capsol!final!publishable!summary!report! ! 1! - cordis

! CAPSOL!Final!Publishable!Summary!Report! !

1!

!

CAPSOL:(Design(Technologies(for(Multi9Scale(Innovation(and(Integration(in(Post9Combustion(CO2(Capture:(From(Molecules(to(

Unit(Operations(and(Integrated(Plants((

Executive(Summary(Power! generation!world=wide!mainly! depends!on! the! combustion!of! fossil! fuels.! Available!capture!technologies!are!predominantly!based!on!the!use!of!intermediate!materials,!namely!solvents!that!enhance!the!separation!efficiency!by!selectively!dissolving!CO2.!Amine=based!organic!compounds!are!among!the!most!common!solvents!employed!in!the!widely!utilized!chemical! absorption! process.! The! globally! observed! preference! towards! solvent=based!absorption! is! largely! because! the! technology! is! well! established,! the! conditions! for! both!absorption!and!solvent!regeneration!(desorption)!are!mild!and!relatively!easy!to!meet!and!the! process! can! be! easily! retrofitted! onto! existing! plants.! A! major! downside! of!absorption/desorption!is!the!increased!energy!required!for!solvent!regeneration.!This!results!in! high! capture! costs,! hence! there! is! a! lack! of! motivation! by! the! industry! to! adopt! this!technology.!!CAPSOL!project!employed!a!truly! innovative!and!holistic!approach!for! the! improvement!of!the!current!state=of=the=art!in!solvent!based!CO2!capture!technologies.!The!approach!aimed!at! enhancing! the! sustainability! features! of! the! entire! process,! and! reducing! the! overall!annualized! costs! through! higher! separation! efficiency! and! better! integration! solutions.! In!order!to!achieve!the!final!goal,!CAPSOL!project!developed!novel!methods!and!techniques!at!multiple!levels!associated!with!the!CO2!capture!system.!!CAPSOL! initially! targeted! the! molecular! level,! where! new! thermodynamic! models! of!transferable! parameters! enabled! the! utilization! of! group! contribution! methods! within! a!computer! aided! molecular! design! framework.! The! outcome! was! the! identification! of!solvents!and!solvent!blends!of!increased!affinity!towards!CO2,!reduced!regeneration!energy!needs!and!environmentally!benign!characteristics.!CAPSOL!developments!resulted!in!a!complete!suite!of!process!models!for!the!absorption!and!desorption! units! or! variable! resolution! utilized! in! the! optimal! design! of! flowsheet!configurations! of! reduced! capital! and! operating! costs! as! well! as! the! design! of! highly!performing! packing!materials! with! extremely! low! pressure! drop! and! adequate! separation!efficiency.!!Major!industrial!case!studies!in!the!area!of!power!generation!as!well!as!materials!production!have! been! thoroughly! analyzed! and! studied! employing! CAPSOL! technology! in! solvent!selection,! process! design! optimization,! equipment! design! manufacturing,! and! heat!integration!options.!The!outcome!provided!strong!evidence!that!the!CAPSOL!technology!is!a!viable!and!highly!competitive!alternative!to!the!current!state=of=the=art!in!CO2!capture.!!Finally,!a!pilot!plant!scale!CO2!capture!system!has!been!set!in!operation!in!order!to!perform!sensible!experiments!that!prove!the!feasibility!and!highlight!the!practicality!of! the!CAPSOL!solvent=equipment!combination.!Overall,! the! CAPSOL! technology! offers! definitely! a! superior! solution! than! the! benchmark!monoethanolamine!(MEA)!capture!plant!! for! lignite! and! coal! power! plants,! as! well! as!quicklime!production!units!and!achieves!a!comparative!performance!for!the!gas!fired!power!plants.!!!


2!

CAPSOL(Project(Context(and(Main(Objectives(The!efficient!capture!of!CO2!is!reasonably!regarded!as!one!of!the!grand!challenges!for!the!21st!century![1],!considering!that!a!single!coal=fired!plant!may!emit!up!to!25!million!tons!of!post=combustion!CO2!per!year![2].!Available!capture!technologies!are!predominantly!based!on!the!use!of!intermediate!materials,!namely!solvents!that!enhance!the!separation!efficiency!by! selectively! dissolving! CO2! [3].! Amine=based! organic! compounds! are! among! the! most!common!solvents!employed!in!the!widely!utilized!chemical!absorption!process.!The!globally!observed!preference!towards!solvent=based!absorption!is!largely!because!the!technology!is!well!established,!the!conditions!for!both!absorption!and!solvent!regeneration!are!relatively!easy! to! meet! and! the! process! can! be! easily! retrofitted! onto! existing! plants! [4].! Major!downsides! involve! the! increased! energy! required! for! solvent! regeneration,! environmental!aspects!associated!with!the!toxicity!of!the!solvent!and!solvent!derivatives,!the!presence!of!contaminants!that!affect!the!solvent!performance!and!lead!to!solvent!degradation!and!the!corrosion!of!equipment!caused!by!the!solvent!itself.!!Clearly,! such! shortcomings! require! significant!advances! in! solvent!performance,! supported!by!the!additional!introduction!of!considerable!improvements!in!the!overall!process!systems!that! emit! and! capture! CO2.! Despite! previously! intense! research! effort! in! this! direction,!solvent=based!absorption!processes!are!reported!to!introduce!a!cost!penalty!of!over!40%!to!the! operation! of! the! plant! [2].! Approximately! 70%! of! these! costs! are! due! to! the! use! of!thermal!separation!processes!for!solvent!regeneration![4].!Such!estimates!bring!the!capture!cost!in!the!range!of!$52=89!(€36=62)/ton!(Note:!The!original!prices!reported!in![5]!are!$45=65!(€!31=45)/ton!of!CO2!for!a!coal=fired!power!plant!with!a!capacity!of!900=300!MW!in!2004.!The! above! prices! correspond! to! 2011! rates! in! U.S.! dollars! accounting! for! inflation! and!transformed!into!€!using!recent!exchange!rates)!of!CO2![5],!which!is!well!above!the!current!trading!price!(at!€16.5!on!24=03=2011).The!planned!carbon!tax!in!the!UK!is!£16!(€18)!in!2013!and! £30! (€34)! in! 2020! (based! on! 2009! prices)! [6].! Therefore,! there! is! a! lack! of! economic!incentive!in!the!industry!to!capture!CO2!at!the!current!high!cost.!A!new!technology!towards!breakthrough! innovation! in! solvent! based! post=combustion! CO2! capture! for! enhanced!energy! efficiency,! improved! cost! effectiveness! and! increased! process! sustainability! and!environmental! benefits! is! developed.! Advances! in! the! identification! of! highly! performing!solvents! and! solvent! blends! in! CO2! absorption,! the! design! of! innovative! separation!equipment! internals,! and! the! development! of! optimal! process! configurations! enable! cost!reductions! of! at! least! 20=30%! per! ton! of! CO2! captured.! Such! achievement! can! have! a!tremendous!impact!in!several!industrial!applications!such!as!gas=fired,!coal=fired,!and!lignite=fired!power!plants! as!well! as! and!quick=lime!production!plants!where! solvent! based!post=combustion!CO2!absorption!can!become!a!viable!solution.!!!The!CAPSOL!project!adopts!a!holistic!approach!towards!the!fulfillment!of!the!outlined!goals!accomplished! through! research! and! development! at!multiple( levels! within! an! integrated(framework.!!At( the( molecular( level,! the! use! of! computer! aided! molecular! design! tools! supported! by!accurate! and! adequately! validated! thermodynamic! models! enables! the! exhaustive!investigation!of!the!performance!of!multiple!solvents!and!solvent!blends!in!post=combustion!CO2!absorption!processes.!The!solvent!blends!are!systematically!assessed!and!rank=ordered!against! their! performance! towards! the! satisfaction! of! relevant! process,! economic,!


3!

operability!and!sustainability!criteria.!The!optimal!solvents!and!solvent!blends!are!expected!to!exhibit!significantly!better!characteristics!than!currently!used!solvents!in!terms!of!energy!requirements!and!overall!environmental!impact.!!!At( the( unit( operations( level,! the! design! of! innovative! process! configurations! and! column!internals! that! are! specifically! tailored! for! the!employed! solvents!enhance! the!efficiency!of!the!absorption!based!separation.!Advanced!modeling!and!optimization!tools!in!conjunction!with!thorough!experimental!procedures!ensure!the!achievement!of!high!mass!transfer!rates!and!optimal!flow!patterns.!!!At(the(plant(level,!the!comprehensive!analysis!of!the!interactions!among!an!existing!power!plant!and!the!added!solvent!based!post=combustion!CO2!capture!unit!enables! the!optimal!allocation!of!resources!for!improved!energy!savings!and!the!efficient!integration!of!the!new!CO2!capture!process! components.! Several! industrial! applications! in!power!production!and!chemicals! manufacture! are! scheduled! for! comprehensive! study,! analysis,! and! evaluation!thus!resolving!all!related!technical!and!engineering!issues.!!Therefore!CAPSOL!aims!to!address!these!challenges!by!seeking:!!•! Solvents! and! solvent! blends! of! increased! affinity! towards! CO2,! reduced! regeneration!energy!needs!and!environmentally!benign!characteristics,!!•! Absorption/! desorption! configurations! and! packing! materials! of! reduced! capital! cost,!supporting!operating!conditions!that!facilitate!the!solvent=CO2!reaction!and!subsequent!CO2!release.!!•!Improvements!in!CO2!emitting!plants!to!facilitate!the!optimal!integration!with!the!capture!units.!!!The!targeted!developments!can!have!a!tremendous!impact!in!several!industrial!applications!such!as!gas=fired,!coal=fired,!and!lignite=fired!power!plants!as!well!as!quick=lime!production!plants! where! solvent! based! post=combustion! CO2! absorption/desorption! can! become! a!viable!solution.!!Scientific(Objectives(The!above! targets! are! approached! through! the!use!of! advanced! computer=aided!methods!and! tools! supporting! the! fast,! cost=efficient,! automated! and! accurate! identification! of!potentially!useful!capture!solvents!and!process!systems.!Few!resulting!solvents!and!process!operating! conditions! indicating! high! performance! are! then! verified! in! focused! pilot! plant!experiments.!The!utilization!of!such!methods!and!tools!requires:!•! The! development! of! property! predictive! methods! in! the! form! of! advanced!thermodynamic!models!able!to!capture!and!model! the!highly!non=ideal!solvent=CO2=water!interactions!!•! The!development!and! implementation!of!computer=aided!molecular!design!(CAMD)!methods!to!investigate!a!very!large!number!of!potential!CO2!capture!solvent!candidates!in!terms!of!thermodynamic,!kinetic!and!sustainability!properties.!•! The! development! of! conceptual! and! rigorous! process! models! able! to! efficiently!capture! different! solvent! process! interactions! both! at! the! level! of! absorption/desorption!flowsheets!and!column!packing!materials.!!


4!

•! The!development!and!utilization!of!systematic!process! integration!and!optimization!tools! for! the! investigation! of! overall! cost=saving! opportunities! in! CO2! emitting! plant!complexes!including!waste!heat!recovery!and!efficient!resources!management.!!!Technological(Objectives(The! scientific! objectives! facilitates! in! the! achievement! of! the! following! technological!objectives:!1) Develop!optimally!designed!novel!solvents,!blends!and!absorption/desorption!flowsheets!

that:!!• Result!in!much!less!energy!requirements!compared!to!a!30!wt!%!MEA!process!,!• Combine! superior! sustainability! (e.g.,! environmental,! safety! etc.)! properties,!

translating!to!a!significant!improvement!in!the!eco=indicator!and!in!the!SHE!(Safety=Health=Environmental)!hazard!assessment!indicator.!!

• Facilitate! minimum! sensitivity! to! process! variations! and! disturbances! (e.g.!impurities),!!

• Enable!efficient!operation!under!different!pressure/temperature!conditions!(e.g.!high!pressure!desorption).!!

• Resolve! issues! such! as! contaminants,! degradation,! removal! of! decomposition!products,!compression!of!CO2,!water!balance!etc.!with!high!efficiency.!!

2) Develop!optimally!designed!absorption/desorption!equipment!that:!!• Enables!large!reductions!in!the!capital!and!operating!expenses!compared!to!a!30!wt!

%!MEA!process,!!• Incorporates! significant! improvements! in! column!packings! including! new! structural!

(e.g.!size,!geometry!etc.)!and!operating!(e.g.!flow,!pressure!drop,!mass!transfer!etc.).!characteristics! of! optimum! performance! that! enable! a! reduction! in! the! required!energy.!!

• Maintain!conditions!that!efficiently!eliminate!flooding,!channelling,!entrainment!and!foaming.!!

3) Integrate! solvent=process! CO2! capture! plants! with! optimally! retrofitted! CO2! emitting!plants! including! a! supercritical! lignite! fired! steam! power! plant,! a! modern! supercritical!hard=coal!fired!power!plant,!a!natural!gas!fired!combined!cycle!plant!and!a!quicklime!plant!aiming!to:!!• Reduce!the!overall!pre=!and!post=combustion!process!costs.!• Accomplish! the! targeted! reductions! by! implementing!methods! for! optimum! plant=

wide!design!and!operation!(e.g.!total=site!integration!etc.)!aiming!at!the!utilisation!of!the! cheapest! waste! heat! available! on! the! sites! (e.g.! condensing! turbine! outlet! for!power! plants! and! industrial! plants,! as!well! as! excess! low=pressure! steam! for! some!industrial!plants).!!

4) Pilot!plant! testing!of! the!CAPSOL!technology!under!operating!condition!encountered! in!practical!applications!ensures!process!stability!and!consistency.!

!References![1]!D’Alessandro!D.M.,!Smit!B.,!Long!R.J.!(2010),!Angew.!Chem.!Int.!Ed.,!49,!6058=6082.!![2]!ScienceDaily!(2007),!http://www.sciencedaily.com/releases/2007/11/071114163448.htm!![3]!Mac! Dowell! N.,! Florin! N.,! Buchard! A.,! Hallett! J.,! Galindo! A.,! Jackson! G.,! Adjiman! C.S.,!Williams!C.K.,! Shah!N.,! Fennell! P.! (2010),! Ener.! Env.! Sci.,!DOI:! 10.1039/c004106h,!3,! 1645=1669!!


5!

[4]!Aaron!D.,!Tsouris!C.!(2005),!40!(1),!3321=348.![5]!Klemes!J.,!Bulatov!I.,!Cockerill!T.!(2007),!Comp.!Chem.!Eng.,!31!(5=6),!445=455.!![6]! Airlie,! C.,! Carr,!M.! (2011),! EU! Carbon! Falls! as! U.K.! Tax! Pushes! Costs! Above! Osborne’s!‘Floor’,!available!in:!http://www.bloomberg.com/news/2011=03=24/u=k=s=new=carbon=tax=is=higher=than=assumed=citigroup=says.html!!CAPSOL(Main(Scientific(and(Technological(Results(!Molecular(level(advances(CAPSOL! technology! has! approached! the! solution! to! the! efficient! CO2! capture! process!through! advancements! at! various! levels.! At( the( molecular( level,! CAPSOL! developed!innovative!computer!aided!molecular!design!based!procedures! supported!by!accurate!and!adequately!validated!thermodynamic!models!in!order!to!enable!the!exhaustive!investigation!of! the! performance! of! multiple! solvents! and! solvent! blends! in! post=combustion! CO2!absorption!processes.!The!developments!in!thermodynamic!modeling!via!group!contribution!methods! and! in! computer! aided! molecular! design! tools! for! CO2! capture! processes! are!presented.!!Thermodynamic(Models(In!solvent!design!where!a!large!number!of!molecular!candidates!needs!to!be!assessed,!group!contribution! (GC)! approaches! are! an! ideal! tool.! The! molecules! are! deconstructed! into!distinct! functional! groups! that! characterize! their! chemical! composition.! The! underlying!assumption!of!such!an!approach!is!that!these!groups!give!rise!to!the!same!thermodynamic!contribution!independently!of!the!molecule!in!which!they!appear.!Once!the!parameters!for!a!group! have! been! determined! via! regression! to! experimental! data! then! this! group! can! be!used!as!a!building!block!to!form!a!molecule.!With!appropriate!use!of!the!group!contribution!method! the!properties!of! the!system!of! interest!can!be!obtained!even! in!cases!where! the!thermodynamic!behavior!might!be!unknown!but! the!parameters!of! the!groups!composing!the!system’s!molecules!are!known.!In!this!sense,!group!contribution!methods!are!essentially!predictive,! since! there! is! only! a! dependency! on! experimental! data! at! the! early! stage! of!obtaining!the!group!parameters!from!a!set!of!selected!systems!(Figure!1).!!!

!Figure(1:!Group!contribution!concept.!

!!A!significant!breakthrough! in!thermodynamic!property!modeling!was!made!by!showing!for!the!first!time!that! it! is!possible!to!develop!a!group!contribution!approach!to!represent!the!challenging! phase! and! chemical! equilibrium! of! CO2! +! water! +! alkanolamine! mixtures! at!different! temperatures! and! pressures.! This!was! achieved! by! proposing! the! use! of! implicit!reaction!models!(i.e.,!by!representing!the!reaction!products!via!association!sites)!within!the!framework!of!the!Stochastic!Associating!Fluid!Theory!with!square!well!potentials!or!SAFT=γ!


6!

SW!equation!of!state.!The!concept!of!second=order!groups!was!introduced!for!the!first!time!in!a!SAFT=type!group!contribution!equation!of!state!to!tackle!the!multifunctional!nature!of!capture! solvents.! A! large! number! of! basic! groups!were! derived.! These! form! the! essential!building!blocks!for!solvent!design.!!!The! quality! of! the! models! obtained! with! the! novel! group! contribution! models! has! been!strictly! verified! through! the! comparison! of! the!model! predictions! with! experimental! data!obtained!from!literature!or!produced!during!the!CAPSOL!project.!This!demonstrates!for!the!first!time!that!the!concept!of!implicit=models,!initially!developed!in!the!context!of!molecular!models,! which! consider! the! reaction! products! as! neutral! aggregates,! can! successfully! be!transferred! to! the! group! contribution! framework;! it! can! thus! provide! the! basis! for! a! fully!predictive!approach!to!the!design!of!novel!solvents!for!carbon!capture.!Implicit!models!also!assist!enormously!the!simulation!of!complex!CO2!separation!units.!They!greatly!facilitate!the!modeling!of!a!complex! reaction!mechanism! in! the!column!without! the!need! for! individual!material!balances!for!all!intermediate!molecular!or!electrolyte!species!that!appear.!!!A!carefully!designed!experimental!schedule!has!been!executed!within!the!CAPSOL!project!in!order! to! generate! additional! experimental! data! for! targeted! solvents! that! showed! good!potential! in! increasing!the!separation!efficiency! in!CO2!capture!units.!Equilibrium!solubility!of! CO2! in! aqueous! solutions! of! amines! and! amine! blends! measurements! have! been!performed! in! a! small! scale! absorption! column! equipped! with! packing! material.! The!experiments!justified!the!major!trends!in!the!behavior!of!the!amine!solutions!and!especially!those!consisted!of!a!mixture!of!amines.!!Such! promising! results! have! been! utilized! to! develop! a! predictive! framework! to!model! (i)!strong!electrolytes!with!SAFT=γ!SW!and!(ii)!weak!electrolytes!with!SAFT=γ!SW.!The!treatment!of!weak!and!non=spherical!electrolytes!required!new!theoretical!developments,!which!were!implemented! in! the! SAFT=γ! SW! software! to! create! SAFT=γE.! Explicit! models! consider! the!reaction!products!as! independent! ionic! species.!A!procedure! for! the!derivation!of!explicit=product! models! which! makes! use! of! the! predictive! capabilities! of! the! implicit=product!models!developed! to!date!has!been!set! in!place.! In!particular,! reliable! speciation!data!are!generated!as!a!basis!for!the!modeling!of!reaction!equilibrium.!In!other!words,!the!strategy!is!a!two=step!approach!to!solvent!selection,!in!which!implicit=product!models!are!first!used!to!identify! promising! solvent! candidates,! and! the! best! options! are! then! investigated! using!explicit=product!models!that!provide!a!more!detailed!description!of!mixture!behavior,!and!of!the!performance!of!the!capture!process.!In!this!regard!a!new!version!of!the!theory!has!been!presented,!the!SAFT=γE!EoS.!This!new!EoS!also!takes!into!account!electrostatic!interactions,!and! is! therefore! capable! of! explicitly! describing! the! ionic! species! obtained! as! reaction!products!in!aqueous!mixtures!of!alkanolamines!and!carbon!dioxide.!!Solvent(Selection(Methodology(A!Computer!Aided!Molecular!Design!(CAMD)!framework!is!developed!which!is!subsequently!used!to!design!and!select!novel!solvents.! Intense!research!efforts! reported! in!recent!years!are!predominantly! based!on! lab! and!pilot=scale! experiments! to! select! solvents!which!may!potentially! improve! the! overall! performance! of! absorption/desorption! CO2! capture.!However,!this!is!very!challenging!due!to!a)!the!highly!non=ideal!solvent=CO2=water!chemical!interactions,! b)! the! countless! combinations! of! potential! capture! solvent! and! blend!


7!

candidates,! and! c)! the! need! for! combined! consideration! of! numerous! thermodynamic,!kinetic!and!sustainability!properties!as!performance!criteria!prior!to!selecting!solvents!with!optimum! capture! features.! CAMD! can! help! address! these! challenges! and! have! been!successful! in! supporting! the! synthesis! of! molecules! with! desired! physical,! chemical! and!environmental!properties!in!non=CO2!separations.!Despite!extensive!developments!in!CAMD!methods,! few! recent!works! reported!before!CAPSOL! their! utilization! in! the!design!of! CO2!capture! solvents! or! mixtures! for! chemical! and! physical! absorption! using! the! Statistical!Associating! Fluid! Theory! with! potentials! of! Variable! Range! (SAFT=VR)! and! for! physical!absorption!using! the!Perturbed!Chain!Polar!Statistical!Associating!Fluid!Theory! (PCP=SAFT).!While! these! approaches! enable! an! accurate! and! reliable! determination!of! solvent=process!vapour=liquid!equilibria,!the!set!of!few!solvents!screened!to!date!will!be!further!expanded!as!research! efforts! extend! the! rigorous! predictive! capabilities! of! SAFT=based!models! towards!additional!molecular!structures.!!In!CAPSOL,!the!use!of!an!optimization=based!CAMD!method!whose!steps!are!shown!in!the!schematic! of! Figure! 2! is! employed! to! select! post=combustion! CO2! capture! solvents! of!optimum! performance! in! molecular! and! mixture! properties! associated! with!thermodynamics,! kinetics! and! sustainability.! For! the! first! time! in! published! literature!numerous! properties! were! considered! as! performance! criteria! reflecting! solvent!characteristics! based! on! thermodynamic! (e.g.! vapor! pressure,! CO2! solubility! etc.),! kinetic!(solvent!basicity,!steric!hindrance!etc.)!and!sustainability!(e.g.!health!and!safety!hazard,!life!cycle! assessment! etc.)! behavior.! The! simultaneous! consideration! of! properties! selected! to!capture!the!molecular!chemistry!effects!on!the!absorption/desorption!process!compensates!for!the!utilization!of!simpler!models!and!ensures!the!selection!of!fewer!but!more!effective!solvents.!Different!functionalities!of!the!employed!CAMD!method!were!used!both!to!design!optimum,! novel! molecular! structures! and! to! screen! a! dataset! of! commercially! available!amine!solvents!suitable!for!CO2!capture.!Several!models!were!considered!simultaneously!for!the!prediction!of!the!properties!used!as!solvent!performance!criteria!in!order!to!account!for!uncertainty! in! the! selection! procedure.! The! obtained! results! (presented! above)! revealed!interesting!structure=property! trade=offs!and!pointed! to!commercial!molecules!which!have!very!recently!been!considered!or!have!yet!to!be!employed!as!capture!solvents.!!The! aim! of! the! work! has! been! further! extended! to! include! the! investigation! of! the!performance!of!binary!mixtures!that!appear!to!be!promising!as!CO2!capture!solvents.!In!this!context! a! broad! range! of! mixture! compositions! (i.e.! structure! of! each! component! in! the!mixture)!and!concentration! (i.e.!amount!of!each!component! in! the!mixture)! is! considered.!Note! that! this! is! the! first! time! that! such! an! approach! has! been! attempted.! The! literature!review!regarding!mixtures!utilized!as!CO2!capture!solvents!indicates!that!few!options!were!previously! examined! using! ad=hoc! selection! approaches.! Instead,! this! CAPSOL! proposes! a!systematic! selection! approach! involving! several! decision! making! stages.! Initially,! we!determine! a! set! of! mixture! properties! as! selection! criteria! and! investigate! the! ability! of!several! different! models! to! provide! valid! property! predictions! compared! to! experimental!data.! The! considered! criteria! reflect! the! impact! of! different! mixture! chemistries! on!important! absorption/desorption! process! characteristics! associated! with! efficient! CO2!capture.!They!are!implemented!in!several!selection!stages!in!order!to!refine!a!rich!initial!set!of!mixtures! and! to! identify! those! that!may! be! considered! as! capture! candidates.! A!multi=criteria! assessment!methodology! is! combined!with! a! systematic!uncertainty!quantification!


8!

approach!to!unveil! important!performance!trade=offs! in!view!of! the!non=ideal!solvent=CO2!interactions.! To!highlight! the! impact!of!uncertainty! in! the!mixture! selection!procedure!we!compare!a!case!where!uncertainty!is!not!considered!during!the!selection!with!a!case!where!uncertainty! is!considered.!The!two!sets!obtained! in!both!cases! indicate!differences! in!both!mixture!components!and!performance!characteristics.! It! is!observed!that!the!consideration!of! uncertainty! in! the! selection! procedure! results! in! a! more! coherent! set! of! CO2! capture!candidates.!Further!analysis!of!the!results!indicates!that!several!highly=performing!mixtures!identified! in! the! two! cases! share! one! of! the! two! components,! while! the! impact! of! each!component!in!the!mixture!performance!is!also!investigated.!!!

!!

Figure(2:!Computer!Aided!Molecular!Design!in!CO2!capture!solvents.!!!Overall!a!database!of!459!molecular!structures!was!generated!from!the!implementation!of!CAMD.!126!amines!were! found! in!publicly!available!databases!or!previously! considered!as!CO2! capture! solvents! in! absorption/desorption! systems,! while! 333! solvents! are! potential!novel! structures.!All! the!molecules!were!evaluated!and! rank=ordered!using!a!performance!index!which!unifies!all!the!properties!considered!as!solvent!selection!and!design!criteria.!The!obtained!results!were!broken!down!into!4!classes!(categories)!of!molecules!based!on!their!performance!ranking.!!!•!The!1st!class!considers!the!top!10!structures!of!the!25!molecules!previously!employed!as!CO2!capture!solvents!(Reference!class).!!


9!

•! The! 2nd! class! considers! the! top! 10! molecules! resulting! from! rank=ordering! the! 459!available!molecules,! denoted! as! class! of! Designed!molecules! although! it! also! includes! the!126!amines!found!in!databases.!!•!The!3rd!class!considers!only!the!top!10!structures!of!the!126!solvents!found!in!databases,!denoted!as!class!of!commercially!available!molecules.!!•!The!4th!class!focuses!only!in!the!top!10!alkanolamines!among!the!126!molecules!denoted!as!the!Commercial!Alkanolamines!class.!!!

!!

Figure(3:!Performance!assessment!of!CO2!capture!solvents.!!!The! obtained! results! depicted! in! Figure! 3! clearly! indicate! that! the! class! of! designed!molecules! performs! better! than! all! other! classes! (the! lower! the! aggregate! performance!index! the!more!preferable! the! solvent! is),!whereas! commercially! available!molecules!exist!that!have!yet! to!be!considered!as!CO2!capture!solvents!and!perform!better! than!available!solvents.!Monoethanolamine!(MEA),!which!the!most!commonly!used!solvent!in!amine!based!CO2! capture! processes! exhibits! a! lower! score! than! most! of! the! other! selected! solvents.!Figure! 4! shows! the! comparative! performance! of! some! selected! solvents! in! properties!(molecular! volume,! Vm,! vapor! pressure,! Pvp,! surface! tension,! σ,! liquid! heat! capacity,! Cp,!viscosity,! n,! CO2! solubility,! RED,! basicity,! pKa)! used! to! form! the! aggregate! performance!criterion.!!In! conclusion,! CAPSOL! advances! in! both! group! contribution! thermodynamic!modeling! and!CAMD!enables!the!identification!of!a!small!set!of!molecules!that!exhibit!high!performance!in!terms! of! desired! properties! associated! with! the! capture! process.! The! list! of! molecules!extends! the! current! state=of=the=art! at! it! includes! molecules! that! have! not! yet! been!researched! in! CO2! capture! studies.! Therefore,! the! list! of! highly! performing! molecules!includes! some! that! have! been! identified! by! other! researchers! as! potential! good! colvent!candidates.!


10!

!(

Figure(4:!Comparative!performance!of!2=amino=2=methyl=1=propanol!(AMP),!2=(methylamino)=ethanol!(MMEA),!N=methyl=1,3=Propanediamine!(MAPA)!and!Hexylamine!

(HEXA).!!!Unit(operations(level(advances(At( the( unit( operations( level,! CAPSOL! developed! innovative! absorption! process!models! of!variable! resolution! and! phenomena! descriptive! capability! that!were! subsequently! used! in!the! identification! of! highly! performing! process! flowsheets! and! column! internals.!Performance!was!assessed!by!considering!a!set!of!economic,!sustainability!and!operational!criteria.!The!presentation!of!the!developments!in!process!models,!optimal!design!of!process!flowsheets!and!column!internals!is!described!in!greater!detail.!!!Process(Model(Development(Process!models!are!essential!elements!for!the!identification!by!design!of!highly!performing!process! flowsheets! in! post=combustion! CO2! capture.! Therefore,! the! development! of! a!framework! for! the! efficient!modeling! of! reactive! absorption! and! desorption! processes! for!the! separation! of! CO2! from! flue! gas! with! the! help! of! aqueous! amine! or! other! type! of!solutions!becomes!of!paramount!importance.!Such!a!framework!is!consisted!of!a!complete!suite!of!mathematical!models! that!would!enable! the!description!of! all! underlying!physical!and! chemical! phenomena! that! occur! in! reactive! absorption! and! desorption! (stripping)!columns! and! further! ensure! good! accuracy! of! predictions! over! a! large! range! of! operating!conditions.!However,!models!of!different!resolution!and!degree!of!detail!are!required!for!the!variety!of! tasks! in!which!process!models!are!used.! Flowsheet! configuration!design! require!conceptual! models! that! capture! the! main! process! trends! whereas! more! detailed! and!rigorous! models! are! more! suitable! for! optimization! of! operating! conditions,! packing!structure!optimization,!and!control!system!design.!Conceptual!models!may!be!quite!simple!and! concise! in! structure! but! must! be! accurate! within! a! reasonable! limit.! More! rigorous!models! require! the! careful! identification! and! estimation! of! multiple! model! parameters!associated!with!the!phenomena!description!but!must!also!provide!the!necessary!flexibility!in!


11!

order! to! enable! the! realization! of! complex! column! configurations.! Concurrently,! models!should!be!computationally!efficient!so!that!they!can!allow!the!simultaneous!optimization!of!large! column! trains! and! sequences! in! the! course! of! complex! flowsheets! synthesis.!Computational! efficiency! is! mainly! judged! based! on! solution! effort! and! convergence!robustness!properties.!!!!Flowsheet(synthesis(and(process(design(A! generalized! framework! is! proposed! for! the! optimal! design! of! post=combustion! CO2!capture! processes! based! on! a! systemic! and! flexible! equilibrium! separation! model! that!employs!orthogonal!collocation!on!finite!elements!(OCFE)!techniques.!Within!this!context,!a!column!section!of!adaptive!separation!capability!and!functionality!serves!as!the!fundamental!structural! block! for! the! identification! of! efficient! separation! schemes.! Separation! column!sections! in! combination! with! heat! transfer! blocks! as! well! as! stream! splitters! and! mixers!enable!the!generation!and!evaluation!of!alternative!flowsheet!configurations!within!a!non=linear! optimization! program! (Figure! 5).! The! main! objectives! for! the! flowsheet! evaluation!involve! separation! and! thermal! efficiency! that! eventually! impact! the! economics! of! the!overall! process.! The! proposed! design! framework! was! used! for! the! optimal! design! of!alternative!flowsheet!configurations!for!the!separation!of!CO2!from!a!flue!gas!stream!using!amine! solutions! identified! by! the! CAMD! procedure.! The! achieved! performance! was!compared!against!the!performance!obtained!by!a!30%!weight!MEA!capture!plant.!!!The! simultaneous! assessment! and! evaluation! of! five! alternative! process! flowsheet!configurations!and! four!different! solvents! for! solvent!based!post! combustion!CO2! capture!processes! is! carried! out! in! this! work.! The! various! flowsheets! are! generated! using! a!generalized!process!design!framework!with!the!concept!of!maximizing!the!driving!forces!in!the!separation!units!and!thus!the!intensification!of!the!process.!Design!optimization!results!for!a!CO2!capture!plant!treating!a!flue!gas!from!a!quicklime!plant!reveals!that:!•! Reductions!in!the!range!of!30=35%!in!the!annual!expenses!can!be!achieved!when!2=Amino=2=methyl=1=propanol!(AMP)!is!used!as!the!CO2!capture!solvent.!•! Absorber! intercooling! enhances! the! process! behavior! significantly! and! leads! to! a!subsequent!reduction!of!both!capital!and!operating!expenses.!•! Reduced! energy! demand! was! achieved! (1.79! GJ/ton! CO2)! using! AMP! and! a!combination!of!stripper!stream!redistribution!and!absorber!intercooling.!Previously!reported!values!from!the!CESAR!project!include!2.9!GJ/ton!CO2!using!absorber!intercooling.!•! Using!a!combination!of!stream!redistribution! in!the!stripper!and!intercooling!of!the!absorber,!process!cost!reductions!in!the!range!of!15=35%!can!be!attained,!depending!on!the!employed!solvent.!!!


12!

(

Figure(5:!Structure!depicting!possible!feed!location!and!stripper!side=draw!alternatives!for!the!classic!CO2!capture!flowsheet.!

!!Sustainability(Despite!the!development!of!several!general!sustainability!indicator!frameworks!in!literature,!there!is!still!a!need!to!adjust!these!and/or!develop!new!indicators!on!a!case!by!case!basis.!The! overall! goal! of! CAPSOL! has! been! to! develop! a! framework! of! sustainability! indicators!suitable!for!assessing!the!different!solvents!and!process!schemes!for!post!combustion!CO2!capture,! focusing! on! the! holistic! environmental! benefit! for! normal! process! operation!through! a! Life! Cycle! Assessment! (LCA)! approach! and! substance/process! Environmental!Health! and! Safety! (EHS)! hazard! identification! for! evaluation! of! the! harm! potential! in!accidental! scenarios.! The! framework! comprises! two! phases! of! assessment! at! the! level! of!basic!design,!substance!and!process!level!assessment.!Both!assessment!phases!are!based!on!methods! that! are! well! established! in! literature.! The! framework! has! been! modified! and!extended! as! more! information! became! available! at! subsequent! solvent/process! design!levels.!For!the!purpose!of!testing!the!methodology!and!concepts!proposed,!a!reference!set!of!solvents!was!compiled!and!assessed!on!a!substance!level.!The!substance!level!assessment!performed! included! the!application!of! two!EHS!hazard!analysis!methods,! the!EHS!method!and!Inherent!Safety! Index!(ISI)!method.!LCA!assessment! included!obtaining!the!Cumulative!Energy!Demand!(CED)!which!is!a!resource!oriented!indicator,!the!Global!Warming!Potential!(GWP)!and!the!Eco=Indicator!(EI)!99!which!are!both!damage!oriented!indicators.!Among!the!open!issues!to!be!investigated!are!the!mechanism!of!dealing!with!data!gaps!and!increasing!the!flexibility!of!different!methods,!estimating!the!LCA!indicators!through!reaction!chemistry!and!the!estimation!of!the!rates!of!solvent!degradation!and!equipment!corrosion.!!The!sustainability!assessment!shows!that!AMP! is!a!superior!solvent! from!both!an!EHS!and!LCA!point!of!view!compared!to!the!other!solvents! in!the!test!group.!However!AMP!suffers!from! slower! kinetics! and! therefore,! it! would! be! more! comprehensive! to! conduct! further!assessment!based!on!a!rate!based!model,!so!that!its!disadvantages!are!more!apparent.!Two!waste! treatment! scenarios! have! been! compared! to! account! for! solvent! loss! through!degradation! and! to! reduce! the! impact! of! degradation! products! formed.! The! reclaimer!scenario! that! involves! the! regeneration! of! the! degraded! amine!was! shown! to! give! better!


13!

performance! from! an! LCA! perspective! (5=15%! improvement! in! different! LCA! metrics),!whereas!the!EHS!assessment!was!mostly!insensitive!to!the!change!as!there!are!no!significant!differences!within! the!process!boundaries!between!both!cases.! It! is! important! to! consider!degradation!products,!although!the!parent!amine!will!still!dominate!the!results!of!most!EHS!metrics,!due!to!its!higher!mass!in!the!system.!!!Control(and(operations(The!optimization=based!approach! in!the!calculation!of!efficient!CO2!capture!process!plants!aims!at!the!simultaneous!determination!of!the!flowsheet!configuration!and!the!equipment!design!parameters.!However,!the!capture!plant!is!required!to!operate!under!variable!process!conditions! due! to! either! production! level! shifts! or! the! influence! of! unexpected! process!disturbances.! In! order! to! ensure! the! satisfaction! of! the! operating! and! economic!specifications! for! the! CO2! capture! plant! a! reliable! and! efficient! control! system! should! be!designed! that! would! be! able! to! alleviate! the! effects! of! disturbances! on! the! process!objectives.! The! plantwide! control! structure! must! be! then! design! and! its! performance!investigated.!To!this!end,!a!set!of!candidate!flowsheet!and!control!structure!configurations!must!be!analyzed!under!the!presence!of!multiple!and!large!in!magnitude!disturbances!that!are! likely! to! affect!process!operation!and!process!economics.! It! is! generally! accepted! that!the!economic!result!of!a!process!system!may!be!significantly!altered!if!the!process!systems!failed!to!quickly!recover!from!the!influence!of!a!disturbance.!!!Specifically,! a! capture! system!must! compensate! for! variable! flue!gas! volumetric! flowrates,!concentration!and!temperature,!changes!in!the!kinetics!of!the!reactions,!uncertainty!in!the!thermodynamic! property! prediction,! and!malfunction! of! the! various! equipment! that! form!the! overall! system.! Such! changes! may! occur! with! different! intensity! and! frequency.! The!influence!of!variability!in!the!operating!environment!will!affect!the!amount!of!CO2!capture!by! the! system,! and! the! conditions! in! the! unit! operations! that! subsequently! influence! the!energy!requirements!for!the!capture!of!CO2!and!the!economics!of!the!plant!(Figure!6).!It!has!been! exhibited! within! the! CAPSOL! project! that! a! specific! solvent! capture! system! that!recorded! good! economic! performance! at! the! nominal! operating! conditions! may! have! its!performance! drastically! deteriorating! under! the! presence! of! commonly! occurring!disturbances.! It! is! then! suggested! that! the! evaluation! of! process! flowsheets! incorporating!commercial!or!novel!solvents!should!consider!the!impact!of!the!disturbances.!Therefore,!the!design!and!implementation!of!a!capable!control!system!is!of!paramount!importance!for!the!efficient!operation!of!a!capture!plant.!((


14!

!!

Figure(6:(Motivating(scenario(for(disturbance(effects(in(CO2(capture(plants.(((The!approach!that!is!employed!involves!the!evaluation!and!screening!of!alternative!process!flowsheet!and!control!structure!configurations!in!a!rigorous,!effective!and!systematic!way.!It!utilizes!an!effective!decomposition!of!the!process!and!control!system!design!tasks,!which!in!sequence!allows! the!enhancement!of! the!process! controllability!properties.! The!quality!of!the! steady! state!behavior! in! response! to! the!detrimental! effects! of!multiple! simultaneous!process!disturbances!and!model!parameter!variations! is!an!essential!prerequisite! for!good!economic! performance! during! operation.! Disturbance! rejection! sensitivity! for! a! candidate!process! flowsheet! is! investigated! in! conjunction! with! decisions! encompassing! plantwide!control!objectives! for! the!process.!The!objectives! reflect! the!hierarchy! in!achieving!certain!targets! and! exploiting! available! resources! for! control! purposes.! The! controllability!framework! enables! the! evaluation! of! control! strategies! outlined! by! the! weighting! of! the!objectives!and!the!input=output!structure!of!the!candidate!controller.!The!method!employs!rigorous!and!detailed!mathematical!models!that!intend!to!capture!nonlinear!effects!arising!from! the! physical! system! and! potentially! intensified! by! the! interactions! of! multiple! and!simultaneously! acting! disturbances.! Disturbance! directionality! and!magnitude! are! two! key!factors! that! are! thoroughly! investigated! and! explored.! The! calculation! of! a! static!controllability! performance! index! representative! of! the! static! disturbance! rejection!characteristics! becomes! the! basis! for! the! assessment! and! ranking! of! the! alternative!flowsheets!and!control!structures.!!!Dynamic!characteristics!of!the!candidate!process!design!play!the!most!dominant!role!in!the!achievable! dynamic! performance! of! the! control! system.! The! performance! of! the! control!system! is! inherently! affected! by! the! dynamics! of! the! designed! process.! Process! dynamic!characteristics! are! influenced! not! only! by! process! design! decisions! but! also! by! model!parameters! variations.! Sensitivity! analysis! determines! the! margins! of! the! process! design!from!undesired!dynamic!behavior!(e.g.,!unstable,!undesired!oscillatory!or!sluggish!response)!at! the! presence! of! uncertainty.! Nonlinear! process! models! act! as! the! basic! tools! for! the!


15!

identification! of! the! process! dynamic! components! during! a! disturbance! scenario! that!involves!multiple!disturbances!of!finite!magnitude.!!!The! modification! of! the! design! decision! variables! using! nonlinear! sensitivity! information!becomes!an!additional! instrument!for!the!design!engineer! in!order!to! improve!the!desired!static! and! dynamic! properties! of! the! plant.! Flowsheet! design! parameters! are! associated!either!with!the!structure!of!the!flowsheet!(e.g.,!selection!of!units,!connectivity!of!units!and!so! forth)! or! the! equipment! design! specifications.! The! disturbance! rejection! exercises! and!their! influence! on! the! static! and! dynamic! controllability! indices! reveal! the! relationship!among! performance! indicators! and! design! parameters.! Proper!modification! of! the! design!parameters! utilizing! nonlinear! sensitivity! analysis! calculations! can! enhance! the! static! and!dynamic! controllability! properties! of! the! design! while! maintaining! the! economic!attractiveness!of!the!final!design.!The!complete!design!procedure!is!outlined!in!Figure!7.!((

((

Figure(7:(Integrated!process!design!and!control!framework.!!((Column(internals(design!The! selection! of! suitable! column! internals! is! an! important! prerequisite! for! an! optimum!operation!of!gas=liquid!separation!processes.!The!removal!of!CO2!from!gas!mixtures!realized!by! absorption! into! a! liquid! solvent! is! usually! performed! in! columns! filled! with! structured!packings.! Standard! structured! packings! have! a! corrugation! angle! of! 45! degrees! or! 60!degrees.! Using! different! possible! corrugation! angles! may! result! in! better! column!performance.!The!corresponding!analysis!can!be!done!with!model=based!simulations.!!The! aim! of! CAPSOL! project! was! to! develop! an! integrated! modeling! framework! for! the!complementary! application! of! three! modeling! approaches,! namely,! Computational! Fluid!Dynamics! (CFD),! Hydrodynamic! Analogy! (HA)! and! the! Rate=based! Approach! (RBA).! This!framework! should! be! used! to! facilitate! design! of! innovative! internals! and! equipment! for!solvent=based!CO2!separations.!The!characteristics!of!the!models!in!terms!of!model!accuracy!


16!

and!flow!complexity!as!well!as!the!information!flow!from!one!model!realization!to!the!others!is!shown!in!Figure!8.!!!

!Figure(8:!Complementary!modeling!in!the!design!of!structured!packing.!

!!Computational! fluid! dynamics! models! aim! at! describing! the! flow! characteristics! in! a!representative! packing! element.! It! is! assumed! that! the! element! is! repeated! in! order! to!represent! the! entire! structure.! The! model! calculates! the! flow! pattern! and! enables! the!prediction! of! the! dry! pressure! drop! in! structured! packing.! The!model! has! been! validated!using!experimental!data!in!equivalent!units.!!Hydrodynamic! analogies!models! represent! real! complex! two=phase! flow! in! a! packing! as! a!combination! of! geometrically! simpler! flow! patterns! (Figure! 9).! In! the! physical! model! the!packing!is!represented!as!a!bundle!of!parallel!inclined!channels!with!identical!cross!section.!The!number!of!the!channels!as!well!as!their!diameter!is!determined!from!the!packing!surface!area!and!corrugation!geometry.!The!gas!flow!behaviour!depends!on!the!operating!conditions!and!varies!from!laminar!to!fully!developed!turbulent!flow.!The!liquid!flows!counter=currently!to!the!gas!flow!in!form!of!laminar!films!over!the!inner!surface!of!the!channels.!Additionally,!a!uniform!distribution!of!the!both!phases!in!radial!direction!is!assumed,!i.e.!no!maldistribution!is!taken!into!account!in!the!model.!The!required!parameter!for!the!proper!description!of!the!gas=phase!turbulence!in!the!HA!model!was!estimated!using!CFD!analysis!of!single=phase!gas!flow!through!structured!packing.!!Rate=based!models!consider!the!entire!separation!column!as!a!series!of!stages!in!which!mass!transfer,! reaction! kinetics! and! equilibrium,! and! fluid! dynamics! (Figure! 10).! Diffusion! and!mass! transfer! coefficients! as! well! as! hold=up! and! interfacial! area! are! being! estimated!through!the!“virtual!simulated!experiments”!using!CFD!and!HA!models.!Rate=based!models!can!then!determine!the!required!packing!height!for!a!given!absorption!rate.!!!


17!

!!

Figure(9:!Flow!pattern!representation!through!hydrodynamic!analogies.!!!

!!

Figure(10:!Rate!based!model!representation.!!!The!integrated!modeling!framework!for!simulation!of!innovative!structured!packings!for!the!CO2!absorption!has!been!utilized!in!MEA!and!other!CAPSOL!solvent!solutions.!The!simulated!procedure! achieved! the! investigation! of! the! influence! of! corrugation! angle! of! structured!packings!on!the!separation!efficiency!and!dry!pressure!drop.!!Modeling! of! gas=liquid! separation! processes! usually! requires! experimentally! determined!parameters! such! as! mass! transfer! coefficients,! which! cannot! be! determined! without!expensive!experimental!work.!A!novel!modeling!approach!based!on!hydrodynamic!analogies!(HA)!has!recently!been!developed!and!successfully!tested!for!distillation!units!equipped!with!structured! corrugated! sheet! packings.! The! HA! approach! is! an! alternative!way! to! describe!hydrodynamics!and!transport!phenomena!n!processes,!in!which!exact!location!of!the!phase!boundaries! is!hardly!possible.!Contrary!to!the!traditional!models!based!on!the!film!theory,!separation!columns!can!be!described!without!using!mass!transfer!coefficient!correlations.!!


18!

In! CAPSOL,! the! HA! approach! was! applied! to! carbon! dioxide! absorption! into! aqueous!monoethanolamine.! The! composition! profiles! were! determined! in! an! absorption! column!filled!with!structured!packings!and!subsequently!checked!against!experimental!data.!The!HA!model!has!been!For!the!gas!phase,!concentrations!at!the!top!and!bottom!were!measured.!For!the!liquid!phase,!full!concentration!profiles!were!determined.!!!Column(packing(manufacturing(Post=combustion!capture!plants,!as!considered!in!the!CAPSOL!project,!apply!absorption!and!desorption!technology!to!separate!CO2!from!flue!gas.!The!project!focused!on!the!absorption!of!CO2! into!amine!based! solvents! followed!by! stripping!of!CO2! in! a!desorber,!which!up! to!date!is!considered!to!be!the!most!promising!technology.!Hence,!columns!for!absorption!and!desorption!are! involved!that!apply!these! internals.! It! is!well!known!that!choosing!the!right!technology! for!mass! transfer! internals! is! very! important,! as! their! specific! characteristics! in!terms! of! pressure! drop,! hydraulic! and! separation! performance! are! significant! factors! for!operating!and!investment!costs!of!CO2!capture!plants.!!The!most! promising! structured! packing! characteristic! to! be! optimized! for! CO2=absorption!purposes!was!identified!to!be!the!specific!pressure!drop.!A!lower!specific!pressure!drop!will!lead!to!reduced!energy!consumption!of!the!flue!gas!blower.!The!predominant!modification!method! to! reduce! the!pressure!drop! is! to! increase! the! inclination! angle! of! the!oppositely!oriented! flow! channels! of! corrugated! sheets! structured! packings! are! made! of.! CFD!simulations! were! performed! and! the! diagram! shown! in! Figure! 11! could! be! derived.! The!diagram! shows! the! dry! pressure! drop! depending! on! the! inclination! angle! for! various! F=factors!(column!loading!factor).!!!

!!

Figure(11:(Changing!of!pressure!drop!with!increasing!inclination!angle.(!!


19!

As! can! be! seen,! at! inclination! angles! above! 70°,! the! pressure! drop! is! only! decreasing!marginal.!At!this!point!it!was!decided!to!manufacture!a!packing!with!an!inclination!angle!of!75°! by! Julius! Montz! GmbH! (MONTZ)! (Figure! 12).! This! packing! would! show! a! very! low!pressure!drop,!while!the!film!flow!at!the!packing!surface!could!still!persist.!!!

!!!!!!!!!!!!!! !

!!

Figure(12:(B1=250.75!packing!at!Julius!Montz!GmbH.(!!Fluid! dynamic! experiments! at! the! University! of! Paderborn! (UPB)! confirmed! the! drastic!reduction! of! the! pressure! drop! for! both! dry! and! irrigated! conditions.! Figure! 13! shows! a!comparison!of! the!measured!dry!pressure!drop! for! a! packing!with!45°! and!75°! inclination!angle.!Figure!14!shows!the!same!comparison!at!irrigated!conditions.!At!F=factors!between!2!and!3!Pa0,5!the(pressure(drop(can(be(reduced(by(90(to(97%.!!!


20!

!!

Figure(13:(Comparison!of!the!dry!pressure!drop!of!packings!with!45°!and!75°!inclination!angle.!

!!

!!

Figure(14:(Comparison!of!the!pressure!drop!of!irrigated!packings!(45°!and!75°!inclination!angle)!at!20!m3m=2h=1.!

!!In! addition,! experiments! were! conducted! to! evaluate! the! absorption! efficiency! using! this!new! packing.! As! expected,! the! absorption! rate! is! slightly! decreased! for! the! new! packing!geometry! with! the! steeper! inclination! angle.! However,! this! reduction! does! not! place! a!critical! burden! in! the! associated! capital! costs! of! the! capture! plant! and! is! therefore!considered!a!reasonable!compromise.!!!!


21!

Pilot(plant(testing((During!the!CAPSOL!project!a!pilot!plant!for!the!absorption!and!desorption!of!CO2!was!built!at!the!University!of!Paderborn.!The!pilot!plant!(Figures!15!to!20)!is!conceived!as!a!multi=purpose!plant.!Experiments!can!be!carried!out! in! four! operation!modes:! batch! absorption,! batch!desorption,! closed! loop! and!fluid!dynamics.! In!order!to!enable!all! four!operation!modes,! the!plant!comprises!two!glass!columns,!one!with!an! inner!diameter! (ID)!of!100!mm!and!another!with!an! ID!of!300!mm.!Both!columns!are!about!5!m!high,!and!each!column!includes!a!packed!section!of!about!3!m!height.! The! smaller! column! is! to! be! predominantly! used! for! absorption.! Due! to! the! small!diameter! and! consequently! considerable!wall! effects,! this! column! is! not! suitable! for! fluid!dynamic!experiments.! In!contrast,! the!bigger!column!can!be!used!both! for!desorption!and!for!fluid!dynamic!experiments.!To!realize!a!closed!loop!mode,!both!columns!are!to!be!linked.!The!absorption!(small)!column!can!be!operated!at!F=factors!varying!between!1!and!3.5!Pa0,5!and! liquid! loads! between! 10! and! 60! m3m=2h=1.! In! desorption! mode,! the! large! column! is!operated!with!the!same!liquid!loads!as!the!absorption!column.!In!fluid!dynamic!mode,!it!can!be!operated!at!F=factors!varying!between!1!and!4!Pa0,5!and!liquid!loads!between!20!and!90!m3m=2h=1.!A!detailed!flow!sheet!of!the!plant!is!given!in!Figure!20.!!!

!!

Figure(15:!Pilot!plant!at!Universität!Paderborn.(!!


22!

!(

Figure(16:(Columns!before!insulation.!!!

!!

Figure(17:(Upper!part!of!the!pilot!plant!with!isolation.!!!


23!

!!

Figure(18:!Isolated!desorption!column.!!!

!!Figure(19:(Gas!blowers!(a),!and!the!system!for!CO2!recycling!consisting!of!a!vacuum!pump,!a!

compressor!and!a!CO2!pressure!tank!(b).!!

(a)$

(b)$

!CAPSO

L!Final!Publishable!Summary!Report!

!

24!

!Figure'20:'Process!flow

!sheet!of!UPB!pilot!plant.!


25!

!

Before!the!plant!was!used!to!test!the!new!CAPSOL!packing!and!solvent! it!was!validated!by!

performing! fluid! dynamic! and! absorption! experiments.! To! this! end,! Figure! 21! shows!

measured!values!of!the!dry!pressure!drop!depending!on!the!FHfactor.!Measurements!at!UPB!

using!both!columns!are!compared!to!measurements!by!Julius!Montz!GmbH!using!a!column!

with! an! inner! diameter! of! 600!mm.! It! can! be! seen! that!UPB!measurements! at! the! bigger!

column!(diameter!of!300!mm)!agree!well!with!the!values!obtained!by!Montz.!

!

!

!

!

Figure'21:'Pressure!drop!of!dry!packing:!UPB!measurements!compared!to!the!values!of!Julius!

Montz!GmbH.!

!

!

Measurements!of!the!pressure!drop!of!irrigated!packing!were!carried!out!at!liquid!loads!of!

10,! 20! and!50!m³mH2hH1.! For! low! liquid! loads,! our!measurements! showed!good!agreement!

with!the!values!by!Montz!(see!Figure!22).!The!slight!deviation!can!be!explained!by!the!clearly!

smaller! diameter! of! our! column! compared! to! the! column! at!Montz.! A! higher! deviation! in!

Figure! 16! at! a! liquid! load! of! 50!m3m

H2hH1! is!most! likely! due! to! water! accumulation! in! the!

pressure!measuring!system!resulting!in!measurement!errors.!

!

Based!on! these! tests,! it! can!be! concluded! that! the!bigger! column!at!UPB! is! applicable! for!

studying!fluid!dynamics!of!different!packings.!

Additionally,! absorption! experiments! with! monoethanolamine! were! performed.! Three!

experiments! A1! to! A3! (summarized! in! Table! 1)! were! carried! out! with! liquid! loads! of! 17!

m3m

H2hH1!and!FHfactors!of!about!1.6!Pa

0.5.!The!solvent!was!a!14!%!wt!aqueous!MEA!solution.!

The!inlet!CO2!mole!fraction!varied!between!0.045!and!0.091.!

!


26!

!

!

!

Figure'22:'Pressure!drop!of!irrigated!packing:!UPB!measurements!compared!to!the!values!by!

Montz.!

!

!

Table'1'/'Process'conditions'of'experiments'A1'to'A3.'! !!"#$%&',!!!"! !!"#$%&',!!!"! !!"#,!!!"! !!"#,!!!"! !!"#,!!!"! !!!!,!!!"!! kg h! °C! g/g! m! h! °C! mol mol!A1! 130.0! 22.8! 0.14! 42.2! 22.8! 0.045!

A2! 130.0! 22.3! 0.14! 43.6! 22.8! 0.091!

A3! 130.0! 21.5! 0.14! 43.0! 22.6! 0.070!

!

!

Figure! 23! shows! the! gasHphase! CO2! concentration! profiles! and! Figure! 24! the! temperature!

profiles!along!the!column!height.!

!

!

!

Figure'23:'Measured!CO2!concentration!profiles!for!experiments!A1!to!A3.!


27!

!

!

!

!

'Figure'24:'Measured!temperature!profiles!for!experiments!A1!to!A3.!

!

!

As!the!profiles!are!showing!reasonable!trends,!we!can!conclude,!that!the!pilot!plant!can!be!

used! with! confidence! for! thorough! experimentation! in! the! field! of! packing! and! solvent!

design.!

!

!

Plant'level'advances'Several! industrial! plants! in! power! generation! have! been! considered! for! the! integration! of!

CO2!capture!plant!units.!The!four!selected!reference!power!plants!are:!

•! Supercritical!lignite!fired!steam!power!plant!of!a!power!output!of!650!MWe!gross.!

•! Supercritical!bituminous!coal!fired!power!plant!of!a!power!output!of!650!MWe!gross.!

•! Natural!gas!fired!combined!cycle!of!420!MWe.!

•! Quicklime!production!plant.!

!

The! 650!MW!bituminous! plant! is! based! in! the! CESAR!WP2!Deliverable!D2.3.1! –! “Baseline!

Powerplant!Documents”!

(http://www.co2cesar.eu/downloadables/Deliverables%20Public%20Summaries/CESARH

D2.3.1HAPPROVEDHBaseline%20Power%20Plants%20Documents%20PUBLIC%20SUMMARYH

2010.03.26.pdf)!.!!

The!natural!gas!fired!combined!cycle!of!420!MWe!from!the!Scottish!Power!report!whereas!

the! 650! MW! lignite! fired! steam! power! plant! as! well! as! the! quick! lime! plant! are! new!

reference!plants!for!the!CAPSOL!project.!!

The! framework! describes! general! technical! and! economic! assumptions! and! a! possible!

procedure! for! evaluation! of! different! CO2! capture! technologies! both! on! quantitative!

evaluation!parameters!such!as!breakHeven!electricity!cost,!specific!CO2!emission!avoidance!

cost! etc.! and!on!18!different!qualitative!evaluation!parameters.! The!assessment! approach!

described!here!is!aligned!with!the!methodology!being!used!in!other!FP7!projects!through!a!


28!

!

joint!working!panel!known!as!the!European!Benchmarking!Task!Force,!whose!activities!are!

reported! under! CESAR! WP2.4!

(http://www.co2cesar.eu/downloadables/Deliverables%20Public/CESARHD2.4.1HAPPROVEDH

EBTF%20Common%20Framework%20Definition%20Document%202009.08.28.pdf).!

!

Heat'Integration'Lignite'Fired'Power'Plant:!The!650!MWe!superHcritical! ligniteHfired!power!plant!with!a!CO2!

capture! process! has! been! considered,!where! the! capture! unit! has! been! in! two! variations:!

operating!with!MEA!and!CAPSOL!capture!system.!When!the!CO2!capture!unit!with!MEA! is!

simply!added!to!the!plant!using!directly!steam!extracted!from!the!turbine!train!for!reboiler!

heating,! the!power!generation!reduction! (power!penalty)!of! the!plant! is!97.8!MWe.!This! is!

equivalent! to! 15!%! comparing! the! nonHoptimized! lignite! power! plant!with! carbon! capture!

and!the!standalone!lignite!power!plant.!The!cooling!requirement!in!this!case!is!760.9!MW.!!

!

The! proposed! heat! integration! options! reduce! the! steam! extraction! from! the! turbine! for!

condensate! return! heating,! and! reduce! the! power! penalty! of! the! turbine! island.! The!

integrated! process! generates! 577.1! MWe! of! power! and! requires! 654.0! MWth! of! cooling!

utility.! The! power! generation! increases! by! 24.8! MWe,! while! the! cooling! demand! of! this!

integrated! process! is! reduced! by! 106.9! MWth.! The! power! generation! penalty! is! 11.2! %!

comparing! the! heat! integrated! lignite! power! plant! with! carbon! capture! and! standalone!

lignite!power!plant!without! carbon! capture!unit.!As! a! result,! the!heat! integration!helps! in!

reducing!the!power!penalty!from!CO2!capture!by!15H11.2!=!3.8!%.!

!

The!revenue! from!gross!power!generation! is!equivalent! to!an!average!of!€!379.1!x!106!/y.!

However,!the!process!integration!options!are!able!to!save!€!25.6!x!106!/y!of!utility!cost.!The!

CAPSOL!capture!system!has!also!been!evaluated,!where!the!heat!integration!is!able!to!save!

5.39!MWe!gross!power.!The!cooling!demand!of! the!carbon!capture!plant!with! the!CAPSOL!

technology!increases!by!404.7!MW,!while!the!gross!power!penalty!reduces!to!10.40!%.!

!

Coal'Fired'Power'Plant:!The!nominal!capacity!of!the!plant!is!650!MW!electricity!generation.!

The!standalone!power!plant!needs!only!a!cooling!utility!for!624.7!MW!and!adding!the!MEA!

based!CO2!capture!increases!that!to!655.8!MW.!Several!heat!integration!options!have!been!

identified!and!implemented.!

!

Adding! the! capture! unit! to! the! standalone! coal! power! plant! introduces! power! penalty! of!

91.9!MW! (14.1!%! of! the! nominal! capacity).! The! Process! Integration!measures! reduce! the!

penalty! to! 10.4!%! (3.7!%! saving).! For! the! CAPSOL! capture! system! the! process! integration!

options!are!able!to!save!€!9.7!x!106!/y!of!utility!cost.!The!gross!power!output! increases!by!

8.46!MWe,!which!is!equivalent!to!reducing!the!power!penalty!to!9.05!%!!(14.1H9.05!=!5.05!%!

saving)!of!the!nominal!plant!rating.!!

!

Gas'Fired'Power'Plant:'The!nominal!power!generation!of!the!plant!is!423.5!MW.!The!total!

minimum! cooling! demand! for! the! standHalone! power! plant! and! the! one! with! MEA! CO2!

capture! unit! is! found! to! be! 123.8!MW! and! 333.2!MW,! respectively.! Process!modification!

options!have!been!identified!for!reducing!the!energy!requirement!and!the!power!penalty.!!

!


29!

!

The!power!penalty!due!to!the!steam!extraction! for!powering!the!CO2!capture! is!30.5!MW!

(7.2! %! of! the! nominal! capacity),! which! is! equivalent! to! an! average! of! €! 20! x! 106! /y.! The!

process!integration!options!are!able!to!save!€!62.89!x!106!/y!of!utility!cost.!!

!

The! CAPSOL! capture! system! is! considered! in! the! last! part! of! the! study.! The! gross! power!

output! increases! by! 5.60!MWe,! as! result! of! the! integration!which! equivalent! to! 5.89!%!of!

power!penalty.!The!total!cooling!demands!of!the!CAPSOL!capture!plant! increased!by!826.7!

MWth.!

!

Quicklime'Plant:! The!quicklime!plant! is! a! simpler!one.! There! is! only!one! viable!option! for!

heat! integration!related!to!the!utilization!of!the!waste!heat!from!the!operation!of!Ca(OH)2!

production!from!CaO.!This!can!be!utilized!by!generating!steam!with!thermal!load!of!969!kW.!

A!portion!of! this!waste!heat! can!be! exploited!within! the!CO2! capture!process! in! order! to!

preheat!the!rich!stream!exiting!the!absorption!column!and!heading!to!the!stripper.!

!

Conclusions'CAPSOL! technology!enables! the! systematic!design!of! solvent! and! solvent!blends!based!on!

Computer! Aided! Molecular! Design! tools! that! employ! accurate! group! contribution!

thermodynamic!property!prediction!models!and!multiHcriteria!optimization!techniques.!The!

process! performance!of! the! identified! new! solvents! and! solvent! blends! against! economic,!

sustainability!and!other!environmental!criteria!is!effectively!utilized!for!the!development!of!

process!flowsheet!configuration!of!improved!ability!to!reduce!the!energetic!requirements!of!

the! CO2! capture! process.! A!multiHscale!modeling! sequence! is! at! the! center! of! a! rigorous!

procedure! to!unveil! the!complex! flow!pattern!and! transfer!phenomena!within! the!column!

internals! and!optimize! the! geometric! characteristics! of! the!packing! structure.! The!CAPSOL!

capture!plant!consisted!of! the!preferred!solvent,! the!optimal! flowsheet!configuration,!and!

the!optimized!structured!packing!has!been!integrated!thermally!with!existing!power!plant!in!

order!to!further!reduce!the!overall!energetic!requirements.!!

!

!

CAPSOL'Impact'of'Results'The!CAPSOL! impact!can!be!characterized!by!major!contributions!at!two!distinct! levels.!The!

first! level! involves! the! development! of! novel! methodologies! in! thermodynamic! property!

model!based!on!group!contribution,!computer!aided!molecular!design!for!solvent!mixtures,!

process! flowsheet! synthesis! and! design! optimization! utilizing! flexible! process!models,! and!

the! multiHscale! modeling! for! the! optimization! of! the! geometric! features! of! structured!

packing.! The! second! level! of! impact! involves! the! development! of! new! technological!

advances!in!solvent!based!post!combustion!CO2!capture!through!the!implementation!of!preH

existing!methods!and!CAPSOL!developed!methods.!!

!

A!significant!breakthrough! in!thermodynamic!property!modeling!was!made!by!showing!for!

the!first!time!that! it! is!possible!to!develop!a!group!contribution!approach!to!represent!the!

challenging! phase! and! chemical! equilibrium! of! CO2! +! water! +! alkanolamine! mixtures! at!

different!temperatures!and!pressures.!This!was!achieved!through!the!use!of!implicit!reaction!

models! (i.e.,! by! representing! the! reaction! products! via! association! sites)! within! the!

framework!of!the!Stochastic!Associating!Fluid!Theory!with!square!well!potentials!or!SAFTHγ!

SW!equation!of!state.!The!concept!of!secondHorder!groups!was!introduced!for!the!first!time!


30!

!

in!a!SAFTHtype!group!contribution!equation!of!state!to!tackle!the!multifunctional!nature!of!

capture!solvents.!A! large!number!of! interaction!parameters! for!basic!groups!were!derived.!

These! form! the! essential! building! blocks! for! novel! solvent! design.! Such!developments! not!

only!assisted! in!the! identification!of!novel!solvents! in!CO2!capture!but!also!set!the!ground!

for!extending!property!prediction!for!a!vast!number!of!applications!in!process!industry!such!

as!separations!(e.g.,!extractive!distillation)!and!catalytic!reactions.!

!

It! is! the! first! time! that! Computer! Aided!Molecular! Design! (CAMD)! has! been! extended! to!

include!the!investigation!of!the!performance!of!binary!mixtures!that!appear!to!be!promising!

as!CO2!capture!solvents.!In!this!context!a!broad!range!of!mixture!compositions!(i.e.!structure!

of!each!component!in!the!mixture)!and!concentration!(i.e.!amount!of!each!component!in!the!

mixture)! is! considered.! Incorporating! LCA! (Life! Cycle! Analysis)! and! SHE! (SafetyHHealthH

Environmental)! hazard! assessment! in! the! CAMD! results! has! identified! existing! and! newly!

proposed!molecules!with!a!potential!reduction!of!the!cradleHtoHgate!environmental! impact!

up!to!50%!(e.g.,! in!EcoIndicator!units)!and!the!hazard!impact!up!to!20%.!CAMD!framework!

assisted!by!group!contribution!thermodynamic!property!prediction!models!and!sustainability!

indices!succeeded!to!identify!multiple!solvents!and!solvent!blends!with!potentially!superior!

performance!than!currently!used!solvent!technologies.!

!

A!systematic!process!flowsheet!synthesis!and!design!optimization!framework!equipped!with!

flexible!and!accurate!process!models!achieved!in!obtaining!process!solutions!that!reduce!in!

the!range!of!39%!the!annualized!capture!plant!expenses!and!56%!the!energy!requirements.!

The! investigation!of! sustainability! in!process! solutions! further! reinforces! the! impact!of! the!

process! design! solution.! This! indicates! a! great! boost! in! CO2! capture! technology! that! can!

have!a!tremendous!impact!in!industry!and!the!environment.!The!reduction!in!the!costs!and!

energy! implies! that! the! attractiveness! of! solvent! based! CO2! capture! increases!with!more!

industry!adapting!the!technology!for!greater!CO2!reductions.!

!

Innovative!column!packing!achieved!a!97%!reduction!in!pressure!drop!for!the!flue!gas!in!the!

absorption!column!hence!minimizing!the!energy!requirements!by!the!blowers.!Considering!

the!extremely!large!volumetric!flow!rate!of!the!flue!this!is!a!significant!factor!in!reducing!the!

overall! energy! footprint.! The! new! packing! has! generated! a! new! type! of! product! that! has!

been!subsequently!used!in!the!CAPSOL!pilot!plant!successfully.!!

!

Heat!integration!in!post!combustion!capture!enables!the!efficient!utilization!by!the!capture!

plant!of!available!thermal!energy!in!the!power!plant.!The!main!aim!is!the!minimization!of!the!

overall!penalty!induced!by!CO2!capture.!Extensive!studies!in!the!most!commonly!used!type!

of!power!plants!with! fuels!varying! from!natural!gas,! to! lignite!and!coal!have! improved!the!

CO2!capture!penalty!by!4!%!H!10!%.!!

!

The!main!developments!within!CAPSOL!project!increase!the!viability!of!the!post!combustion!

CO2! capture! process,! which! subsequently! enhance! the! attractiveness! of! the! technology.!

Solvent!based!CO2!capture!remains!one!of!the!most!suitable!technologies!for!the!mitigation!

of!the!hazardous!effects!of!CO2.!CAPSOL!advances!have!added!significantly!to!the!benefits!of!

the!technology.! It! is! therefore!expected!that!more! industrial!players!will!seek!CO2!capture!

technology!that!will!increase!investments!and!employment!in!manufacturing!of!columns!and!

process!equipment,!engineering!companies!and!process!personnel.!


31!

!

!

Exploitation'potential'CAPSOL!created!exploitation!potential!in!several!areas!as!outlined!below.!

!

Advanced!solvents!and!blends.!

A!list!of!novel!solvents!with!high!potential!has!been!identified!as!a!result!of!CAPSOL!project.!

Some!of! these!solvents!have!never!been!studied!before! theoretically!experimentally.!Such!

outcome!enriches! knowledge! in! the! field! and! sets! the! ground! for! opportunities! in! further!

exploring!the!potential!use!of!these!solvents!or!solvent!blends!in!CO2!industrial!applications.!

A!plan!to!run!experimental!and!simulation!studies!for!these!solvents!will!eventually!validate!

their!performance.!!

!

Property!prediction!models.!

Process! Systems! Enterprise! Ltd! (PSE,! www.psenterprise.com)! has! acquired! the! exclusive!

rights! to! the! SAFT! software! developed! at! Imperial! College! London.! As! part! of! the!

collaboration! agreement!between!PSE! and! Imperial! College,! the! Imperial! team! is! assisting!

PSE! in!developing!applications! for! SAFT.!PSE!have! recently!developed!a!modelling! tool! for!

carbon! capture! and! storage! applications! (gCCS,!

http://www.psenterprise.com/power/ccs/gccs.html)! in! which! the! SAFT! equation! of! state!

provides! key! thermodynamic! information! for! capture! plants! and! carbon! dioxide!

transmission.!The!gCCS!tool!was!developed!in!collaboration!with!major!players!in!the!energy!

industry.!The!SAFT!models!within!gCCS!are!currently!based!on!a!molecular!representation!of!

the! components! involved,! as! developed! in! previous! work! by! the! Imperial! team.! PSE! are!

aware!of!the!progress!made!in!the!CAPSOL!project!and!CAPSOL!partners!and!PSE!will!work!

together! in! the! future! to! come! to! incorporate! the! groupHbased! representation! developed!

through! the!CAPSOL!project.! This!will! significantly! improve! the!predictive! capability!of! the!

approach!and!make! the!advances! realized!within!CAPSOL!accessible! to!all!gCCS!users,!and!

more!broadly!all!users!of!PSE!products.!The! framework!and!theoretical!advances!achieved!

will! also! be!used! to! extend! the! capabilities! of! the! commerciallyHavailable! version!of! SAFT,!

enabling! for! the! first! time! the!modeling! of!weak! electrolytes!within! a! group! contribution!

equation!of!state.!

!

CustomHmade!ComputerHAided!Molecular!Design!Procedure!and!Software.!!

A! new! framework! for! the! design! of!molecules! of! desired! properties! and! optimal! process!

performance!has!been!the!outcome!of!CAPSOL!project.!New!improvements!over!previously!

developed! software! include! the! option! for! the! design! of! specialized! solvents! and! solvent!

blends!for!CO2!capture.!The!new!advances!in!CAMD!procedure!will!enable!the!extension!of!

the!application!to!other!separation!systems.!!

!

MultiHscale!computer!aided!design!of!postHcombustion!CO2!plants.!

A! method! has! been! available! for! multiHscale! generation! and! multiHcriteria! assessment! of!

process!alternatives!for!solventHbased!postHcombustion!CO2!capture!that!is!computationally!

efficient!and!facilitates!reliable!screening!in!early!phases!of!conceptual!process!design.!The!

method!should!be!able!to!generate!and!screen!a!large!number!of!process!alternatives!with!

respect! to! diverse! process! features! (i.e.! solvent! molecules,! process! layout! and! process!

operating!conditions)!and!prioritize!a!reduced!number!of!superior!process!alternatives!to!be!

tested!in!subsequent!rigorous!design!stages.!Notwithstanding!the!innovative!features!of!this!


32!

!

multiHscale! approach,! the! method! should! also! be! easily! compatible! with! existing! design!

frameworks! and! software! tools! widely! used! by! process! system! engineering! companies.!

Therefore,!the!enhancement!of!existing!screening!tools!in!early!phases!of!process!design!will!

be!realized!via!the!complementary,!specialized!features!of!the!developed!method.!!

!

Novel!absorption/desorption!flowsheet!features!

The!development!of! innovative!absorption/desorption! flowsheets! is! a!definite!outcome!of!

the! research! activities! of! CAPSOL! project.! Novel! flowsheet! configurations! for! various!

solvents! that! have! not! been! tested! thoroughly! prior! to! CAPSOL! project! have! been!

determined.!Models!of!variable!resolution!assist!in!the!quick!but!efficient!screening!among!

multiple!flowsheet!alternatives!and!options.!!

!

Novel!or!improved!column!equipment!and!process!design!

Partners! involved!in!the!development!of! improved!column!equipment!(structured!packings!

and! nonHseparating! internals,! e.g.,! distributors)! and! process! design! will! create! relevant!

software! tools! that! can! be! brought! to! a! commercial! level.! To! date,! the! available! mass!

transfer! contactor! characteristics!have! so! far!basically!been!empirically!derived! from!early!

performance! tests! of! some! standard! applications! not! taking! any! specific! and! detailed!

characteristics!of! the!application! system! itself! into!account.!The!methodology!proposed! in!

the! CAPSOL! project! is! different! as! it! applies! a! modelHbased! contactor! optimization!

methodology!including!hydrodynamic!analogy!(HA)!and!computational!fluid!dynamics!(CFD)!

models!in!order!to!propose!a!contactor!designed!for!one!specific!application!thereby!taking!

all! relevant! and! specific! system! parameters! into! consideration.! The! optimization! work! is!

focused! on! the! main! process! parameters,! primarily! it! tries! to! find! the! ideal! compromise!

between!separation!performance!and!pressure!loss!characteristics.!

Academic!partners!will!use!their!software!for!educational,!research,!and!training!purposes,!

whereas! industrial! partners!will! utilize! it! for! the! design! of! innovative! packings! at! reduced!

development!time!and!cost.!

Highlights:!MONTZ!has!already!designed!a!new!commercial!packing!material!product!using!

the!software!tools.!!

!

Innovative!power!cycles!and!retrofitting!options!!

New!integrated!flowsheet!configurations!incorporating!CO2!capture!plants!in!existing!power!

plants!will!provide!the!exploitable!item.!Beneficiaries!will!mainly!be!the!two!industrial!users!

in! the! consortium.! In! addition! the! academic! partners! will! be! able! to! promote! the! new!

knowledge!to!their!industrial!consortia.!!

!

TechnoHeconomic!studies!

Detailed!technoHeconomic!studies!on!CO2!capture!technology! incorporation! in! lignite! fired!

steam! power! plant,! supercritical! hardHcoal! fired! power! plant,! natural! gas! fired! combined!

cycle,!quicklime!production!plant.!A!complete!technoHeconomic!study!on!solvent!based!CO2!

capture!technologies! for!a!variety!of!power!plants!and!other!CO2!emitting!plants!provides!

the!basis!for!exploitation!of!the!acquired!knowledge!from!the!project.!!

!

Experimental!and!pilot!plant!data!!

Partners!involved!in!the!performing!of!pilot!plant!tests!will!setHup!a!database!consisting!of!all!

measured!data! (e.g.,! temperature! and! concentration!profiles;! energy! consumption! values;!


33!

!

degradation! phenomena! evaluation).! A! part! of! this! data! will! be! published! in! established!

scientific!journals!and!presented!on!conferences!thus!providing!a!valuable!input!to!industry!

and!academia.!The!rest!will!be!made!available!for!industrial!use.!The!University!of!Paderborn!

pilot!plant!will!further!be!used!for!educational!and!training!purposes.!

!

SHE!(SafetyHHealthHEnvironmental)!hazard!assessment!method!for!CO2!capture!!

Various! SHE!hazard!assessment!methods!have!been!developed! for!early! stages!of!process!

design! in! the! last! two! decades.! In! CAPSOL! the! most! relevant! features! of! these! general!

methods! for! the! solventHbased! postHcombustion! CO2! capture! have! been! screened! and!

prioritized.! The! output! is! a! list! of! applicable! rules! for! SHE! hazard! assessment! that! can! be!

either!used!as! a! standHalone!assessment!method! for!preliminary! screening! in! early!design!

stages! or! integrated! in! risk! assessment! toolboxes! for! chemical! and/or! power! plants.! The!

promotion!of!the!method!and!the!potential!for!market!exploitation!will!be!first!explored!by!

the! Safety! &! Environmental! Technology! group! via! its! collaboration! network! with! Swiss!

chemical!and!insurance!companies!and!public!offices!for!environment!and!energy.!!

!

Methods!for!estimation!of!supply!chain!relevant!Life!Cycle!Assessment!(LCA)!impacts!!

LCA!impacts!often!suffer!from!data!gaps,!especially!with!respect!to!supply!chain!information!

of!chemicals! required! for!a!comprehensive!cradleHtoHgate! impact!analysis.!For! the!solventH

based!postHcombustion!CO2!capture,! an! important! issue!of!data!gaps! refers! to! the! supply!

chain!of! solvents! considering!also! their!degradation! rate.!Here,! it! is! intended! to!provide!a!

framework! of! complementary! methods! depending! on! available! information! and! the!

required! detail! of! design.! The! framework! will! mainly! consist! of! QSAR! correlations! of! LCA!

impacts!to!molecular!structures,!but!will!also!account!for!decomposition!of!the!supply!chain,!

where!more!accurate!information!is!available!from!existing!data!sources.!The!framework!will!

focus! on! compatibility! with! existing! LCA! databases! (e.g.,! Ecoinvent! Center)! and! software!

tools! (e.g.,!SimaPro®)! to!enhance!the!applicability!of! the! framework!by! the!process!design!

and!LCA!community.!

!

Optimization!of!structured!packings!

The! CAPSOL! exploitation! potential! lies! in! the! methodology! for! optimising! structured!

packings!by!adapting!its!geometric!parameters!according!to!the!specific!characteristics!of!the!

separation!task.!This!is!a!fundamentally!new!approach!compared!to!what!the!manufactures!

have! been! following! within! the! last! decades,! and! this! approach! may! lead! to! significant!

process! intensification! for! many! applications.! Even! though! the! investigations! have! been!

carried!out!for!one!process!example!only!(CO2!absorption!with!MEA),!the!methodology!for!

the! equipment! optimization! followed! in! the! project! is! in! principle! transferable! to! diverse!

distillation! and! absorption! applications.! This! offers! vast! opportunities! to! apply! the!

methodology!developed!in!the!CAPSOL!project!for!future!optimization!activity.!

!

Flowsheet!design!for!CO2!capture!and!heat!integration!for!the!quicklime!process!

Heat! integration! opportunities! in! quicklime! production! the! energy! released! from! the!

production!line!of!another!product.!The!production!line!of!calcium!hydroxide!(slaked!lime)!is!

a!net!energy!supplier.!The!heat!released!by!this!process!can!be!efficiently!utilized!by!a!CO2!

capture! unit! hence! significantly! reducing! the! energy! penalty.! This! is! a! sort! of! symbiotic!

processes!for!the!production!of!a!useful!product!while!the!emissions!from!the!initial!process!

are!being!captured.!


34!

!

!

Educational!and!training!activities!

Several!academic! initiatives!have!been!originated!from!CAPSOL!project.!Academic!partners!

and! those! involved! in! scientist! training!will! utilize! the! new! results! and! technology! for! the!

enrichment! of! their! educational! programs! and! training! modules.! In! particular,! the!

experimental! and! pilotHplant! setHup! will! be! integrated! in! the! education! and! training! of!

students!and!researchers.!The!developed!tools! for!the!design!optimization,!the! integration!

of!the!CO2!capture!units!within!existing!power!plants!will!form!the!basis!to!further!enhance!

the!links!of!academic!and!research!oriented!organizations!with!industry!!

!

!

Dissemination'of'Results'The! CAPSOL! website! (www.capsolHproject.eu)! provides! a! comprehensive! overview! of! the!

main!achievements!and!results.!The!consortium!will!maintain!the!project!website!for'at'least'five'years!after!the!completion!of!the!project!and!update!its!contents!with!new!publications!

and!presentations!arising! from!the!project!results.!A!specific!section! in!the!website!will!be!

devoted! to! the!exploitation!of! the!CAPSOL! foreground!knowledge!by! the!project!partners.!

CAPSOL!project!was!part!of! the!organizing! team!along!with! four!other!active!FP7!projects!

(DemoCLoCk,!iCap,!Innocuous!and!IOLICAP)!for!the!Carbon!Capture!and!Storage!technologies!

conference!that!took!place!in!Antwerpen,!Belgium,!between!May!28!H!29th,!2013.!'The! key! instrument! for! the! dissemination! of! the! CAPSOL! results!was! the! preparation! and!

publication! of! mainly! scientific! articles! in! peer! reviewed! journals! and! periodicals.! The!

complete!list!of!publication!along!with!a!designation!regarding!accessibility!of!the!article!in!

some!form!(publisher’s!edition,!postHrefereed!or!preHrefereed)!is!given!below:!!

!

1. Rodriguez!J,!N!MacDowell,!F!Llovell,!CS!Adjiman,!G!Jackson,!A!Galindo,!“Modelling!the!

fluid! phase! behaviour! of! aqueous! mixtures! of! multifunctional! alkanolamines! and!

carbon!dioxide!using!transferable!parameters!with!the!SAFTHVR!approach”,!Molecular)Physics:) An) International) Journal) at) the) Interface) Between) Chemistry) and) Physics,!110(11H12),!2012,!1325H1348.!(access!in!public!institutional!repository)!

2. Papadopoulos!AI,!M!Stijepovicb,!P!Linke,!P!Seferlis,!S!Voutetakis,!“Molecular!Design!of!

Working! Fluid! Mixtures! for! Organic! Rankine! Cycles”,! Computer) Aided) Chemical)Engineering,!32,!2012,!289H294.!(access!in!public!institutional!repository)!

3. Papadopoulos!AI,!Stijepovic!M,!Linke!P,!Seferlis!P,!Voutetakis!S,!“MultiHlevel!Design!and!

Selection! of! Optimum! Working! Fluids! and! ORC! Systems! for! Power! and! Heat!

Cogeneration! from! Low! Enthalpy! Renewable! Sources”,! Computer) Aided) Chemical)Engineering,!30,!2012,!66H70.!(access!in!public!institutional!repository)!

4. Yildirim!O,!AA!Kiss,!N!Hueser,!K!Lessmann,!EY!Kenig,!“Reactive!absorption!in!chemical!

process! industry:! A! review!on! current! activities”,!Chemical) Engineering) Journal,! 213,!2012,!371H391.!(access!in!public!institutional!repository)!

5. Čuček! L,! PS! Varbanov,! JJ.! Klemeš,! Z! Kravanja,! “Potential! of! Total! Site! Process!

Integration!for!Balancing!and!Decreasing!the!Key!Environmental!Footprints”,!Chemical)Engineering)Transactions,!29,!2013,!61H66.!(access!in!publisher’s!website)!

6. Čuček!L,!PS!Varbanov,!JJ.!Klemeš,!Z!Kravanja,!“Reducing!the!Dimensionality!of!Criteria!

in! MultiHObjective! Optimisation! of! Biomass! Energy! Supply! Chains”,! Chemical)Engineering)Transactions,!29,! 2013,!1261H1266.!(access!in!publisher’s!website)!


35!

!

7. Damartzis! T,! AI! Papadopoulos,! P! Seferlis,! “Generalized! Framework! for! the! Optimal!

Design! of! SolventHBased! PostHCombustion! CO2! Capture! Flowsheets”,! Chemical)Engineering)Transactions,!35,!2013,!1177H1182.!(access!in!publisher’s!website)!

8. Kakaras!EK,!AK!Koumanakos,!AF!Doukelis,!“Greek!LigniteHFired!Power!Plants!with!CO2!

Capture!for!the!Electricity!Generation!Sector”,!Chemical)Engineering)Transactions,!35,!2013,!331H336.!(access!in!publisher’s!website)!

9. Chremos!A,!E!Forte,!V!Papaioannou,!A!Galindo,!G!Jackson,!CS.!Adjiman,!“Modelling!the!

Fluid!Phase!Behaviour!of!Multifunctional!Alkanolamines!and!Carbon!Dioxide!Using!the!

SAFTHγ! Approach”,!Chemical) Engineering) Transactions,! 35,! 2013,! 427H432.! (access! in!publisher’s!website)!

10. Pan!M,! Bulatov! I,! Smith!R,! “New!MILPHbased! iterative! approach! for! retrofitting! heat!

exchanger! networks! with! conventional! network! structure! modifications”,! Chemical)Engineering)Science,!104,!2013,!498H524.!(access!in!public!institutional!repository)!

11. Pan!M,!Bulatov! I,! Smith!R,! “Intensifying!heat! transfer! for! retrofitting!heat!exchanger!

networks! with! topology! modifications”,! Computer) Aided) Chemical) Engineering,! 32,!2013,!307H312.!(access!in!public!institutional!repository)!

12. Pan!M,!Bulatov!I,!Smith!R,!“Heat!Transfer!Intensified!Techniques!for!Retrofitting!Heat!

Exchanger!Networks!in!Practical!Implementation”,!Chemical)Engineering)Transactions,!35,!2013,!1189H1194.!(access!in!publisher’s!website)!

13. Papadopoulos! AI,! Stijepovic! M,! Linke! P,! Seferlis! P,! Voutetakis! S,! Toward! Optimum!

Working! Fluid! Mixtures! for! Organic! Rankine! Cycles! using! Molecular! Design! and!

Sensitivity!Analysis,! Industrial) and) Engineering) Chemistry) Research,! 52,! 2013,! 12116H12133.!(access!in!public!institutional!repository)!

14. Yazgi! M,! EY! Kenig,! “HydrodynamicHanalogyHbased! modelling! of! CO2! capture! by!

aqueous!monoethanolamine”,!Chemical)Engineering)Transactions,!35,!2013,!349H354.!(access!in!publisher’s!website)!

15. Damartzis!T,!Papadopoulos!AI,!Seferlis!P,!“Optimum!Synthesis!of!SolventHBased!PostH

Combustion! CO2! Capture! Flowsheets! through! a! Generalized!Modeling! Framework”,!

Clean)Technologies)and)Environmental)Policy,!16(7),!2014,!1363H1380.!(access!in!public!institutional!repository)!

16. Papadopoulos! AI,! Badr! S,! Chremos! A,! Forte! E,! Zarogiannis! T,! Seferlis! P,!

Papadokonstantakis! S,! Adjiman! CS,! Galindo! A,! Jackson! G,! “Efficient! Screening! and!

Selection! of! PostHcombustion! CO2! Capture! Solvents”,! Chemical) Engineering)Transactions,!39,!2014,!211H216.!(access!in!publisher’s!website)!

17. Damartzis! T,! Kouneli! A,! Papadopoulos! AI,! Seferlis! P,! Dimitriadis! G,! Vlachopoulos! G,!

“Optimal! Design! of! Solvent! Based! Post! Combustion! CO2! Capture! Processes! in!

Quicklime!Plants”,!Chemical)Engineering)Transactions,!39,!2014,!1327H1332.!(access!in!publisher’s!website)!

18. Liew! PY,! Klemeš! JJ,! Doukelis! A,! Zhang! N,! Seferlis! P,! “Identification! of! Process!

Integration! Options! for! CO2! Capture! in! Greek! LigniteHfired! Power! Plant”,! Chemical)Engineering)Transactions,!39,!2014,!1447H1452.!(access!in!publisher’s!website)!

19. Pan! M.,! Agulonu! A.,! Gharaie! M.,! Perry! S.,! Zhang! N.,! Bulatov! I.,! Smith! R.,! “Optimal!

Design!Technologies!for!Integration!of!Combined!Cycle!Gas!Turbine!Power!Plant!with!

CO2! Capture”,! Chemical) Engineering) Transactions,! 39,! 2014,! 1441H1446.! (access! in!publisher’s!website)!


36!

!

20. Hüser! N.,! Kenig! E.Y.,! “A! New! AbsorptionHdesorption! Pilot! Plant! for! CO2! Capture”,!

Chemical) Engineering) Transactions,! 39,! 2014,! 1417H1422.! (access! in! publisher’s!website)!

21. Li!B.H.,!Zhang!N.,!Smith!R.,!“RateHbased!Modelling!of!CO2!Capture!Process!by!Reactive!

Absorption!with!MEA”,!Chemical)Engineering)Transactions,!39,!2014,!13H18.!(access!in!publisher’s!website)!

22. Dufal!S,!Papaioannou!V,!Sadeqzadeh!M,!Pogiatzis!T,!Chremos!A,!Adjiman!CS,!Jackson!G,!

Galindo!A,!“Prediction!of!Thermodynamic!Properties!and!Phase!Behavior!of!Fluids!and!

Mixtures! with! the! SAFTHγ! Mie! GroupHContribution! Equation! of! State”,! Journal) of)Chemical)and)Engineering)Data,!59(10),!2014,!3272H3288.!(access!in!public!institutional!repository!from!August!2015)!

23. Pan! M,! Bulatov! I,! Smith! R,! “Efficient! Retrofitting! Approach! for! Improving! Heat!

Recovery! in! Heat! Exchanger! Networks! with! Heat! Transfer! Intensification”,! Industrial)and) Engineering) Chemistry) Research,! 53(27),! 2014,! 11107H11120.! (access! in! public!institutional!repository!from!June!2015)!

24. Pan!M,!Bulatov!I,!Smith!R,!“Recent!methods!for!retrofitting!heat!exchanger!networks!

with! heat! transfer! intensifications”,! Chemical) Engineering) Transactions,! 39,! 2014,!1435H1440.!(access!in!publisher’s!website)!

25. Yazgi!M,!A!Olenberg,!EY!Kenig,!“Complementary!Modelling!of!CO2!Capture!by!Reactive!

Absorption”,!Computer) Aided) Chemical) Engineering,! 33,! 2014,! 1243H1248.! (access! in!public!institutional!repository)!

26. Hüser!N,!Dubjella!P,!Hugen!T,!Rietfort!T,!Kenig!EY,!“Untersuchung!und!Bewertung!einer!

strukturierten! Packung! mit! 75°HNeigungswinkel! für! die! CO2HAbscheidung”,! ChemieCIngenieurCTechnik,!86,!2014,!1451H1452.!(access!in!public!institutional!repository)!

!

Consortium'Members'

!

Centre!for!Research!and!Technology!–!Hellas!(CERTH),!Greece!

Chemical!Process!Engineering!Research!Institute!(CPERI)!

Laboratory!of!Process!Systems!Design!and!Implementation!!

Contact!person!(Coordinator):!Dr.!Panos!Seferlis!

Website:!http://psdi.cperi.certh.gr/!

!

University!of!Manchester,!U.!K.!

School!of!Chemical!Engineering!and!Analytical!Science!

Centre!for!Process!Integration!

Contact!person:!Dr.!Nan!Zhang!

Website:!http://www.ceas.manchester.ac.uk/research/centres/cpi/!

!

!

University!of!Paderborn,!Germany!

Faculty!of!Mechanical!Engineering,!

Chair!of!Fluid!Process!Engineering!

Contact!person:!Prof.!Eugeny!Y.!Kenig!

Website:!http://www.uniHpaderborn.de/fvt!

!

Imperial!College!of!Science,Technology!and!Medicine,!U.!K.!

Centre!for!Process!Systems!Engineering!

Contact!person:!Prof.!Claire!Adjiman!

Website:!

http://www3.imperial.ac.uk/centreforprocesssystemsengineering!


37!

!

!

University!of!Pannonia,!Hungary!

Faculty!of!Information!Technology!!

Research!Institute!of!Chemical!and!Process!Engineering!

Centre!for!Process!Integration!and!Intensification!–!CPI2!

Contact!person:!Prof.!Jiři!Klemeš!

Website:!http://cpi.uniHpannon.hu/!

!

Eidgenössische!Technische!Hochschule!Zürich,!Switzerland!

Safety!&!Environmental!Technology!Group!(S&ETG)!

Contact!person:!Dr.!Stavros!Papadokonstantakis!

http://www.sustHchem.ethz.ch/!

!

National!Technical!University!of!Athens!,!Greece!

School!of!Mechanical!Engineering!!

Laboratory!of!Steam!Boilers!and!Thermal!Plants!

Contact!person:!Prof.!Emmanuel!Kakaras!

Website:!http://www.lsbtp.mech.ntua.gr/!

!

Julius!Montz!GmbH,!Germany!

Contact!person:!Dr.!Thomas!Rietfort!

Website:!http://www.montz.de!

!

Public!Power!Corporation!S.A.,!Greece!

Contact!person:!Mr.!Charalambos!Papapavlou!

Website:!http://www.dei.gr/!

!

CaO!Hellas!Macedonian!Lime!S.A.,!Greece!

Contact!person:!Mr.!Georgios!Dimitriadis!

Website:!http://www.caohellas.gr/!

!

Process!Design!Center!B.v.,!The!Netherlands!

Contact!person:!Mr.!Evert!van!der!Pol!

Website:!http://www.processHdesignHcenter.com/!

!

Scottish!Power!Generation!PLC,!U.!K.!

Contact!Person:!Mr.!Euan!Fenelon!

Website:!http://www.scottishpower.com/!

!

!