Reclama ion o ca bon ibe s and added- alue gases in a py olysis-based
composi es ecycling p ocess
A. Lopez-U ionaba enechea1*, N. Gas elu1, E. Acha1, B.M. Caballe o1, A. O ue2, A. Jiménez-
Suá ez3, S.G. P olongo3, I. de Ma co1
1
Chemical and En i onmen al Depa men , Facul y o Enginee ing o Bilbao. Uni e si y o he
Basque Coun y (UPV/EHU). Plaza Ingenie o To es Que edo 1, 48013 Bilbao (Spain).
2
Chemical and En i onmen al Depa men , Facul y o Enginee ing o Gipuzkoa. Uni e si y o
he Basque Coun y (UPV/EHU). Plaza Eu opa 1, 20018 Donos ia-San Sebas ian (Spain).
3
Ma e ials Science and Enginee ing A ea, ESCET. Uni e si y Rey Juan Ca los. C/Tulipán s/n,
Mós oles, Mad id (Spain)
Co esponding au ho in o ma ion:
This is he accep ed manusc ip o he a icle ha appea ed in inal o m in Jou nal o Cleane P oduc ion 273 :
(2020) // A icle ID 123173, which has been published in inal o m a h ps://doi.o g/10.1016/
j.jclep o.2020.123173. © 2020 Else ie unde CC BY-NC-ND license (h p://c ea i ecommons.o g/licenses/by-
nc-nd/4.0/)
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Abs ac
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Ca bon ibe s eclama ion om was e composi es by py olysis is de eloping as . Py olysis
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allows he eclama ion o he ibe s by he mal decomposi ion o he polyme ic esin, bu he
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ma e ial alue o hese esins is no ye eco e ed. In his esea ch wo k, he possibili y o
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ob aining high- alue gaseous ac ions by ea ing he apo s gene a ed in he decomposi ion
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o a poly(benzoxazine) con aining ca bon ibe was e composi e has been s udied. The
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expe imen s ha e been ca ied ou in a lab-scale acili y consis ing o wo eac o s in se ies. In
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he i s eac o , he py olysis o he was e is ca ied ou a 500 °C, while in he second eac o
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he apo s coming om he i s eac o a e ea ed a 900 °C. Such ea men enables o iple
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he amoun o gas in compa ison o con en ional py olysis. Besides, his gas con ains 56% by
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olume o H2, which means he eco e y o app oxima ely 60% o he hyd ogen con ained in he
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esin. On he o he hand, clean ca bon ibe s wi h mechanical p ope ies wi hin comme cial
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alues ha e been also ob ained.
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Keywo ds: ca bon ibe , py olysis, ca bon composi es, ecycling, poly(benzoxazine), seconda y
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aw ma e ials.
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Wo dcoun : 7915
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1. In oduc ion
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Ca bon ibe (CF) is a e y low-densi y ma e ial wi h excellen mechanical, elec ical and he mal
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p ope ies, which is almos exclusi ely used as ein o cemen o plas ic ma ix composi e
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ma e ials, called ca bon ibe ein o ced plas ics/polyme s (CFRP) (Gio gini e al., 2015). Behind
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he gene ic de ini ion o CFRP, he e is a wide a ie y o p oduc s co e ing la ge anges o
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physical-chemical p ope ies. This is because such p ope ies depend undamen ally on he
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quali y o he ibe s - which can be manu ac u ed almos o measu e acco ding o he needs in
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se ice - and he quan i y, leng h and o ien a ion o he ibe s wi hin he plas ic ma ix - bo h
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leng h and alignmen inc easing he ein o cemen capaci y o he ibe s - (Newcomb, 2016;
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William D. Callis e J ., 2014). This ci cums ance gi es CFRP a e sa ili y ha explains hei
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massi e and g owing indus ial and u ban use (Holmes, 2017a; Liu e al., 2019; Vo Dong e al.,
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2019).
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Howe e , CF p oduc ion is a p ocess wi h high en i onmen al and ene gy impac . 96% o CF is
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p oduced om poly(ac yloni ile) (PAN) ibe s (Newcomb, 2016). PAN is ob ained by
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polyme iza ion o ac yloni ile, which in u n is he p oduc o he eac ion be ween p opylene
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and ammonia, bo h o hem o iginally coming om oil (Naq i e al., 2018). PAN ibe s a e
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ca bonized in a empe a u e ange be ween 1000 °C o 3000 °C, depending on he speci ic
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p ope ies desi ed o he CF. Finally, CF a e condi ioned h ough su ace ea men s (Naq i e
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al., 2018; Newcomb, 2016). In summa y, CF is a ossil p oduc ha is manu ac u ed h ough a
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mul i-s age p ocess whe e e y high empe a u es, sol en s, inishing oils and su ace ea men
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esins a e equi ed. Addi ionally, a mosphe ic emissions o oxic compounds such as HCN, NH3
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o NOx om u naces and eac o s a e p oduced (Le eu e e al., 2017; Vo Dong e al., 2018).
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One way o educe he impac o he g owing CF p oduc ion is o eco e hem om esidual
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CFRP and e-manu ac u e composi e ma e ials wi h he eclaimed ibe s (He mansson e al.,
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2019). The e is s ill much o be de eloped in his ield, as al hough se e al me hods o CF
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eco e y ha e been in es iga ed, land ill and incine a ion a e oday he wo mos common ways
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o managing CFRP was e (Liu e al., 2017; Vo Dong e al., 2018; Yang e al., 2012). In o de o
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eco e he CF om a composi e ma e ial i is necessa y o emo e he polyme ic esin whe e
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hey a e embedded. This can be done by dissolu ion (chemical me hods) and by decomposi ion
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( he mal me hods) (Pimen a and Pinho, 2011; Rybicka e al., 2016). Recen ly published
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economic, en i onmen al and human heal h impac assessmen s compa ing hese al e na i es
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poin o he la e as he op ion wi h lowes impac , pa icula ly when he he mal me hod is
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py olysis (Khalil, 2018; Vo Dong e al., 2018). Consequen ly, py olysis is he mos ma u e
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echnology, wi h he highes TRL and he la ges numbe o indus ial implemen a ions, despi e
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he ac ha chemicals a e no eco e ed om he esin (i is bu ned) while dissolu ion me hods
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a e heo e ically capable o eco e ing he ibe s and some monome s, mainly phenol and
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de i a i es (Kim e al., 2019; La Rosa e al., 2016).
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Py olysis is hea ing in he absence o oxygen. In he case o CFRP was e, he inal empe a u e is
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usually be ween 400 and 600 °C, a which mos esins a e b oken down bu do no CF (Meng e
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al., 2018; Meye e al., 2009; Wong e al., 2010). The decomposi ion o he polyme ic esin
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p oduces gases, apo s (liquids a oom empe a u e) and a ca bonaceous p oduc (cha ) ha
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o ms a ligh laye co e ing he ca bon ibe s. This laye o cha can p e en he p ope adhesion
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o he eclaimed ibe s wi h new esins a he ime o euse, so i is necessa y a pos - ea men
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in he p esence o ai o elimina e i (Onwudili e al., 2016). This pos - ea men mus be
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con olled (no e y high empe a u e and no e y long ime) in o de o a oid he deg ada ion
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o he ibe s by combus ion (López e al., 2013; Nahil and Williams, 2011). Acco ding o
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specialized li e a u e, his p ocess does no signi ican ly damage he CF, which e ain hei
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ensile modulus o elas ici y and 90% o hei ensile s eng h (Holmes, 2018; Pimen a and Pinho,
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2014).
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Howe e , he ecycling o CFRP was e by py olysis has no been launched de ini i ely. The
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s udies indica e ha i is s ill necessa y o make he ecycling p ocess mo e p o i able. The e a e
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wo a eas wi h g ea po en ial o imp o emen : (1) ob aining longe ibe s and de eloping
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echniques o aligning sho and long ecycled ca bon ibe s (Holmes, 2018, 2017b; Meng e al.,
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2018) and (2) ma e ial eco e y om polyme ic esins (Cousins e al., 2019; Vo Dong e al., 2018).
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The la e is no an easy ask since CFRP py olysis liquids a e complex mix u es o ni ogenous,
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oxygena ed and sulphu o ganic compounds, o en mixed wi h wa e . On he o he hand, he
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gases, composed o ca bon monoxide and dioxide, hyd ogen and ligh hyd oca bons, a e
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gene a ed in low quan i y (López e al., 2013; Nahil and Williams, 2011; Yang e al., 2015).
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The gases could be used as an al e na i e uel, bu he bene i ob ained om hem would no
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compensa e o he p oblem gene a ed by he liquid p oduc , whose indus ial use is unlikely,
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wi h he esul ha i would be classi ied as a haza dous was e. The e o e, i is e iden ha a
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ea men is necessa y o y o imp o e he composi ion o liquids and/o o elimina e hem in
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a o o he gaseous ac ion. Howe e , as a as we a e conce ned, he e is no e idence om
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any esea ch g oup ha has in es iga ed his issue o da e. The au ho s o his a icle ha e
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de eloped a me hod based on he he mo-ca aly ic ea men o such gases and apo s be o e
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condensa ion (Gas elu e al., 2019, 2018). This me hod a oids he emission o gaseous p oduc s
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om esin combus ion and eco e s added- alue gases. The objec i e o he p esen pape is o
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de e mine he maximum pe o mance o he ea men in he absence o ca alys , by s udying
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he in luence o he ille used ea men eac o .
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2. Ma e ials and me hods
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2.1. CFRP was e
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The CFRP was e a e p e-p eg pieces om ae onau ical indus y composed o a
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poly(benzoxazine) ype polyme ic esin and To ay T300/3k ca bon ibe s ab ic in he o m o
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plain wea e. Table 1 shows some chemical p ope ies o he CFRP sample. A deepe discussion
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o hese p ope ies and he he mal beha io o his sample has been epo ed elsewhe e
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(Gas elu e al., 2018).
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Table 1. Fibe con en , p oxima e analysis and elemen al analysis o he was e CFRP (w .%).
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Fibe con en
61.0
P oxima e analysis
Mois u e
0.5
Vola iles
28.4
Fixed ca bon1
71.0
Ash
0.1
Elemen al analysis
C
86.2
H
2.2
N
4.8
S
1.3
Cl
u.d.l.2
O he s3
4.9
1 By di e ence
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2 Unde de ec ion le el (<0.1 w .%)
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3 O he s = 100-(C+H+N+S+Mois u e+Ash)
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2.2. Lab-scale ins alla ion o ca bon ibe eclama ion
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The expe imen s we e ca ied ou in a lab-scale ins alla ion consis ing o wo eac o s connec ed
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in se ies and a sec ion o condensa ion o liquid p oduc s and cleaning o gases (see Figu e 1).
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The i s eac o (3) is a non-s i ed ank eac o 15 cm in diame e and 21 cm in heigh . The
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second eac o (6) is a ixed bed ubula eac o 2.5 cm in diame e and 50 cm in leng h. The wo
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eac o s a e made o 316 s ainless s eel and a e ex e nally hea ed by elec ic u naces. The
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ou pu o he second eac o (9) is connec ed o h ee condense s (11, 12, 13) and an ac i a ed
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ca bon column (Pan eac Ac i a ed Ca bon No. 1 QDP). The non-condensable p oduc s pass
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h ough he ac i a ed ca bon column (14) and hen hey a e collec ed in gas sampling bags (16,
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17).
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Ro ame e
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Condense 1
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Py olysis / oxida ion eac o
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Condense 2
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Py olysis / oxida ion u nace
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Condense 3
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Fu nace he mocouple
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Ac i a ed ca bon column
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Reac o he mocouple
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T al e
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Tubula eac o
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Gas bag 1
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Tubula u nace
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Gas bag 2
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Tubula eac o he mocouple
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Tubula u nace empe a u e-con ol
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Vapo and gas ou le
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Py olysis / oxida ion u nace empe a u e-con ol
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Solid bed ma e ial
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Compu e
Figu e 1. Flowshee o he py olysis ins alla ion.
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In a ypical expe imen , 100 g o CFRP was e (cu in o 20 x 2 cm shee s) is in oduced in o he
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i s eac o , which is hea ed up a 3 °C min-1 o 500 °C o 30 minu es and is ed wi h a 1 L min-
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1 low a e o N2. The gene a ed gases and apo s pass h ough he ubula eac o , hea ed a
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900 °C, whe e a second he mal c acking akes place. This eac o is illed wi h a solid bed
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ma e ial in o de o imp o e luid dynamics and a oid empe a u e g adien s. Once he py olysis
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s age is comple ed, he eed gas is changed o syn he ic ai in o de o accomplish an oxida ion
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s age a 500 °C o 45 minu es, using an ai low a e o 1.5 L min-1. This pape p esen s he esul s
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o i e di e en expe imen s. The i s one (E1) is a con en ional py olysis es , wi hou
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ea men o gases and apo s. In he o he ou expe imen s (E2-E5) such ea men does occu
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and he in luence o he cha ac e is ics o he solid bed placed wi hin he ubula eac o is
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s udied.
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2.3. Ma e ials employed in he solid bed
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Th ee ypes o ma e ials we e used as ille s o he ubula eac o . On he one hand, silicon
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ca bide (CSi) p o ided by Na a osic S.A., wi h wo di e en pa icle size dis ibu ions, 1.5 mm
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< x < 2 mm and 0.5 mm < x < 1 mm. CSi is a e ac o y ma e ial p esen ing good he mal
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conduc i i y and high s abili y in he condi ions o he apo s ea men (Dey e al., 2014). I is
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widely used as solid bed in chemical eac o s on a labo a o y scale, since i imp o es luid
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dynamics and hea anspo h oughou hem (O ega e al., 2018; Song e al., 2018; Tillmann
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e al., 2018).
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The second solid bed ma e ial was made om de ec i e b icks o composi ion 50-65% Al2O3, 30-
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40% SiO2, 1-2% Fe2O3, 0.5-1.5% Na2O+K2O in weigh , p o ided by Be oa S.L. O iginally b ick
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shaped, hey we e g ound o 1.5 < x < 2 mm pa icle size. This is a highly e ac o y ma e ial
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(Sege Cone num. 37), so i s unc ion was expec ed o be equi alen o ha o CSi bu a a much
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lowe cos ( hey a e was e b icks). In addi ion, he p esence o alkali me al oxides and i on oxide
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could ha e some ca aly ic e ec ha could be bene icial o he p ocess.
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Finally, a me allu gical coke o low ola ile con en p o ided by Be esa Zinc Ase S.A. was also
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employed as solid bed ma e ial. O iginally i was in he o m o small b ique es, so i was g ound
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o 1.5 < x < 2 mm pa icle size. The objec i e o using a ca bonaceous subs ance as solid bed is
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o obse e i s ca aly ic ac ion capaci y in con ac wi h CFRP decomposi ion subs ances, since
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ca bonaceous ma e ials a e widely es ed subs ances o he ea men o oxygena ed
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subs ances and a s (Elkasabi e al., 2017; Ra enni e al., 2018). In his speci ic case, a
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me allu gical coke has been selec ed because i is a “low-in- ola iles” ma e ial and he e o e
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ela i ely s able a he empe a u e o he ea men ca ied ou a he ubula eac o (900 °C).
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Table 2 shows he mos ep esen a i e ex u al pa ame e s o he ille s. In gene al, hey show
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a e y low su ace a ea, so hey can p ac ically be conside ed non-po ous, especially CSi. As
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ega ds he o he analyses ca ied ou on hese ma e ials, he acidi y analyses do no show any
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app eciable acidic cha ac e is ics, so ha nei he coke no e ac o y can be conside ed as an
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acid ma e ial. In addi ion, he e ac o y does no exhibi educible species wi h H2 (TPR) o
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in e ac ion wi h CO, so i can be conside ed a subs ance wi h s able me al oxides. The da a
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ob ained in hese analyses a e no p esen ed in he manusc ip because hey lack ele an
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in o ma ion, bu some analysis esul s a e included in he appendix o he a icle.
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Table 2. Tex u al p ope ies o he ma e ials employed in he solid bed.
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CSi
Coke
Re ac o y
Su ace a ea (m2 g-1)
0.085
1.18
0.28
Po e olume (cm3 g-1)
4.18·10-4
3.48·10-3
6.15·10-4
Po e diame e (Å)
34.8
33.9
55.8
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2.4. Analy ical echniques
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The ca bon ibe con en o he CFRP was de e mined using he ASTM D3171 (P ocedu e B),
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which consis s o he chemical dissolu ion o he esin in a mix u e o sul u ic acid and hyd ogen
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pe oxide. The ul ima e analysis was de e mined wi h he LECO T ueSpec CHN and LECO
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T ueSpec S elemen al analyze s espec i ely. Addi ionally, he p esence o elemen al chlo ine
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was examined by applying Me hod 5050 o he US En i onmen al P o ec ion Agency (EPA). This
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me hod is based on he combus ion o he sample in a calo ime ic pump (LECO AC-500) and
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he subsequen abso p ion o he combus ion gases in a basic solu ion, which is analyzed by ion
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ch oma og aphy (Dionex ICS 3000, equipped wi h conduc i i y and ampe ome ic de ec o s).
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The p oxima e analysis was pe o med wi h he LECO TGA-500 he mobalance, which ollows
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he ASTM D3173-85 and D3174-82 s anda ds.
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The ex u al p ope ies o he solid bed ma e ials was de e mined using he N2 adso p ion-
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deso p ion me hod in an Au oso b 1C-TCD. The samples we e p e iously degassed a 300 °C o
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12 h. The su ace a ea was calcula ed using he B unaue -Emme -Telle (BET) me hod, while
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he po e dis ibu ion was calcula ed using he Ba e -Joyne -Halenda (BJH) me hod. The acidi y
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o he e ac o y ma e ial was analyzed by empe a u e p og ammed deso p ion o ammonia
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(NH3-TPD) while he educible me als we e sough by empe a u e-p og ammed educ ion
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(TPR), bo h o hem by using he Mic ome i ics® Au oChem II equipmen . This equipmen was
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also used o analyze he p esence o ca aly ically ac i e me als on he su ace o e ac o y by
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chemiso p ion wi h CO.
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The py olysis solids we e cha ac e ized h ough ul ima e and p oxima e analysis, ollowing he
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p ocedu e used wi h he CFRP sample. The composi ion o he liquid p oduc s was de e mined
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using a gas ch oma og aph (GC, Agilen 6890) coupled o a mass spec ome e (MS, Agilen
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5973), conside ing as iden i ied only such chemicals p o iding an iden i ica ion quali y
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pa ame e g ea e han 85%. The gaseous p oduc s we e analyzed in a gas ch oma og aph
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(Agilen 7890A) wi h he mal conduc i i y and lame ioniza ion de ec o s (TCD and FID,
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espec i ely). This ch oma og aph is calib a ed o de e mine he composi ion o he so-called
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" e ine y mix u e", which includes H2, CO, CO2, CH4, C2, C3, C4, C5 and C6. The highe hea ing
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alue (HHV) o he gases was calcula ed om he HHV o he pu e compounds ha a e pa o
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hei composi ion.
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The eclaimed CF we e also subjec ed o ul ima e and p oxima e analyses acco ding o he
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p ocedu e men ioned abo e. The mo phological cha ac e is ics we e e alua ed by scanning
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elec on mic oscopy (SEM), wi h ene gy-dispe si e X- ay spec oscopy (EDX) o he
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de e mina ion o he su ace composi ion, using he Hi achi S-2400N mic oscope. Mechanical
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p ope ies we e measu ed by means o Minima 2000 es e (Rheome ic Scien i ic) equipped
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wi h a load cell o 200 N a a es ing speed o 1 mm min-1. CF we e moun ed and glued on a
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pape ab ha was placed in he g ips. Then, he middle po ion o he pape s was cu , so ha
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only he ca bon ibe ca ied he load (Luo and Ne a ali, 2001). 10 mm clamping leng h was
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used and a leas 10 specimens we e es ed, being he a e age alues epo ed.
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3. Resul s and discussion
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3.1. Py olysis s age
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Table 3 shows he py olysis yields and he composi ion o he gases and liquids ob ained in he
219
i e es s. These py olysis yields a e he a e age alue o a leas wo iden ical expe imen s
220
whe e he e was no a a ia ion g ea e han 3% in he yields hemsel es. These yields a e
221
quan i ied as ollows: (1) solids yield co esponds o he emaining sample in he eac o a e
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he py olysis s age, (2) he yield o o al condensa es is de e mined by he di e ence in weigh
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o he pipes and condense s be o e and a e he expe imen , and (3) he gas yield is calcula ed
224
by di e ence. The "collec ed liquids" is he amoun o liquids in he condense s, which is
225
dis inguished wi hin he o al condensa es yield wi h he in en ion o gi ing ep esen a i e
226
in o ma ion o he p ocess pa ame e s and no so much o he geome y o he ins alla ion,
227
which can ha e much in luence on he amoun o condensa es gene a ed in he pipes and o he
228
elemen s. These collec ed liquids ha e been used o de e mine he composi ion o condensa es
229
and he p opo ions o aqueous phase and o ganic phase. The gas composi ion shown in he
230
able is d y and ee o N2.
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Figu e 3. SEM images o eclaimed ca bon ibe s.
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Ene gy-dispe si e X- ay spec oscopy (EDX) has been used o de e mine he su ace composi ion
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o he CF, as well as ha o he pa icles seen on SEM mic og aphs. The esul s a e p esen ed in
402
Figu es 4 and 5. Fi s ly, one smoo h a ea has been analyzed, ha is, he su ace o he ibe s
403
(Figu e 4). The spec og am shows ha he only elemen de ec ed on ha su ace is ca bon,
404
which could indica e ha i is he su ace o he clean ibe , and he e o e would indica e a good
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eclama ion o he ma e ial. P e ious esea ch on oxida i e ea men s o CFRP was e has also
406
shown small amoun s o oxygen on he su ace o he eclaimed ibe s (Yip e al., 2002). In
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gene al, he amoun o su ace oxygen inc eases wi h he agg essi eness o he oxida ion
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p ocess (long ime, high empe a u e), so he absence o su ace oxygen could be indica i e o
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con olled and no excessi e oxida ion.
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Figu e 4. Ca bon ibe s su ace composi ion analysis.
413
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Figu e 5 shows he spec og ams o wo pa icles deposi ed on he ibe s. I can be seen ha he
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main elemen o hei composi ion is again ca bon, ollowed by oxygen, sodium and sulphu .
416
The p esence o oxygen and sulphu may indica e some aces o he polyme ic esin, while he
417
appea ance o sodium on he su ace is a p io i qui e su p ising. Howe e , he e is a p eceden
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epo ing he p esence o sodium in eclaimed ibe s om CFRP. In ha wo k, he exis ence o
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sodium was a ibu ed o he manu ac u ing p ocess o he ca bon ibe s (Jiang e al., 2008).
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Figu e 5. Composi ion o su ace pa icles.
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The mechanical cha ac e iza ion o he eclaimed ibe s is p esen ed in Table 5. The pa ame e s
426
measu ed a e he usual ones in mechanical cha ac e iza ion o his ma e ial, ha is, ensile
427
s eng h, ensile modulus and elonga ion a b eak. The alues o he same pa ame e s o some
428
comme cial CF ha e been also included in his able, ob ained om comme cial ca alogues and
429
a ailable echnical da a shee s. I can be seen ha he eco e ed ibe s ha e a conside ably
430
lowe ensile modulus han he comme cial ibe s o he TORAYCA and he YS se ies o GRANOC,
431
all o hem common in s uc u al ae onau ical applica ions. Howe e , he ensile s eng h,
432
al hough also lowe , is in he o de o magni ude o he TORAYCA T300 and GRANOC YS-90A-
433
30S ibe s.
434
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Table 5. Mechanical p ope ies o eclaimed ca bon ibe s and some comme cial ca bon ibe s.
436
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The CFRP was e used in his wo k has been gene a ed in p oduc ion asks o he ae onau ical
438
indus y, bu bo h i s speci ic applica ion and he p ope ies o he o iginal ibe s a e unknown,
439
so i is no possible o de e mine he deg ee o de e io a ion ha he mechanical p ope ies o
440
he ibe s may ha e su e ed du ing he ecycling p ocess. Howe e , he conse a ion o he
441
mechanical p ope ies o CF eco e ed by py olysis is a ac ha is p o en in he scien i ic
442
li e a u e ela ed o CFRP ecycling, as discussed in he in oduc ion o his a icle (Naq i e al.,
443
2018; Pimen a and Pinho, 2014, 2011). The low alues obse ed in his s udy may be due o he
444
speci ic cha ac e is ics o he eac o used o o he unce ain y and dispe sion o he esul s
445
ob ained in he analysis o such small diame e ibe s, as some esea che s ha e poin ed ou
446
(Gille e al., 2015).
447
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In any case, he elonga ion a b eak and ensile modulus o he eclaimed ibe s a e equi alen
449
o hose o he GRANOC XN se ies ibe s, which a e classi ied as low modulus and high elonga ion
450
ibe s. In addi ion, hei ensile s eng h is signi ican ly highe han he s eng h o hese
451
comme cial ibe s. The e o e, i is clea ha he CF eco e ed in his wo k can ha e alue and
452
Tensile s eng h (MPa)
Tensile modulus (GPa)
Elonga ion a b eak (%)
Reclaimed ibe s
2678 ± 700
96 ± 20
2.6 ± 0.8
TORAYCA T300
3530
230
1.5
TORAYCA T800S
5880
294
2.0
GRANOC YS-90A-30S
3530
880
0.3
GRANOC XN-10-30-S
1700
110
1.6
GRANOC XN-05-30-S
1100
54
2.0
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comme cial applica ions and compe e wi h i gin ca bon ibe s o ossil o igin. These esul s
453
demons a e he compe i i eness o eclaimed ca bon ibe s as seconda y aw ma e ials.
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4. Conclusion
456
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The main conclusions ha can be d awn om he wo k p esen ed in his a icle a e he
458
ollowing:
459
460
- Py olysis and oxida ion o poly(benzoxazine) ype CFRP was e allows he eco e y o ca bon
461
ibe s ha p esen mos ly clean su aces and mechanical p ope ies simila o some comme cial
462
i gin ca bon ibe s.
463
- The cooling and condensa ion o he apo s om he py olysis s age gene a es a liquid and a
464
gaseous ac ion. The liquid ac ion is composed o an aqueous and an o ganic phase, bo h o
465
which a e o low alue due o hei complex composi ion based on ni ogenous and oxygena ed
466
a oma ic compounds. The gaseous ac ion is composed o CH4 and CO2, i has low calo i ic alue
467
and is gene a ed in small quan i ies.
468
- I he apo s a e ea ed a high empe a u e (900 °C) in a CSi- illed eac o , he amoun o
469
liquids gene a ed is signi ican ly educed, inc easing he p opo ion o gases o mo e han
470
double. These gases imp o e hei composi ion signi ican ly, en iching hemsel es wi h H2 and
471
educing hei CO2 con en , which doubles hei calo i ic alue.
472
- I has been p o en ha he ma e ial used as solid bed in he ubula eac o has an app eciable
473
in luence. The bes esul s ha e been ob ained by using a esidual e ac o y ma e ial, hanks o
474
which he p o i abili y o he p ocess inc eases conside ably. This is why: (1) i is a was e ma e ial
475
and (2) i gene a es a H2 p opo ion highe han 50% by olume in he gases, which enables he
476
sepa a ion o H2 as a pu e compound, p esen ing a wide ange o applica ions.
477
- The esul s ob ained in his wo k show ha he ma e ial eco e ing o he polyme ic esin in
478
he CFRP was e ecycling p ocess is possible, which ep esen s a conside able ad ance in he
479
ield. This is go by a echnically simple and scalable me hod, e y usual in he chemical indus y.
480
As a as cos s a e conce ned, he only ele an cos is he ene gy consump ion o each he
481
ea men empe a u e, since solid bed ma e ial is a eusable was e ma e ial. Besides, his
482
ene gy could be ob ained om he gases h ough he sepa a ion o H2 by p essu e swing
483
adso p ion (PSA) and he employmen o he by-p oduc gas, which would e ain high HHV, o
484
gene a e ha ene gy.
485
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Acknowledgemen s
487
The au ho s wan o hank he Minis y o Economy and Compe i i eness o he Spanish
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Go e nmen o he unding (Re . CTM2013-48887-C2-1-R). The au ho s also hank he Basque
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Go e nmen o he Resea che T aining G an awa ded o N. Gas elu in 2015 call and he
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inancing g an ed o he “Sus ainable P ocess Enginee ing” esea ch g oup o he 2016-2021
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pe iod.
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