ContentslistsavailableatScienceDirect
Chemical
Engineering
Research
and
Design
j o u r n a l ho me p a g e : w w w . e l s e v i e r . c o m / l o c a t e / c h e r d
Process
development
for
biomass
delignification
using
deep
eutectic
solvents.
Conceptual
design
supported
by
experiments
Dion
Smink,
Sascha
R.A.
Kersten,
Boelo
Schuur
∗UniversityofTwente,FacultyofScienceandTechnology,SustainableProcessTechnologyGroup,TheNetherlands
a
r
t
i
c
l
e
i
n
f
o
Articlehistory:Received10April2020
Receivedinrevisedform26August 2020
Accepted12September2020 Availableonline19September2020
Keywords: Delignification Deepeutecticsolvent Conceptualprocessdesign Liquid–liquidextraction
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Deepeutecticsolvents(DES)havebeenproposedassolventsforbiomassdelignification.This paperdescribesaconceptualprocessdesignforthedelignificationofEucalyptusglobulus usingaDEScomprisedof30wt%cholinechlorideand70wt%lacticacid.Inthisdesign, theligninandhemicelluloseby-productsarerecoveredbyliquid–liquidextractionusing 2-MTHFassolvent.Materialandenergybalancesweremadeandtheenergyusageofthe processwasoptimizedwithadditionalexperiments.TheamountofDESwasreducedto theminimalamountrequiredtofilltheporousbiomass(5kgperkgwood),whichonly reducedthedelignificationfrom94%to87%andincreasedtheyieldfrom57to59%.Direct recyclingoflignin-in-DESmixtureswithoutligninremovalbyliquid–liquidextractiontothe delignificationstagemaysaveenergy,butincreasedrepolymerizationincreasesthelignin’s molarweight,whichdecreasesitsvalueandmakesrecoverybyliquid–liquidextractionmore difficult.Afteroptimization,thetotalheatdutyoftheproposedprocessis7.9GJ/tpulp,which is28%lowerthanthekraftprocess.ThemainbenefitofDESbaseddelignificationprocesses isthepossiblevalorizationofbyproducts,suchasligninandfuransfromhemicellulose.
©2020TheAuthor(s).PublishedbyElsevierB.V.onbehalfofInstitutionofChemical Engineers.ThisisanopenaccessarticleundertheCCBY-NC-NDlicense(http:// creativecommons.org/licenses/by-nc-nd/4.0/).
1. Introduction
Deepeutecticsolvents(DES,plural:DESs)arecompositesolventsthat exhibitdeepeutecticbehavioruponmixingtheconstituents.Various authorsproposedadefinitionforaDES(Zhangetal.,2012;Paivaetal., 2014;Smithetal.,2014;Martinsetal.,2019;Schuuretal.,2019)but nofinaldefinitionorconsensushasbeenachievedyet.Regardlessof whataformaldefinitionofDESsshouldbe,thesecompositesolvents thatexhibittheirlowtransitiontemperatures(Franciscoetal.,2013b) duetohydrogenbonding,attractedwideattentioninacademia.Since thesesolventscaneasilybepreparedinnumerouswaysby combin-ingahydrogenbonddonorandacceptor(Gomezetal.,2018)andare oftenbiocompatible,biodegradable(Luetal.,2012)andcanhavealow toxicity(Macárioetal.,2018),DESshavebeenusedforvarious appli-cations.ExamplesincludeCO2capture(López-Salasetal.,2014;García
etal.,2015;Mirzaetal.,2015),airpollutantremoval(Mouraetal.,2017),
∗ Correspondingauthor.
E-mailaddress:b.schuur@utwente.nl(B.Schuur).
extractivedistillation(Panetal.,2019),metalextractions(Söldneretal., 2019),desulfurization(Limaetal.,2018,2019)andbiomass fractiona-tion(Jablonsk ´yetal.,2019;Miˇsanetal.,2019;Sminketal.,2019).
Lignocellulosicbiomassisarenewablerawmaterialsourceandcan beconvertedintocellulosefibersand,amongotherbyproducts,lignin bydelignificationtechnologies.Theobtainedcellulosepulpcanbeused forpaperproduction,productionofothermaterials,orcanbeconverted tobio-ethanolorotherplatformchemicals(Naiketal.,2010;Rosatella etal.,2011;Dusselieretal.,2013).Ligninisanaromaticbiopolymerwith advocatedpotentialforthechemicalindustryandcurrentresearchis focusingonligninvalorization(Rinaldietal.,2016;Westwoodetal., 2016).Otherbyproducts,suchashemicelluloseandextractablescan beconvertedintofuransandturpentinerespectively(Houetal.,2018b; Lietal.,2018).
Mostconventionalcellulosefiberproducinginstallationsmakeuse ofthekraftprocess,inwhichlignocelluloseisdelignifiedusingsodium hydroxideandsodiumsulfidetoformcellulosefiberssuitablefor paper-making.Theligninisdepolymerizedbyanucleophilicsubstitution reactionwiththesulfide,meaningtheligninthatisfinallyobtained ishighlysulfurized.Asaconsequence,tobeabletorecyclethesodium sulfide,theligninhastobecombusted.Kraftmillsmayalsoproduce https://doi.org/10.1016/j.cherd.2020.09.018
0263-8762/©2020TheAuthor(s).PublishedbyElsevierB.V.onbehalfofInstitutionofChemicalEngineers.Thisisanopenaccessarticle undertheCCBY-NC-NDlicense(http://creativecommons.org/licenses/by-nc-nd/4.0/).
ligninasbyproduct,butthescaleandapplicationsarelimited.Kraft ligninismainlyusedforlow-valueapplications,suchasheat recov-ery(Chen,2015).Alsootherprocesses,suchasorganosolv,canbeused forcelluloseproduction,buttheseprocessesrequirehighamountsof organicsolvents,whichareoftenvolatileandflammable(VanOsch etal.,2017).Othersolvents,suchasionicliquids(Sunetal.,2009)may alsobeconsideredforbiomassdelignification,buttheirhighercosts maylimitindustrialapplicability.
Althoughkraftplantsarehighlyintegratedandenergyeffective plants(RudieandHart,2014),theystillhaveanaverageheatusage around11GJ/t(Suhretal.,2015).Thisheatisprovidedfromthe com-bustionoftheextractedligninandotherpartsofthetreethatare unsuitableofpapermaking,suchasthebark.Mostmodernkraftmills haveanenergysurplus,whichismostoftenusedtoprovidepowerto thegrid.
DESshavebeenreportedforthedelignificationofvarioustypesof lignocellulose.AnoverviewofthesestudiesisshowninTable1.Lignin thatisproducedusingDESsoftenshowsverylittlesignsof condensa-tion(Alvarez-Vascoetal.,2016)andtypicallyhasalowmolarweight (Alvarez-Vascoetal.,2016;Lyuetal.,2018).Manystudieshavebeen per-formedonbiomassdelignificationusingDESandmanyDES,biomass typesandprocessingconditionshavebeenstudied.However,tothe bestofourknowledge,noanalysisoftheoverallprocessenergy effec-tivenesshasbeenmade,andtheconceptualdesignasmadeinthis study,hasnotbeenmadeforbiomassdelignificationusingDESyet.
EspeciallyDESscomprisedoflacticacidandcholinechloridewere veryoften used forbiomass delignification(Jablonsk ´y etal., 2015; Alvarez-Vascoetal.,2016;Changetal.,2016;Kumaretal.,2016;Zhang etal.,2016;Lietal.,2017,2019a,2019b;Houetal.,2018a;Lyuetal.,2018; Mamillaetal.,2019;Muleyetal.,2019;Shenetal.,2019;Sminketal., 2019;Tianetal.,2019).Althoughtheoptimallacticacidtocholine chlo-rideratiosfordelignificationarebetween10:1and50:1,(Sminketal.,
2019)aDEScomprisedof30wt%cholinechlorideand70wt%lactic acidwasusedinthisstudysinceitispossibletoregenerateligninfrom thisDESbyliquid–liquidextraction,whichhaspotentialfor signifi-cantenergysavings(Sminketal.,2020a).Thisequalsa1:3.6Mratioof cholinechloridetolacticacid.
Althoughthetechnicalconceptofbiomassdelignificationusing DESsiswellproven,thelackofaprocessevaluationbasedona con-ceptualdesignhindersmakingestimationsontheeconomicfeasibility oftheconcept.Eventhoughmanydetailsarestillunknown,makinga conceptualdesignwithallthenecessaryestimationsisafirststepthat wepresentheretoidentifywhethertheconceptofDES-based pulp-inghaspotentialtobecomeindustriallyviableornot.Basedonthis study,thereadershallbeabletovaluethepotentialofthe technol-ogy,andinadditionbeabletoindicatewhichadditionaldataisstill requiredtomakeafullydetailedprocessdesign.Inthiswork,a con-ceptualdesignwasmadeaccordingtothemethoddescribedbyDouglas (Douglas,1988),whichiseasytouseandrelevantforindustrial applica-tions(Harmsen,2004).Usingthisapproach,acomplexprocessdesignis dividedintomultiple,muchsimplerproblems.FollowingtheDouglas method,theinput–outputstructureoftheprocesswasdefinedfirst, afterwhichtheseparationsweredefined.Later,themassandenergy balancesweremadeusingrigorouscalculations.Therefore,itis rela-tivelyeasytoscreenalternativesandtherebyoptimizethedesign.In thiswork,theprocesswasoptimizedforenergyusage.Energyusage isaveryimportantparameter,notjustfromanenvironmentalpoint ofviewandfortheoperationalcostsoftheprocess,butenergylosses typicallydictatetheinvestmentcostsforaprocessaswell(Lange,2001).
2.
Methods
and
materials
2.1. Materials
Air-dryE.globuluschipsweredonatedbyTheNavigator Com-pany from their mill in Portugal and free from impurities, suchasstones,soilormetal.Thecommerciallysizedchips (typically25–35×10–25×2.5–6mm,L×W×T)weremilledto producewoodmealusingahammermillandsieved(mesh −25/+70) and contained 5.6wt% moisture, as determined accordingtotheNRELmethod(Sluiteretal.,2008a).Thewood contained21.6%lignin,50.6%glucose,14.0%xylose,and1.1% galactose(ovendrybasis),asdeterminedbyacidhydrolysis usingthestandardNRELmethod(Sluiteretal.,2012).Lactic acid(>85%),cholinechloride(>98%)andsulfuricacid(95–98%) werepurchasedfromSigma-Aldrich.2-MTHF(Emplura)was purchasedfromVWR.
2.2. Experimentalprocedures
2.2.1. Biomassdelignificationexperiments
1to2geucalyptusmeal(ovendrybasis)wasaddedtogether with10gDEStoaTeflon-linedautoclave.Thisautoclavewas insertedintoadirectcontactheater,whichheatedthe auto-claveto130◦Cinacoupleofminutes.After1h,theautoclave wastakenoutoftheheaterandgentlycooleddowntoroom temperature. Thecontents werewashedusing ethanoland filteredoveraWhatmanglassfiberfilterbeforedryingofthe residuetoaconstantweightat105◦Cinaconvectionoven. Allexperimentswereperformedinduplo.Theyieldwas cal-culatedaccordingtoEq.(1).
yield (%)= Drysolidresidue (g)
Eucalyptusmealaddedtoautoclave (g)∗
1−Moisturecontentineucalpytusgg∗100 (1) Theacidinsolublelignininthesolid residuewas deter-mined by acid hydrolysis according to the NREL method (Sluiteretal.,2012).Thedegreeofdelignificationwas calcu-latedaccordingtoEq.(2)Delignification (%)=100−Yield (%)∗LigninLigninininresidue (%)wood (%) (2) Theerrorinthedelignificationwasdeterminedfromone experimentthatwasrepeated 5times.The95%confidence intervalwasdeterminedusingthet-teststatisticmethod.For duploexperiments,theerrorindelignificationwas1.2%.
2.2.2. Ligninextractionexperiments
3mLlignininDESmixture(seesection2.2.3.forthe prepara-tionprocedure),3mL2-MTHFand0.5–3mLwaterwereadded toaglassvialwithascrewcap.Thevialswereplacedina JulaboSW22shakingbathat50◦Candshakenovernightat 200rpm. The phases were settled under gentle shaking at 20rpmuntiltheywerefullyseparated.Thelignincontentsin bothphasesanalyzedbyGPC.
2.2.3. PreparationoflignininDESmixture
700glacticacidand 300gcholinechloridewereaddedtoa round bottomed flask(2L) with a condenser. The mixture washeatedto130◦Cand200g(ovendrybasis)commercially sizedchipswereaddedtotheflask.Themixturewasstirred gentlyfor3or8handthemixtureswerefilteredwhilehot overa53msteelmesh.Thelignincontentinthemixtures
Table1–OverviewofpreviousworksonbiomassdelignificationusingDES,sortedbybiomasstype.
Woodtype Author Year DES Delignification(%)and/or
remarks
Softwoods
Spruce Wahlströmetal.(2016) ChCl+boricacidand glycerol,betaine+glycerol
Thepretreatmentefficiency ofDESforenzymatic hydrolysisislimited. Schäferetal.(2018) ChCl+3-phenylpropionic
acid
21%,Particlesizehasalarge influenceondelignification Pine
Alvarez-Vascoetal.(2016) ChCl+aceticacid,lactic acid,levulinicacidand glycerol.
58%,delignificationusing ChCl+glycerolineffective. Lietal.(2019a,2019b) ChCl+lacticacid 67%,treatmentusing
microwavereduced delignification Muleyetal.(2019) ChCl+lacticacidandoxalic
acid
90%,microwaveheating reducedprocessingtime
Hardwoods
Beech Jablonsk ´yetal.(2019) Lacticglycineacidand+betaine,alanine, ChCl+ethyleneglycoland glycolicacid
15%,ChClandglycolicacid mosteffective
Mamillaetal.(2019) ChCl+lacticacid,oxalic acid,KOHandurea
OxalicacidandKOHcould dissolvemorewood polymers
Poplar
Alvarez-Vascoetal.(2016) ChCl+aceticacid,lactic acid,levulinicacidand glycerol.
78%,delignificationusing ChCl+glycerolineffective. Tianetal.(2017) Lacticacid+betaine 69%,DEShadahigher
selectivityandrequireda lowertemperaturethan soda/AQororganosolv pulping
Tianetal.(2019) ChCl+formicacid,acetic acidandlacticacid
77%,Producedpulpswere comparabletokraftpulps Lietal.(2019a,2019b) Lacticacid+ChCland
glycine
90%withChClDES,but only58%withglycineDES
Eucalyptus
Changetal.(2016) ChCl+lacticacid 90%,1:9ratiooptimal. Achievedat90◦Cand12h Liangetal.(2019) ChClandethyleneglycol 90%,DESrecoveredusing
membranes
Shenetal.(2019) ChCl+lacticacid 93%,obtainedligninhad lowweightandawell preservedstructure Sminketal.(2019) ChCl+lacticacid 92%,chlorideistheactive
ingredientincholine chloride
Willow Lietal.(2017) ChCl+lacticacid,glycerol andurea
92%,usingChCl+lacticacid at120◦Cand12h
Songetal.(2019) Lacticacid+betaine 53%,moreselectivethan hydrotropes,butrequired highertemperatures.
Agricultural byproductsand grasses
Miscanthus Guoetal.(2019a) ChCl+glycerol+acid catalyst
90%,Suitablepretreatment forenzymaticdigestion Wheat
straw
Jablonsk ´yetal.(2015) ChCl+Urea,malonicacid, lacticacid,malicacid,lactic acidandoxalicacid
58%byChCl+oxalicacid, butChCl+lacticacidhad thehighestselectivity Wahlströmetal.(2016) ChCl+boricacidand
glycerol,betaine+glycerol
Thepretreatmentefficiency ofDESforenzymatic hydrolysisislimited. Zhaoetal.(2018) ChCl+monoethanolamine 71%,suitablepretreatment
forenzymatichydrolysis Jablonsk ´yetal.(2019) Lacticacid+alanine,
glycineandbetaine, ChCl+ethyleneglycoland glycolicacid
24%,lacticacidandalanine wasmosteffective
Ricestraw
Kumaretal.(2016) ChCl+lacticacidand betaine
60%,additionofwater enhanceddelignification Houetal.(2018a) 6lacticacidand13ChCl
basedDESs
51%,withChCl+lacticacid Houetal.(2018b) ChCl+oxalicacid 70%,suitablepretreatment forenzymatichydrolysis
–Table1(Continued)
Woodtype Author Year DES Delignification(%)and/or
remarks
Limetal.(2019) K2CO3+glycerol AlkalineDESsuitablefor
ricestrawpulping Corncob
Procenteseetal.(2015) ChCl+glycerol,imidazole andurea
88%,DEStreatment enhancedenzymatic digestibility. Zhangetal.(2016) ChCl+7acidsand2
polyalcohols
98.5%,delignification enhanceswithacid strength
Guoetal.(2019b) Lacticacid
+Benzyltrimethylammonium
63%,suitablepretreatment forenzymaticdigestion Chlorideand
benzyltriethy-lammonium chloride
Cornstover Xuetal.(2018) 9ChClbasedDESs 60%,DESsuitablefor
biofuelproduction Songetal.(2019) Lacticacid+betaine 79%,moreselectivethan
hydrotropes,butrequired highertemperatures. wasdetermined byacid hydrolysis,forwhich20mLofthe
lignin-in-DESmixturewasaddedtoaTeflon-linedautoclave, togetherwith60mLwater.3mL72%Sulfuricacidwasadded tothemixtureusingapipetteandtheautoclavewasinserted intoadirectcontactheaterat120◦Candkeptthereforone hour.Themixturewascooleddowntoroomtemperatureand filteredoveraWhatmanglassfiberfilter.Theresiduewasdried inaconvectionovenat105◦Candtheacidinsolublelignin contentwasdeterminedgravimetrically.
2.3. Analysismethods
2.3.1. Acidhydrolysis
Theacidinsolublelignincontent ofthesamplewas deter-minedbyhydrolysisofthesampleaccordingtostandardized NRELprocedure(Sluiteretal.,2012).0.3gSamplewasadded toaTeflon-linedautoclave,togetherwith3mLsulfuricacid (72%)andthemixturewaskeptat30◦Cfor1hwhilestirring every10min.Afterthis,84mLwaterwasaddedandthetube waskeptat120◦Cforanotherhour.Thesolidswerefiltered anddriedovernightat105◦C.Theacidinsolublelignincontent wascalculatedaccordingtoEq.(3).
Acidinsolublelignin (%)
= Residue (g)
sample (g)∗
1−Watercontentgg∗100 (3)2.3.2. GPC
AnAgilent1200serieswasusedforthegelpermeation chro-matography(GPC)witharefractiveindexdetectorandaUV detectoroperatingat254nmusing3GPCPLgel3mMIXED-E columnsinseries.Thecolumnwasoperatedat40◦Canda95:5 (v:v)tetrahydrofuranandwatermixturewasthesolventata flowrateof1mL/min.Molecularweightdistributionswere cal-ibratedusingpolystyrenesolutionshavingmolecularweights rangingfrom162to27,810g/mol.
2.3.3. HPLC
Thelactic acidcontent inthehydrolysisliquidswas deter-minedbyhigh performanceliquidchromatography (HPLC).
AnAgilent1200systemwasequippedwithaHi-Plex-H col-umnoperatedat60◦Candarefractiveindexdetectorat55◦C. 5mMsulfuricacidinwaterwasusedasmobilephasewitha flowrateof0.6mL/min.
2.3.4. Karl–Fischertitration
ThewatercontentoflignininDESmixturewasdetermined by Karl–Fischer titration using a Metrohm 787KF Titrino. Hydranal composite 5 (5mg water/mL) was titrated from a 20mL burette in a 3:1 (v:v) mixture of methanol and dichloromethane.Thesamplewasmeasured induplowith arelativeerror<2%.
2.3.5. Determinationofashcontent
Theashcontentintheeucalyptuswasdeterminedaccording tothestandardNRELprocedure(Sluiteretal.,2008b).1.5–2g biomass was pre-driedin aconvection oven at105◦C and addedtoaporcelaincruciblewhichwaspre-driedat575◦C. Thiscruciblewasinsertedintoanovenat575◦Ctooxidizeall organicmaterial.Theanalysiswasperformedinduplo.The ashcontentwasdeterminedgravimetricallybyEq.(4).
Ashcontent (%)=Residueafteroxidation (g)
Drybiomass (g) ∗100 (4)
2.4. Calculationmethods
Allcalculationsinthisworkarerigorouscalculations,based on literature data, and sometimes based on experimental results reported in this paper. In order to make calcula-tions on the mass balances and energy balances of unit operations,informationisneededonphasebehavior.Where liquid–liquid equilibria of DES and 2-MTHF and lignin are involved,thisinformationistakenfromearlierpublications (Sminketal.,2020a,b).Theliquid–liquidequilibriumandvapor liquid equilibrium data for 2-MTHF and water was taken fromGlassetal.(2016)andStephenson(1992).Furthermore, it is assumed that the DES is completely non-volatile, as shownbyFranciscoetal.(2013a), andforthe enthalpiesof evaporationofwaterfromblackliquorsalsoliteraturedata wasused.For kraftblackliquor,theinformationwastaken fromFerreiraetal.(2011)(Hvap,BL=54.1kJ/mol),whileforthe
Table2–Assumptionsmadeforthemassbalanceoftheconceptualprocesswiththeirjustifications.
Symbol Description Value Unit Justification
DB DEStobiomassratio 10 kg/kg Commonratiousedinliterature
(Alvarez-Vascoetal.,2016) lB Ligninfractioninbiomass 0.216 kglignin/kgbiomass Measuredbyacidhydrolysis,see
(Sminketal.,2019) MP,out Totalcelluloseproduction 1000 kg/h Forconveniencea
SF Solventtofeedratio 0.5 kg/kg Estimatedfrom(Sminketal.,
2020a)
WFL Washingfactorlignin 2 kg/kgDES
WFP Washingfactorpulp 3 kg/kg Estimatedfromwaterwashing
datab
XDES,MTHF SolubilityofDESin2-MTHF 0.3 kg/kg Estimatedfrom(Sminketal.,
2020a)
xMTHF,DESrecycle Solubilityof2-MTHFinDES 0.1 kg/kg Estimatedfrom(Sminketal.,
2020a)
xW,B Waterfractioninbiomass 0.5 kg/kg (BownandLasserre,2015)
xW,DESrecycle WaterfractioninDESafter
liquid-liquidextraction
0.5 kg/kg Estimatedfrom(Sminketal., 2020b)
XW,P Waterfractioninpulp 0.67 kg/kg Typicallyachievablebypressing
(Eketal.,2009b) yL Ligninremovalfrombiomass 0.94 kgligninin
biomass/kglignin removed
Measuredinthiswork
yp Solidyieldafterdelignification 0.57 kg/kgbiomass Measuredinthiswork a Normalizedto1t/hforconvenience.Allnumberscanbescaledlinearlytoanydesiredproductioncapacity.
b Onlydataaboutwaterwashingsareavailable,whichstatethat2.5m3water(Eketal.,2009b)pertofpulpisrequired.Basedonthedensityof
DES,beinghigherthanwater,3kgDESperkgpulpwasassumedtobetheminimumforDESwashingofpulp.
DESblackliquor,Hvap,DESwascalculatedusingtheClausius
ClapeyrontheorywithVLEdataobtainedbyFranciscoetal. (2013a),Hvap,DES=44.3kJ/mol. Othernecessaryinformation
wasmeasuredinthecasethatnoreasonableestimatecould begiven.Allrelevantequilibriumvaluesforthemassbalance arereportedinTable2(videinfra).
3.
Results
and
discussion
3.1. Conceptualprocessdesignandinitialenergy requirementestimation
3.1.1. Input–outputstructure
First, the typeoflignocellulosic biomassmust beselected. Inprinciple,everytypeoflignocellulosicbiomass(hardwood, softwood,grasses,agriculturalwastes)canbeselectedforthe process.WeselectedE.globulusforfurtherstudiesbecausethis speciesisthemostcultivatedspeciesinfastgrowing planta-tions(Dillenetal.,2016)andbecauseeucalyptuswasalsoused inourpreviousstudies(Sminketal.,2019,2020a).However, the methodology applies to majority of the lignocellulosic biomasssources.
Next, the morphology of the feed must be selected. AlthoughtheDESimpregnationrateincreasesiftheparticles aresmallerandtherefore,thecookingwillbefasterandmore homogeneous,cuttingwoodinherentlycutsandthereby dam-agesthecellulosefibersinthe woodandthereforereduces thequalityoftheproducedcellulosefibers.Thus,smallerchip sizesincreasethepulpingrate,butcompromisesthequality oftheproducedcellulosefiber.Inthepaperindustry,where fiberqualityisveryimportant,chipsaregenerally20–30mm long.Forotherapplications, suchascellulosefermentation tobio-ethanol,thefiberqualityisirrelevant.Inthesecases, theusedchipsizeswillbemuchsmaller.Thechipsizeisvery importantforthedesignofthedigester,butnotforfurther
processingofthepulpandDESrecovery.Therefore,thisisno factorintherigorouscalculations.
Feedimpuritiesareimportantforany(chemical)process. Inthecaseoflignocellulosicbiomass,threemajorimpurities arepresent:water,extractablesandash.Presenceofwaterin thefeedisnotexpectedtoposeanyproblemsintheprocess, sincetheamountsofwaterpresentinthewoodare negligi-blecomparedtheamountsthatarerequiredforpulpwashing. AdditionofsomewatertoDESwilldecreasetheviscosityand isbeneficialintherecoveryprocess.However,littleisknown yeton theinfluenceofwateronthepulpingprocess.Also, highwatercontentsmayresultinsignificantevaporationat thepulpingtemperature,whichmayrequiretheuseof pres-surizedequipmentorventingduringpulping.Extractablesare low molar weightcompounds, suchas fatty acids, sterols, terpenoids and waxesthat can beextracted from biomass usingneutralsolvents.Consideringthe hydrophobicnature ofthesecompounds,theywillendupinthe2-MTHFduring theligninextraction.Extractablesmayberemovedby steam-ing biomasspriortofurtherprocessing.Ashpresentinthe feeddissolvesintheDESandwillaccumulateintheDES recy-cleloop.Therefore,itcouldbedesirabletoremoveashprior toDESprocessing,forinstancebyacidleaching(Oudenhoven etal.,2016).IncasesaltsdoendupintheDESrecyclethey willaccumulateandhavetoberemoved,forinstanceusing a bleedstream intherecycle. Purgingofthis bleedstream willbeveryexpensive,sothesaltswillhavetoberemovedby techniquessuchaselectrodialysisorprecipitationinanother solvent, such as ethanol. The ash content inthe eucalyp-tus usedforthis study wasonly0.38wt%. Incase1%ash isallowedintheDESrecyclestream,0.38kgDES hastobe bleadfromtherecycleperkgeucalyptusinthefeed(0.38kg DES*1%salt=3.8gsalt,whichisequaltotheamountin1kg eucalyptus). However,theashcontent canbemuchhigher in other biomasssources. For example,straw can havean ashcontentof6–8%(Oudenhovenetal.,2015).Forthe
rigor-Fig.1–Theinput-outputstructureoftheconceptual process.
ouscalculationsonlythepresenceofwaterinthefeedwas included.
Theoutletstreamsofthisprocessmustatleastconsistof astreamfortheproducedcelluloseandlignin.Besidesthese products,someofthehemicelluloses willalsobreakdown during DES processing. During treatment with acid DESs, hemicellulosebreaksdowntosugarfractions,whichfurther reacttofurans.Lietal.(2018)andHouetal.(2018b)studied thefractionation ofricestraw using acidbased DESs.Both authors(Houetal.,2018b;Lietal.,2018)couldonlyrecover lessthanhalfofthehemicelluloseremovedaseithersugaror furaniccompound,withtheremainderreferredtoas‘Loss’. Weexpecttheselossestobefuranicsandsugarsthatreacted furthertoformpolymericbyproductscalled‘humin’. Sepa-rationofsugarsfromDES iscomplicated.Bothcompounds arecompletelynon-volatile,excludingseparationby distilla-tion.Furthermore,bothcompoundsarehighlypolar,making affinitybasedseparationverychallenging.Theonlyoptions appeartobeadelicate membrane-basedprocess basedon thesmalldifferenceinsizeofthemoleculesandionsinthe system,another optionistoletthe sugarsreact furtherto furans.Thesefuransmaybeseparatedbyliquid–liquid extrac-tionusingorganicsolvents,suchas2-MTHF(Rosatellaetal., 2011;Duttaetal.,2012;Mikheenkoetal.,2019).Smallsugars producedinthecookingwillforamajorpartalreadybe con-vertedintofurans,andintheproposedprocessitseemslikely thatproducedfuranswillalsobeextractedby2-MTHFand thusleavetheprocesstogetherwiththelignin.Littleisknown about the humins, but withits furanicstructure, it seems possiblethattheseby-productsarealsoextractedby2-MTHF and thus leavethe process together with thelignin. Alter-natively,huminsmayprecipitateduringtheprocessonthe reactionequipment,asinthecommercialproductionof fur-furalfromhemicelluloserichagriculturalwastes(Hoydonckx etal.,2007).Intheusedlignin-in-DESmixtures,only3%of theinitialamountofxylosepresentinthebiomasswasfound backbyHPLC.Fortherigorouscalculations,weassumedthat allhemicellulosethatisremovedfromthebiomassstructure leavestoprocessas‘hemicellulosebyproduct’(HBP)together withthelignin.Thismeansthattheinput–outputstructure looksasdescribedinFig.1.
3.1.2. Batchversuscontinuous
In kraft pulping, continuous digesters have become stan-dard.Although somebatchdigesters are stillin operation, batchpulpinghasbecomeoutofdate.Inatypicalcontinuous digester,woodchipsarefedatthetopofthereactorvesseland slowlysinkthroughcookingliquorwithvariouscompositions. Comparedtothecurrentaqueouspulpingliquors,DESshave
amuchhigherdensityandviscosity(Franciscoetal.,2013c). TheincreaseddensityoftheDESincreasesthebuoyantforces exertedonawoodchipandtheincreasedviscosityincreases the dragforce onawood chip.Thiswilldecrease the flow rate ofchips throughacontinuousdigester filledwithDES and thusgreatlycomplicatesthedesignofsuchadigester. Asaconsequence,muchdatamustbegatheredtomakea detailed design. More than half ofall Europeanpulp mills hadacapacityexceeding200ktperyearin2018(CEPI,2018). Althoughsomeoldermillsstilloperatesemi-batchwise,this ishighlyunusualatthisscale.Therefore,pulpingmustbe exe-cutedcontinuously,justasotheroperations,suchassolvent recoveryandpulpwashing.
3.1.3. Theseparationsystem
Afterthe pulpingreactor, amixtureofcellulosepulp,DES, ligninandhemicelluloseby-productsmustbeseparated.In this mixture, the lignin and hemicellulose by-productsare dissolved intheDES. Itisconvenient toseparatethe solid pulpfromtheliquidDESfirst,forinstancebypressing. Dur-ingpressing,partoftheliquidremainsasstagnantliquidin the fibersin theporous pulpbeds.Therefore,the liquidin thepulpmustbedisplacedbyanotherliquid.Washingwith waterisveryconvenientsincewaterisinexpensive,non-toxic andnon-flammable.However,ifwaterisusedtodisplacethe DESinthecellulosefibers,thewaterwillmixwiththeDES, causinglignintoprecipitateonthefibers,whichisvery unde-sirable.Therefore,theDESinthecellulosefibersmustfirstbe displacedbycleanDES,beforeitcanbedisplacedbywater.
AftertheseparationbetweentheDESandpulp,theliquid mixturecontainingDES,water,ligninandhemicellulose by-productsmustbeseparated.Inourpreviouspaperwemade abriefcomparisonbetweentheregenerationofligninfrom DESusingcoldwaterprecipitation(Sminketal.,2020b)and concludedthatthe lowmolarweightligninfractionscould not berecovered bycold waterprecipitation.Furthermore, liquid–liquid extraction using 2-MTHFhas the potential to save95%energycomparedtocoldwaterprecipitation(Smink etal.,2020b).Therefore,ligninisrecoveredfromtheDESusing liquid–liquidextraction.Waterisremovedlaterfromthe mix-ture,sinceitaidsliquid–liquidextractionofligninfromthe DES.Weassumethatthehemicellulose-byproductsarealso extractedby2-MTHF(seeSection3.1.1.).The2-MTHFcanbe recoveredbyevaporationandtheligninandhemicellulose by-productsremainintheevaporationresidue,togetherwithany DESthatmayhaveleachedtothe2-MTHFduringextraction. ThisDEScanbewashedfromtheproductsusingwaterand thewashingwaterisrecycledbacktotheextractionstage.
Atlast,the DES mustbe separated from the waterand any 2-MTHF that leached to the DESphase during extrac-tion.Waterand2-MTHFmaybeseparated fromtheDESby evaporation.Aftercondensation,thewaterand2-MTHFcan beseparatedinasettlervesselbecauseoftheimmiscibility between waterand 2-MTHF. TheLLEbetween 2-MTHFand water was reported byGlass et al. (2016) and Stephenson (1992). At70◦C,the solubility of2-MTHFinwateris5wt% andthesolubilityofwaterin2-MTHFis6wt%.Remarkably, thesolubilityof2-MTHFinwaterdecreaseswithincreasing temperatures.Altogether,theflowsheetasshowninFig.2is obtained.
Massbalance
In the conceptual process, biomass is fractionatedinto pulp, lignin and hemi-cellulose by-products. Any other byproductsorlossesarenottakenintoaccountinthisprocess
Fig.2–Structureoftheconceptualprocess.Inthetopfigure,theprocessisshownbyfunctionandinthebottomfigure,the processisshownbyoperations.Afterpulping,thepulpinusedDESsuspension(3)ispressedandwashedtoformaclean pulpsuspension(6).AllUsedDESandwaterfromthewashingandpressingstagesarecombinedinstream(7),whichis mixedwithwaterfromtheligninwash(13)andtheligninandhemicellulosebyproductpresentinthismix(8)areextracted using2-MTHF(9and10).ThecleanDESrecycle(16)isdriedandthecleanDES(18)isusedagainforpulping(2)andwashing (4).
design.Therefore,theamountofbiomassenteringtheprocess (stream1,Fig.2)(MB,in)isequaltotheamountsofpulp(stream
6,Fig.2)(Mp,out),lignin(ML,out)andhemicellulosebyproducts
(MHBP,out)produced(stream15,Fig.2),asshowninEq.(5).
MB,in=MP,out+ML,out+MHBP,out (5)
Theamountofpulpproducedisthesumoftheamountof biomassenteringtheprocess,multipliedbythepulpyield(yP),
asshowninEq.(6).Thisyieldwasdeterminedexperimentally at57%.
MP,out=MB,in∗yP (6)
Theamount oflignin produced isequal tothe amount ofligninremovedfrom thebiomass.Thisisthe amountof biomassentering theprocess,multipliedbythe lignin frac-tioninthebiomass(xL,B)andthedegreeofdelignification(yL),
asshowninEq.(7).Thesefractionsweredetermined experi-mentallyatrespectively21.6%and94.1%.
ML,out=MB,in∗xL,B∗yL (7)
Forconvenience,thepulpproductionissetto1000kg/hand therewith,thesystemof3equationscanbeusedtosolvethe 3unknowns(MB,in,ML,outandMHBP,out).
TheamountofDESusedforpulpinginthedigester(stream 2,Fig.2)(MDES,pulping)isequaltotheamountofbiomass,
mul-tipliedbytheDEStobiomassratio(DB),asshowninEq.(8).
Priortooptimizingtheflowsheet,thisratioissetto10since thisisacommonratioinliterature(Alvarez-Vascoetal.,2016).
MDES,pulping=MB,in∗DB (8)
Afterpulping,thepulpisfirstwashedusingDEStoremove ligninfromthepulp.Tothebestofourknowledge,nodatais availableonpulpwashingusingDESyet.Therefore,dataused onwaterwashingisusedtogiveanestimateontheamount ofDES requiredforwashing,but morework isrequiredto provewhetherthisassumptionisjustified.Itiscommonto usearound3kgwaterperkgpulpinindustry(Eketal.,2009a). Thiswashingfactor(WF)ismultipliedbytheamountofpulp producedtocalculatetheamountofDESrequiredforwashing (MDES,wash),asshowninEq.(9).
MDES,wash=MP,out∗WFP (9)
Waterisrequiredtoaidliquid–liquidextractionoflignin fromtheDES.Therefore,thewaterfractionintheDES recy-clestream(stream16,Fig.2)(xW,DESrecycle)isdefinedasthe
amountofwaterintherecycle(stream16,Fig.2)(MW,DESrecycle)
overthesumoftheamountsofwaterandDES(frompulping andwashing),asshowninEq.(10).Awatermassfractionof 0.5isassumed,sincethisissufficientforfullligninrecovery usingliquid–liquidextraction(Sminketal.,2020b).
xW,DESrecycle=
MW,DESrecycle
MDES,Pulping+MDES,washing+MW,DESrecycle
(10)
Theamount ofsolventrequiredfortheextractionstage (stream9+10,Fig.2)(MMTHF,extraction)isequaltothetotalmass
oftheDESandwaterintherecycle(stream16,Fig.2), multi-pliedbythe solventtofeedratio (SF),asshowninEq.(11). Aratioof0.5wasused,sincethisissufficientforfulllignin recovery(Sminketal.,2020b).
xW,DESrecycle=
MW,DESrecycle
MDES,Pulping+MDES,washing+MW,DESrecycle
(11)
SincetheextractionsolventandDESarepartiallymiscible, someoftheextractionsolventleachestotheDESrecycle(from stream9tostream16,Fig.2).Thisamount(MMTHF,leached)is
determinedbythesolubilityfactor(xMTHF,leached)of2-MTHFin
DES,asshowninEq.(12).Thisfactorwasestimatedat0.1from equilibriumdata(Sminketal.,2020a).
MMTHF,extraction
=
MDES,pulping+MDES,washing+MW,DESrecycle∗SF (12)
BesidesleachingofsolventtotheDESrecycle,someDES willalsoleachtothesolvent(fromstream 8tostream11). ItmustbenotedthatDESsarenotpseudo-purecompounds, andespeciallyduringliquid–liquidextraction,their compo-sition changes sinceevery DES constituent has adifferent leachingcharacteristics.Inthiscase,lacticacidhasamuch highersolubilityin2-MTHFthancholinechloride(Sminketal., 2020a)andthus,relativelymorelacticacidthancholine chlo-ridewillleachtothe2-MTHFphase(fromstream8tostream 11,Fig.2).However,afterextractionanyleachedDESwillend up instream 12 ofthe process,where it iswashed ofthe ligninandhemicellulosebyproductandfurthermorerecycled directlybacktotheextractionstageviastreams13and8(see Fig.2).Therefore,itisnotexpectedthatthecompositionof theleachedDESwillhaveanyinfluenceontheenergyusage oftheprocessandisthereforenottakenintoconsideration. Thisamount(MDES,MTHFleach)isdeterminedfromthe
solubil-ityfactorofDESin2-MTHF(xDES,MTHF),asshowninEq.(13).
Thisfactorwasestimatedat0.3fromequilibriumdata(Smink etal.,2020a).
MDES,MTHFleach=MMTHF,extraction∗xDES,MTHF (13)
Atlast,thewaterbalanceismade.Somewateris natu-rallypresentinthiswood.Sinceitwasdecidednottopre-dry thewood,thisamounthastobetakenintoaccountaswell. Thefractionofwaternaturallypresentinbiomass(xW,B)is0.5
(Bownand Lasserre,2015).Thisisdefinedasde amountof waterinthebiomass(MW,B),dividedbytheamountsofwater
andbiomassenteringtheprocess,asshowninEq.(14).
xW,B=
MW,B
MB,in+MW,B
(14)
Sincepulpisaporousmaterial,somewaterwillalways remaininthepulpafterwashing(stream6,Fig.2).Ifthe pro-cessisintegratedwithforinstanceapapermakingplant,this amountdoesnotneedtoberemovedsincecellulosepulpmust befedtoapapermakingmachineinanaqueoussuspension. Alternatively,thewatercanberemovedifthepulpissoldon themarket.Thewaterfractioninthepulp(xW,P)isdefinedby
theamountofwaterinthepulp(MW,P),dividedbytheamount
ofpulpandwaterinthepulp,asshowninEq.(15).Thewater
fractioninpulpwassetat0.67,sincethisamountcantypically beachievedbypressingofthepulp(Eketal.,2009b).
xW,P=
MW,P
MP,out+MW,P (15)
Afterevaporationof2-MTHFfromtheligninand hemicel-lulosebyproduct,anyDESthatremainswiththeligninand hemicellulosebyproduct(stream12,Fig.2)mustberemoved fromtheligninbywashingwithwater.Theamountofwater required for lignin and hemicellulose byproduct washing (stream14,Fig.2)(MW,Lwash)isdeterminedbytheamountof
DESthatmustbewashedfromtheligninandhemicellulose byproduct,multipliedbyawashinfactor(WFL),asshownin
Eq.(16).Thewashingfactorisestimatedat2,itisassumed that2kgwaterisrequiredtowash1kgDESfromthelignin andhemicellulosebyproduct.
MW,Lwash=MDES,MTHF∗WFL (16)
Inaddition,theamountofwaterrequiredforthewashing ofpulpmustbedetermined.Industrially,3kgwaterisused towash1kgpulp.Afterthepulpwashingstep,theDESand watermixtureissenttoaliquid–liquidextractionoperation toremovelignin.Inthis step,waterisalsorequiredforan efficientligninextraction.Itisexpectedthattheamountof waterpresentinthismixtureisnotsufficientforaneffective ligninextraction.Therefore,extrawatermustbeaddedtothis mixture.Itispossibletodothisattheextractionstage,butitis alsopossibletousemorewaterduringthewashingstep.This amountwillthen(viastream7and8,Fig.2)alsoendupinthe extractionstage.Sinceusingextrawaterinthewashingstage willeasethewashingoperation,thisispreferredoverthefirst option.Therefore,theamountofwaterusedforpulpwashing (MW,Pwash,stream5)iscalculatedfromamassbalanceonthe
waterrequiredintheDESrecycleforefficientligninextraction (MW,DESrecycle,stream16).Theamountsofwaterthatalready
endedupinthisstreamfromthewaternaturallypresentin thebiomass(MW,B,stream1)andtheamountthatisadded
fromtheligninwash(MW,Lwash,stream14)arereducedfrom
thisamountandtheamountofwaterthatwaterthatleaves theprocessinthecellulosepulp(MW,P,stream6)mustbemade
upfor.ThefinalequationisshowninEq.(17).
MW,Pwash=MW,DESrecycle−MW,B−MW,Lwash+MW,P (17)
Theamountofwaterusedfrompulpwashingmustalways behigherorequaltotheminimumamountofwaterrequired forpulpwashing.Thisamountis3kgwaterperkgpulpand calledthewashfactor(WFP),showninEq.(18).Incasethe
amountofwatercalculatedbyEq.(17)islowerthanthelower boundary stated in Eq.(18), the amount ofwaterrequired forwashingwillbedeterminedaccordingtoEq.(18)andthe waterfractionintheDESrecycle(calculatedfromEq.(10))will increase.
MW,Pwash≥MP,out∗WFP (18)
UsingEqs.(5)–(18)andthementionedassumptions,which aresummarizedinTable2,themassbalanceoftheprocess canbecalculated,whichisshowninTable3.
Table3–Massbalanceoftheconceptualprocess.
Materialsinprocessstreams(kg/h) Processstream
1 2 3 4 5 6 7 8 9 10 Wood 1754 DES 17,544 17,544 3000 20,544 25,979 Water 1754 1754 5065 2000 8819 19,689 2-MTHF 18,116 3623 Pulp 1000 1000 Lignin 356 356 356 HBP 398 398 398
Materialsinprocessstreams(kg/h) Processstream
11 12 13 14 15 16 17 18 19 20 Wood DES 5435 5435 5435 20,544 20,544 Water 10,870 10,870 15,689 15,689 194 20,350 2-MTHF 18,116 3623 3623 3038 1071 Pulp Lignin 356 356 356 HBP 398 398 398 3.2. Energybalance
Duringpulping,themixtureofDESandwoodiskeptat130◦C. Afterpulping,thepulpisfirstwashedusingcleanDESfrom theevaporationplant.ThecleanDESisnotheated,norcooled beforethewashingstage.AfterthecleanDESwash,thepulp iswashedusingfreshwater.Theuseofhotwaterisbeneficial becauseitincreasesdiffusionratesanddecreasesthe viscos-ityoftheliquidmixtures.Franciscoetal.(2013a).determined theviscosityofasimilarDES, comprisedoflactic acidand cholinechlorideina2:1Mratioat13temperaturesfor11 mix-turesofthisDESwithwater.Itisassumedthatwaterenters thewashingplantat80◦C.Atthistemperature,theviscosityof thecomparableDESusedbyFranciscoetal.(2013a)is25mPas andisreducedtoapproximately 1mPasina50wt%DESin watersolution(∼0.14mol/mol).Furthermore,nopressurized equipmentisrequiredatthistemperatureanditcaneasilybe achievedusingwasteheatoftheprocess.Eitherwaterfrom theevaporationplantmay beuseddirectly inthe washing stage,or the heat in this stream may beused topre-heat waterforthewashingstage.Itisassumedthatthe suspen-sionofcellulosefibersinwaterexitsthewashingplantatthe inlettemperatureofthewashingwater(80◦C)andthatthe restoftheliquidsfromthewashingplantaremixed.Before liquid–liquidextraction,thisstream(stream7,Fig.2)iscooled downto75◦C.Thisisslightly lower thanthe boilingpoint ofpure2-MTHF(whichis80◦C),andbasedontheVLEdata reportedbyGlassetal.(2016),weestimatethatnopressurized equipmentisrequiredforliquid–liquidextraction.
Afterliquid–liquidextraction,waterisremovedfromthe DESrecycle(stream16,Fig.2.)bymulti-effectflash evapora-tion.Itisassumedthatthesemulti-effectflashevaporators havethesamecharacteristicsasthemulti-effectflash evap-oratorscurrentlyusedinthekraftprocess.Furthermore,itis assumedthattheDESiscompletelynon-volatile,asshown byFranciscoetal.(2013a).Typically,theseevaporatorsusea 7effectevaporationtrainandhaveasteamefficiencyof5.95 (Valmet,2015)(1tonofsteamisusedtoevaporate5.95tonof water).However,theheatrequiredtoevaporatewaterfrom kraftblackliquor(Hvap,BL)isdifferentthantheheatrequired
to evaporatewater from the DES (Hvap,DES). Hvap,BL was
determinedbyFerreiraetal.(2011)andis54.1kJ/mol.Hvap,DES
wascalculatedusingtheClausiusClapeyrontheorywithVLE dataobtainedbyFranciscoetal.(2013a)andequals44.3kJ/mol. Ifitisassumedthattheheatcontentofsteamis2.2GJ/t[75], theheatdutyofthewaterevaporationstepcanbecalculated usingEq.(19). Qwaterevaporation=2.2∗ MW,DESrecycle steamefficency∗ Hvap,DES Hvap,BL (19)
Inmultieffectflashevaporation,thefirststageorstages areheatedusingdirectsteam.Thesteamthatevaporatesfrom thisliquidisusedtoheatthenextstage,andsoforth.TheDES entersatthelasteffectandisthusheatedfurtherwitheach consecutivestage.Itisassumedthatthetotalheatincrease isequaltotheheatincreaseinakraftevaporator,whichis typically 40◦C [76]. Thismeans that the dry DES exits the evaporationtrainat75+40=115◦C.
Afterliquid–liquidextraction,the2-MTHFisalsorecovered using multi-effectflashevaporation.Itisassumedthat the setupofthemultistage flashevaporationissimilar tothe setupofthewaterevaporation.However,theheatof evap-oration of2-MTHFisonly 0.40MJ/kg, whichismuch lower thantheheatofevaporationofwater,whichis2.2MJ/kg.This meansthatinthefirststage,1kgsteamisrequiredto evapo-rate2.2/0.4=5.5kg2-MTHFandthustheheatdutyisreduced bythisfactor.The2-MTHFvaporfromthefirststageisthan usedtoheatthenextstage,andsoforth.Itisassumedthat thesameevaporationefficiencyisachievedasforthe evap-orationofwaterfromDES,thustheheatdutyisreducedby thesameefficiencyfactorof5.95.Thetotalheattoevaporate the 2-MTHFafterliquid–liquid extractioncanbecalculated accordingtoEq.(20). QMTHFevaporation=2.2∗ 0.40 2.2 ∗ MMTHF,extraction Evaporationefficiency (20)
Aftertheevaporationtrain,theDESiscleanandreadytobe usedagaininthepulpingstep.TheDESandwoodchipsare addedtoadigester.For theenergycalculationsweassume thatthewoodchipsenterthedigesteratroomtemperature. Both the DES and the chips(withwater inthem)must be heatedto130◦Cinthedigester.Thisheatcanbecalculated usingtheheatcapacitiesofwood,waterandDES,according
Table4–Energyusageintheconceptualprocessbefore andafteroptimization.
Operation Heatbefore optimization(GJ/t) Heatafter optimization(GJ/t) Digester 1.7 1.3 Waterevaporation 6.2 2.7 2-MTHFevaporation1.4 0.7 Pulpdrying 3.0 3.0 Total 12.3 7.7 toEq.(21).
QDigester= (CP,wood∗MB,in+CP,water∗MW,B)∗
Tdigester−Troom
+CP,DES∗MDES,pulping∗
Tdigester−Tevaporation,end
(21)
LittleisknownabouttheheatsofreactioninDES delig-nification.Tothebestofourknowledge,onlyonestudywas performedon the heats ofkraft delignification(Courchene etal.,2005).However,theseresultscannotbeusedtomake anestimation forDES delignification since the delignifica-tionchemistryiscompletelydifferent.Courcheneetal.(2005) found that the heat released during kraft pulping indicat-ing an exothermic process,is due to the neutralization of acidiccarbohydratebreakdownproductswithNaOH,a reac-tionthatdoesnotoccurinDESdelignification.Thequestion whether biomassconversion processesare endothermicor exothermicalsoplaysinotherfields,suchaspyrolysis.Inthe pyrolysisprocess,manyendothermicandexothermicreaction zoneswereobserved.Overall,itisbelievedthatpyrolysisof woodisslightlyendothermicwithaheatofreactionaround 0.6MJ/kg(Sinhaetal.,2000),althoughitmustalsobenoted thatligninbreakdown reactions aremoreexothermic than cellulosebreakdown reaction(Roberts,1971)(whichremain mostlyinertduringpulping).Furthermore,thefractionofthe polymersthatreactsinthepulpingismuchsmallerthanin pyrolysis.Taken together,itappearsjustifiedtoneglectthe heatthatisproducedorrequiredduringDESpulping,but fur-therresearchisnecessarytofindoutwhetherthisassumption isrealistic.
Atlast,thepulpmaybedried.Formanycellulose applica-tions,suchaspapermakingorenzymatichydrolysisforthe productionof other chemicals, the celluloseis used in an aqueousslurry.Whenthisplantisintegratedwiththe pulp-ingplant,dryingofthepulpisunnecessary.Inthisstudythe heatofdryingistakenintoaccount,sincewestudya non-integratedpulpmill.Itisassumedthattheheatrequiredfor pulpdryingisthesameasinacommercialpulpmill,which is3GJ/t(Suhretal.,2015).Inshort,heatisrequiredforthe digesterandtoevaporatewaterand2-MTHFandcoolingofthe DESisrequiredbeforeliquid–liquidextraction.Anoverview oftherequiredheatfortheprocessisshowninTable4. Fur-thermore,theproducedpulpmaybedried.Unfortunately,the heatsformulti-effectflashevaporationandpulpingmustbe providedathightemperatures(>120◦C)andthus,thereare littleopportunitiesforheatintegration.
3.3. Processimprovement
Theamountofheatrequiredforanon-integratedDESbased pulping process was estimated at 12.3GJ/t using rigorous calculations.Toputthis numberinto perspective;atypical
Fig.3–DelignificationofeucalyptusasfunctionoftheDB ratio.Thethreeexperimentaldelignificationsofeucalyptus wereobtainedbytreatingthewood1hat130◦C.The regioninwhichtheDBratioistoolowtofilltheporous biomassbedwithDESisindicatedinredblocksandthe regionbelowthefiberliberationpointisindicatedwith orangestripes.(Forinterpretationofthereferencesto colourinthisfigurelegend,thereaderisreferredtothe webversionofthisarticle).
kraftprocess uses11.0GJ/t inheat. InordertomakeaDES based pulpingprocess competitive tothe kraft,the energy usageshould belower than inthekraftprocess. Consider-ing thatmanydecadesofoptimizationhavetakenplacein the development ofthe kraftprocess, alsooptimizationof the DES-based process should be done, and startingfrom thevaluestakenfromlaboratoryobservations,afirstsetof improvementsisconsideredbasedonacombinationof exper-imentsandcalculations.
3.3.1. DEStobiomassratio
Themostobviousparametertochangeintheprocessisthe DBratio.UsinglessDESwillreducethedutyinthedigester andrequirelesswaterand2-MTHFforextraction.However, a decreasedDBratio willincreasethe ligninconcentration intheDES,whichmaydecreasethedelignificationrate. Fur-thermore,thereisaminimumDBratiobecausebiomassitself isaporousstructureandbiomassinadigesterhasa pack-ingdensity.Thistypicallyresultsinapackingdensityaround 230kg/m3forhardwoods(Eketal.,2009b).Assumingthe
den-sityofwoodis1500kg/m3(Eketal.,2009b)andthedensity
oftheDESappliedinthisstudyis1140kg/m3(Franciscoetal.,
2013c),atleast4.2kgDESisrequiredtofilltheemptyspacesin thewoodpacking.Forconvenience,theDBratiowasreduced from10:1to5:1kg/kg.Itwasfoundthatdelignificationdegree decreasedfrom94.1%to87.0%andtheyieldincreasedfrom 57%to59%.Althoughthedelignificationdegreedecreased,it isstillwellabovethefiberliberationpoint,whichisat80% delignification(Brännvall,2017).Thisisschematicallyshown inFig.3(Brännvall,2017).Thetotalenergyuseintheprocess decreasedto8.6GJ/tpulp.
3.3.2. Wateraddition
Reducing the amount of water used in the liquid–liquid extraction ofligninfrom the DES willdecrease the energy requirementinthewaterevaporator.Thewatercontentinthe DESmustbebetween25and50wt%forfullligninrecovery
Fig.4–SinglestageligninrecoveryfromDESusing2-MTHF forvariousamountsofwaterintheDESraffinateat equilibrium.Thewatercontentsintheraffinatethatare obtainedintheproposedprocessbymixingtheminimum amountsofwater(seeEq.(18))areindicatedbydashed linesfortwoDBratios.Thesearetheminimumamountsof waterthatcanbereachedfromaprocesspointofview. (Sminketal.,2020a).Theligninrecoveriesinoneextraction stageweredeterminedfor6watercontentsintheraffinates between20 and 55wt%. Itwasfoundthat the singlestage recoverydidnotimprove muchwhen thewatercontent in theraffinateincreasedmorethan40%.
Waterhastwofunctionsintheprocess,itisrequiredfor fullextractionoftheligninfromtheDES,anditisrequired forthewashingofthecellulosefibersandlignin.Thewater thatisrequiredforwashingthecelluloseandligninis recy-cledtotheextractionstage.Whentheminimumamountsof washingwateraremixedwiththeDES,thewatercontentsin theraffinatearebetween38%and43%foraBDof1:10and1:5 respectively.ThesevaluesareshowninFig.4asthedashed anddash-dotlines.Itcanbeseenfromthefigurethatthe sin-glestagerecoverydoesnotincreasemuchfurtherwhenmore waterisaddedthanthewaterthatisalreadypresentfrom therecyclingofthewaterwashings.Therefore,theamount ofwaterrequiredforthe processislimited bytheamount requiredforthewashingstages,ratherthanthelignin recov-ery.AtaDBratioof5:1and43%waterintheraffinate,thetotal energyusageoftheprocessdropsto7.7GJ/tcellulosepulp.
3.3.3. RecyclingofwashingDES
TheDESthatiscurrentlyusedforwashingissentdirectlyto theliquid–liquidextractionstage,whereligninand hemicel-lulosebyproductareremovedfromit.Thelignincontentsin theeluentstreamsarehoweverlowerthanthelignincontents intheDESthatexitsthedigester.Thus,theligninthatexits thewashingstreammaybeconsideredasnotfullysaturated. Therefore,itmaybeconsideredtosendtheeluentfromDES washingwithalowlignincontentbackdirectlytothe pulp-ingstage.IfthisDESisrecycledbackdirectlytothedigester, the total energyusage can befurther reduced from 7.7 to 6.8GJ/t.However,whenmoreligninispresentinthedigester, thismaycauseligninandhemicellulosepolymerization reac-tions,whichmayinhibitthedelignificationrateandincrease theligninmolarweight.Toinvestigateontheseverenessof therepolymerization, delignificationexperimentswere car-riedoutwithpreviouslypreparedlignin-in-DESmixtures.
FromFig.5itcanbeseenthatthedelignificationdecreases withthe initiallignincontent.However, thedelignification
Fig.5–Delignificationofeucalyptusasfunctionofthe initiallignincontentoftheDES.Eucalyptuswastreated1h at130◦C.
staysabove80%,evenwhentheinitiallignincontentexceeded 2.5wt%. The lignin molar weightdistribution in these liq-uids was also investigated by GPC. First, the lignin molar weightdistributionsinthepreviouslypreparedlignin-in-DES mixture,andintheDESthatwasobtainedafterthe delignifi-cationexperimentusingcleanDESweredetermined.When the lignin-in-DES mixture is used for a consecutive delig-nification experiment, the lignin that is added to the DES duringthedelignificationexperimentisaddedtothelignin thatwasalreadypresent inthemixture.Ifweassumethat theligninthatwasinitiallypresentinthelignin-in-DES mix-tureisinertduringthedelignificationexperiment,itwouldbe expectedthattheligninobtainedbythedelignification exper-imentusingthelignin-in-DESmixtureisthesumofthelignin inthe initiallignin-in-DES mixtureandtheligninobtained usingthecleanDES.Wecanthenexpectthemolarweightof theligninobtainedfromthedelignificationexperimentusing thelignin-in-DESmixturetobetheweightedaverageofthe lignininthe lignin-in-DESmixtureand theligninobtained by delignification using a clean DES. This expected molar weightdistributionwascomparedtothedistributionthatwas actuallyobtained inthe delignificationexperiment usinga lignin-in-DES mixture, as shownin Fig. 6. In this figure, it canclearlybeseenthattheobtainedmolarweightismuch higherthantheexpectedmolarweightandthus,additional condensationreactionsmusthavetakenplacewiththelignin thatwasinitiallypresentinthemixture.Thiswillnotonly makeithardertovalorizetheobtainedlignin,butitwillalso makeligninrecoverybyliquid–liquidextractionmuchharder. Therefore,recyclingofwashingDESwithoutligninrecoveryis notconsideredfortheconceptualdesign.
3.4. Solventlosses
Lactic acid can form esters withhydroxyl groups in other molecules,justlikeanyothercarboxylicacid.Thismeansthat lacticacidmayalsoformesterswithhydroxygroupsinlignin andcellulose.Forexample,Kajimotoetal.(2008)produced cel-lulosefibersfromSugipineusinglacticacidandfoundthatthe producedfiberscontained6–9%lacticacid,whichwas poly-merizedtothecellulosefibers.Thelacticacidfractioninthe ligninandcelluloseproducedbyDESwasdeterminedbyacid hydrolysis.Itwasfoundthatthecellulosecontained3.6wt% lacticacid,whilethelignincontained6.4wt%lacticacid.By massbalancethismeansalossof36kglacticacidinthepulp
Fig.6–Obtainedandexpectedmolarweightdistributions foradelignificationexperimentusingalignin-in-DES mixture.TheobtainedgraphistheGPCspectrumfromthe trialwith2.6wt%initiallignin.Theexpectedmolarweight graphistheweightedaverageoftheGPCspectrumofthe lignin-in-DESmixtureandtheGPCspectrumobtainedfrom thedelignificationexperimentusingcleanDES.
and20kgintheligninpertcelluloseproduced,addinguptoa totallossof56kglacticacidpertcellulosepulp.Possibly,lactic acidcanberemovedfromcellulosefibersbyozonebleaching (NeumannandBalser,1993).
Moreresearchisrequiredtodeterminethelossesby sol-ventdegradationduringDESprocesses.Rodriguezetal.(2019) researcheddegradation byesterification betweenthe lactic acidandcholinechloride.However,theseesterification reac-tionsareequilibriumreactions.Thismeansthattheformed degradationproduct(theesterbetweenlacticacidandcholine chloride)reactsbacktotheinitialDES,andespeciallyby oper-atingthepulpingstagewet,thepresenceofwaterdramatically reducestheesterificationoflacticacid.Hazetal.(2016) deter-minedthataDEScomprisedoflacticacidandcholinechloride wasstableupto197◦C,meaningtheusedDESisthermally stableattheoperatingconditionsusedinthiswork.
4.
Outlook
Theenergyuseinthisprocessismainlyduetotheevaporation ofwaterusedforwashingthecellulosefibers.Thismeansthat thereisrelativelylittleroomforanimprovementinenergy usebythe optimizationofpulpingandregeneration condi-tions.Nevertheless,theheatdutyoftheproposedDESprocess is28%lowerthanthekraftprocess.Washingwithother sol-vents,suchasethanolinsteadofwatermayfurtherdecrease theenergyusageoftheprocess sincetheheat of evapora-tionofethanolismuchlowerthan water.Anotherpossible reductionoftheheatdutycanbeobtainedbyreducingthe evaporationofwater,by(atleastpartially)dewatertheDES usingamembrane.Furtherresearchonthissubjectis nec-essarytoaccuratelyestimatethetechnicalfeasibilityofsuch processandtoestimatethepossiblesavingsinenergyuse.
PulpingwithDESsofferspotentialadvantagesoverthe cur-rentkraftprocessfromtheviewpointofthe12principlesof greenchemistry(AnastasandEghbali,2010).First,the poten-tialtoproducevaluablebyproductsfromthefeedstockismuch higher,meaningmoreproductscanbemadefromthesame feedstock,whichincreasestheatomeconomy.Reasonforthe
higherpotentialonvaluablebyproductsisthatnonucleophlic substitutionusing bisulfidehastobeusedtodelignifiy the biomass(DaCostaLopesetal.,2020).Thismeansthatthe pro-cessislessdestructivetothelignin,whichmaybeobtained withhighervalue.Second,theenergyefficiencyofthe pro-cessispotentiallyimprovedsignificantlyasfollowsfromour energyanalysis.Third,becausenopressurizedequipmentis requiredtooperatetheprocess,thecookingissafer.However, therearealsosomedrawbacksrelatedtotheuseof2-MTHF, whichisusedintherecovery.Although2-MTHFabio-based solvent, it isveryvolatile and flammable.Althoughits use seemsjustifiedbythesignificantenergysavings,itis desir-abletofindnon-flammablealternativesto2-MTHF.Allinall, weconsiderthebenefitsoftheproposedprocess,intermsof the12principlesofgreenchemistry,tobemuchbiggerthan thedrawbackscomparedtothekraftprocess.
Itseemsthatalloperationscanbeperformedusingreadily availabletechnology.Furthermore,nopressurizedequipment isrequiredsincetheproposedDESisnon-volatile.Thismeans thattheprocessmayhaveaverylowcapitalexpenditure. Fur-thermore,theenergyusageoftheproposedprocessisvery low,whichisnotonlyfavourablefortheoperationalcosts,but sincetheinvestmentcostsofchemicalprocessesaretypically dictatedbyenergylosses(Lange,2001),thisisalsofavourable fortheinvestmentcostsoftheproposedprocess.However,the biggestopportunityforDESbasedproductsisthevalorization ofby-products.Nexttotheproducedcellulose,ligninsmaybe producedalwell.Furthermore,theprocessmaybeadjusted toproducevaluablefuranicproductsfromthehemi-cellulose, suchas(hydroxymethyl)furfural(Huetal.,2008;Zhangetal., 2014).Thesechemicalmaybeusedasfeedstockforchemical industryasareplacementoffossilresources,asschematically showninFig.7.Allinall,theproppedDESbaseddelignification processshowsagreateconomicpotential.
In the proposed process,DES losses are significant due topolymerizationoflacticacidtoligninandcellulose.This means that the process either has high solvent losses, or expensivepost-treatmentstorecoverDES.Furthermore,some 2-MTHFleaches tothe DESduringliquid–liquid extraction. This is evaporated from the DES together with the water andcanbeseparatedusingasimplesettlersince2-MTHFis immisciblewithwater.However,2-MTHFandwaterdohave amutualsolubility (Glasset al., 2016). Asolubility calcula-tionusingthedatafromGlassetal.(2016)resultsinalossof 456kg2-MTHFpertcellulose.Thisamountmustalsobe recov-eredfromthewater,forinstancebyextractionusingeither ahighboilingsolvent,suchasdodecane,orsolvent impreg-natedresins.Inthiscase,the2-MTHFcanberecoveredfrom theextractantbyflashevaporation,meaningheatof evapo-rationof2-MTHFmustbeaddedtothetotalheatduty.This amountis0.456*0.4=0.18GJ/tcellulose.Alternatively, mem-braneseparationsmaybeconsideredforthisseparation,but moreworkisrequiredtofindoutwhetheramembrane sep-arationistechnicallyfeasible.Membraneseparationsdonot requireadditionalheat,butwillrequiresomeadditional elec-tric power (Kujawski,2000). The kraft process is currently favoredoverotherbiomassfractionationprocessessincethe cellulosefibersproducedbythisprocesshavegoodproperties forpapermaking.IthasnotyetbeenproventhatDESbased delignificationprocessescanproduceasimilarfiberqualityto thekraftprocess,whichmaylimitpossibleindustrial appli-cation.ConsideringthemanypossibleDESconstituentsand ratios,whichwillallaffectthefiberquality,wethinkthatit mustbepossibletofindaDESthatcanproducecellulosefibers
Fig.7–ConceptualcomparisonofthefeedstocksandproductsinthecurrentindustrialsituationandthedesiredDES process.PicturewasadaptedfromtheProviDESfinalreport(DeepEutecticSolventsinthepaperindustry,Institutefor SustainableProcessTechnology,2018).
withtherightpropertiesforpapermaking,butmoreresearch isrequiredtoproofthis.
5.
Conclusions
Aconceptualprocessdesignwasmadeforthedelignification oflignocellulosicbiomassusingadeepeutecticsolvent com-prisedoflactic acidand cholinechloride.Massand energy balancesweremadeusingrigourouscalulations.Optimizing theamountsofwaterandDESusedintheprocessreduced theestimatedheatdutyfrom12.3to7.9GJ/tcellulose,which is28%lowerthan thekraftprocess.TheamountofDESin theprocess could bereduced tothe amountthat is physi-callyrequiredtofilltheporousbiomassbed.Theamountof waterrequiredforsufficientligninrecoverybyliquid–liquid extractionisalreadyachievedwhenthewaterusedfor wash-ingofthecelluloseandligninarerecycledtotheliquid–liquid extractionstage.Recyclingoflignin-in-DESmixturesdirectly backtothedelignificationstagemaysaveaminoramountof energy,butwillincreasethemolarweightofthelignin,which decreasesits potentialforvalorizationand makesrecovery byliquid–liquidextractionmoredifficult.Valorizationof by-products,suchasligninandfuranicsfromhemi-celluloseis keyinDESbaseddelignificationprocesses.
Declaration
of
interests
The authors declare that they have no known competing financialinterestsorpersonalrelationshipsthatcouldhave appearedtoinfluencetheworkreportedinthispaper.
Acknowledgements
Theauthors would like tothankthe members ofthe ISPT “DeepEutecticSolventsinthepulpandpaperindustry” con-sortium for their financial and in kind contribution. This cluster consists of the following organisations: CTP, CTS Twente,ISPT,Mayr-MelnhofKarton,MidSwedenUniversity, Mondi, Sappi, Stora Enso, University of Aveiro, University ofTwente,ValmetTechnologiesOy,VTTTechnicalResearch CentreofFinlandLtd,WEPAandZellstoffPöls.Thisproject receivedfundingfromTKIE&Iwiththesupplementarygrant ’TKI-Toeslag’forTopconsortiaforKnowledgeandInnovation (TKI’s)ofthe<GS1>MinistryofEconomicAffairsandClimate Policy.
Eucalyptuschipswere kindlyprovidedbyTheNavigator Company.
Appendix
A.
Supplementary
data
Supplementary material related to this article can be found,inthe onlineversion,atdoi:https://doi.org/10.1016/j. cherd.2020.09.018.
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