-O: Commercial!scale demonstration o0 the liAuid phase methanol )L#M2OH 7M, process ! Clean Coal 7echnology 7opical Report C-- C F/ -epartment o! :ner"y, 1....
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