Jou nal o Cleane P oduc ion 441 (2024) 141072
A ailable online 1 Feb ua y 2024
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Low-p essu e oligome iza ion o dilu ed e hylene on a HZSM-5
zeoli e ca alys
Zu ia Tabe nilla
*
, Aina a A eka , And ´
es T. Aguayo , Ja ie Bilbao , E a Epelde
**
Depa men o Chemical Enginee ing, Uni e si y o he Basque Coun y (UPV/EHU), P. O. Box 644, 48080, Bilbao, Spain
ARTICLE INFO
Handling Edi o : Jin-Kuk Kim
Keywo ds:
Dilu ed e hylene
Gasoline
Oligome iza ion
HZSM-5 zeoli e
Coke deac i a ion
ABSTRACT
The oligome iza ion a low p essu e o dilu ed e hylene coming om seconda y s eams is an a ac i e ou e o
hyd oca bon p oduc ion, by means o a low cos and ene gy e icien p ocess. To e alua e he iabili y o his
p ocess, he e ec o dilu ion wi h N
2
o syngas on he low-p essu e oligome iza ion o e hylene (1.5 ba ) was
s udied on a ca alys p epa ed wi h a HZSM-5 zeoli e agglome a ed in a mesopo ous ma ix o
α
- and γ-Al
2
O
3
,
aiming o p oduce C
5+
hyd oca bons (gasoline). The expe imen s we e pe o med in a ixed bed eac o a 325 ◦C
and a space ime o 10.6 g
ca alys
h mol
C
−1
. Fo an e hylene pa ial p essu e o 0.33 ba , con e sion su passed 80 %
and high C
5+
hyd oca bon yield was ob ained: >40 % wi h N
2
as diluen ; and, >30 % wi h syngas. The g ea e
e ec o syngas dilu ion on supp essing he o ma ion o a oma ics is explained by he ole o H
2
in dec easing
he ex en o dehyd ocycliza ion eac ions. The dilu ion o e hylene limi s he ex en o he eac ion s ages, bu i
also a enua es he s ages o coke o ma ion, by acili a ing he di usion o so coke in he mesopo ous ma ix
and con ibu ing o dec ease he deposi ion o ha d coke in he zeoli e mic opo es. Consequen ly, a pseudo-
s eady s a e o he ca alys is eached wi h a no able emnan ac i i y o he o ma ion o highe hyd oca bons.
1. In oduc ion
In he ansi ion pe iod owa ds he gene al use o enewable en-
e gies, he ul illmen o he deca boniza ion commi men by he
de eloped coun ies calls o he imp o emen o new p ocesses o
p oduce uels and chemicals om sus ainable sou ces and o in ensi y
he alo iza ion o ossil uels (Rissman e al., 2020; Zhang e al., 2022).
In his scena io, he oligome iza ion o ligh ole ins o liquid uels is
p esen ed as an a ac i e oppo uni y o alo ize s eams in which hese
ole ins a e p esen , al hough hei dilu ion makes uneconomical hei
sepa a ion o be used as eeds ock in he syn hesis o polyole ins. This
si ua ion is ela ed o su plus gas s eams in na u al gas (Ghashghaee,
2018) and d y gas om e ine y luidized ca aly ic c acking (FCC) uni s
(Palos e al., 2020), whe e he des ina ion o he dilu ed e hylene p esen
is ene gy eco e y. Simila ly, in he as py olysis o polyole inic plas-
ics, he ligh ole ins p oduced a e dilu ed in he N
2
used as ine gas
(A e xe e al., 2012). Also, in he hyd ogena ion o syngas o CO
2
o
ole ins (by he modi ied Fische -T opsch ou es and wi h me hanol as
in e media e), ligh ole ins a e dilu ed wi h H
2
, CO, CO
2
and me hane
(Po illo e al., 2022). Addi ionally, e hylene is also dilu ed in he
oxida i e coupling o me hane (OCM) p oduc s eam (Liu e al., 2022).
The on-line oligome iza ion o e hylene in hese s eams in o liquid
uels, wi hou he inhe en cos s o sepa a ion and a oiding comp es-
sion, is an in e es ing ini ia i e in he con ex o p ocess in ensi ica ion
s a egies, wi h he imp o emen o ene gy e iciency and i s economy as
main goals (K i ´
an e al., 2016; Moioli, 2022).
The echnologies o he oligome iza ion o ligh ole ins ope a e a
ele a ed p essu e, and among hem, he one based on he use o HZSM-5
based ca alys s is well es ablished, wi h he his o ical e e ence o he
Mobil Ole ins o Gasoline and Dis illa e (MOGD) p ocess (Quann e al.,
1988; Tabak e al., 1986). The cha ac e is ic mic opo es o he MFI
s uc u e o HZSM-5 zeoli e (wi h a high deg ee o connec ion be ween
he channels and wi hou cages in he in e sec ions) acili a es he
di usion o ligh ole ins and he de elopmen o he ca boca ionic
mechanism o oligome iza ion, by also limi ing he con inemen o he
oligome s. In addi ion, he acidi y o he HZSM-5 zeoli e can be modu-
la ed o a o he selec i e p oduc ion o highe ole ins o uels wi h a
educed con en o a oma ics (Mlina e al., 2012; Co ma e al., 2013).
To explain he ole o he acid si es, Jin e al. (2021) p oposed a de ailed
kine ic model, whe e he ac i i y o he zeoli e o he indi idual
* Co esponding au ho . Depa men o Chemical Enginee ing, Uni e si y o he Basque Coun y (UPV/EHU), P.O. BOX 644, 48080, Bilbao, Spain.
** Co esponding au ho . Depa men o Chemical Enginee ing, Uni e si y o he Basque Coun y (UPV/EHU), P.O. BOX 644, 48080, Bilbao, Spain.
E-mail add esses: [email p o ec ed] (Z. Tabe nilla), [email p o ec ed] (E. Epelde).
Con en s lis s a ailable a ScienceDi ec
Jou nal o Cleane P oduc ion
jou nal homepage: www.else ie .com/loca e/jclep o
h ps://doi.o g/10.1016/j.jclep o.2024.141072
Recei ed 17 July 2023; Recei ed in e ised o m 22 Janua y 2024; Accep ed 31 Janua y 2024
Jou nal o Cleane P oduc ion 441 (2024) 141072
2
eac ions is ela ed o he p esence o acid si es o di e en acidic
s eng h.
The a o emen ioned s udies in he oligome iza ion o e hylene ha e
been pe o med a high p essu e and by paying li le a en ion o ca alys
deac i a ion. S udies o e hylene oligome iza ion a low p essu e and
wi h p esence o diluen s ha en been mainly di ec ed o he con e sion
o bioe hanol in o hyd oca bons, whe e e hylene is conside ed as a eal
eac an because i is apidly o med a he eac o inle by dehyd a ion
o bioe hanol. These s udies ha e shown he no able impac o dilu ion
on p oduc dis ibu ion and on ca alys deac i a ion (Gayubo e al.,
2001; Aguayo e al., 2002; Ding e al., 2009; And ei e al., 2020; Fe -
nandes e al., 2020, 2021). Th ough he cha ac e iza ion o he occluded
in e media es (Johansson e al., 2009) and wi h di e en echniques
(iso opic labeling, empo al analysis o p oduc s, and ab ini io mic o-
kine ic modeling) (Van de Bo gh e al., 2016; Ba chu e al., 2017; Zeng
e al., 2022), a dual cycle mechanism, simila o ha es ablished o he
con e sion on me hanol o hyd oca bons, wi h ole ins and a oma ics
(alkylbenzenes) as in e media es in each cycle, has been jus i ied o
bioe hanol con e sion.
Pa icula ly, e hylene con e sion o highe hyd oca bons is hinde ed
by he limi ed eac i i y o his ole in, which is lowe han ha o o he
ole ins o highe molecula weigh (Ga wood, 1983). The e o e, a highe
empe a u e is needed han he one equi ed o he oligome iza ion o
p opylene o bu enes, which a o s he ex en o seconda y eac ions o
c acking and coke deposi ion. Consequen ly, a challenge in he oligo-
me iza ion o e hylene on HZSM-5 based ca alys s is he a enua ion o
ca alys deac i a ion. The cause o his deac i a ion is he e en ion o
oligome s in he mic opo es o he ca alys and hei e olu ion owa ds
polya oma ic s uc u es, blocking he acid si es and mic opo es o he
zeoli e (Monama e al., 2020). In a p e ious s udy (Díaz e al., 2020a)
he good beha io o a HZSM-5 based ca alys wi h a hie a chical po ous
s uc u e in he oligome iza ion o 1-bu ene a 1.5 ba was s udied.
In his wo k he oligome iza ion o e hylene dilu ed wi h N
2
o wi h
syngas has been s udied a educed p essu e (1.5 ba ) aiming o de e -
mine he e ec o e hylene pa ial p essu e and o he na u e o he
diluen s on he con e sion and yield o he p oduc ac ions, and on he
deac i a ion o he ca alys (a HZSM-5 zeoli e agglome a ed in a mes-
opo ous ma ix). I has been p e iously p o en ha he p esence o he
ma ix is a key ea u e o imp o e he s abili y o he HZSM-5 zeoli e
(Díaz e al., 2020b; Tabe nilla e al., 2023), whose o e all good pe -
o mance in he oligome iza ion o ligh ole ins is well es ablished in he
li e a u e (Li e al., 2017; Chen e al., 2020). I is ema kable ha he
p esence o a mesopo ous ma ix acili a es he di usion o he oligo-
me s owa ds he ex e io o he ca alys pa icle, by a oiding he o al
blockage o he zeoli e mic opo es and a enua ing he ex en o olig-
ome condensa ion in o polya oma ic s uc u es o ha d coke. This e ec
o he ma ix enables he ca alys o each a pseudo-s eady s a e wi h a
subs an ial emnan ac i i y, as i has been p e iously p o en in he
con e sion o oxygena es in o ole ins (P´
e ez-U ia e e al., 2016) and in
he oligome iza ion o 1-bu ene (Díaz e al., 2021). Special a en ion has
been paid in his wo k o he p oduc ion o C
5+
hyd oca bons and o
hei composi ion, due o he in e es o being added in o he e ine y
gasoline pool. The moni o ing o he e olu ion o he esul s wi h he
ime on s eam and he analysis o he na u e and loca ion o he coke
has allowed o de e mine he e ec o he dilu ion on a enua ing he
deac i a ion and on acili a ing a pseudo-s eady s a e o he ca alys
wi h ema kable ac i i y. The esul s a e o in e es o he alo iza ion
o dilu ed e hylene-con aining s eams om di e en p ocesses o hy-
d oca bon p oduc ion om sus ainable sou ces.
2. Expe imen al
2.1. Ca alys p epa a ion and cha ac e iza ion
The p ocedu e o ca alys p epa a ion and cha ac e iza ion is e-
po ed in de ail elsewhe e (Díaz e al., 2020b; Tabe nilla e al., 2023). In
he p epa a ion o he ca alys , a HZSM-5 zeoli e (Zeolys In e na ional,
SiO
2
/Al
2
O
3
mola a io o 30) was agglome a ed wi h pseudoboehmi e
(Sasol Ge many, 32 w %) as binde and a colloidal dispe sion o
α
-Al
2
O
3
(Al a Aesa , 18 w %) as ine ille . I should be men ioned ha he
colloidal na u e o he ille acili a es he p epa a ion by inc easing he
homogenei y o he mix u e. The ca alys pa icles we e ob ained by
ex usion o he mix u e o hese ma e ials, and he ex uda es we e i s
d ied a oom empe a u e (24 h) and la e in an o en a 110 ◦C (24 h).
Subsequen ly, he pa icles we e sie ed o a pa icle size ange be ween
0.12 and 0.3 mm (sui able o i s use in a ixed bed eac o ). P io o i s
use, he ca alys is calcined a 575 ◦C o 2 h (hea ing amp o 5 ◦C
min
−1
). A e his calcina ion, he zeoli e adop s i s acid o m and i is
hyd o he mally s able (p ope y equi ed o eco e i s acidi y in suc-
cessi e eac ion- egene a ion cycles o coke combus ion). Mo eo e ,
du ing his calcina ion s ep he pseudoboehmi e is con e ed in o
γ-Al
2
O
3
. No e ha he me hod o he agglome a ion o he zeoli e and
he nominal composi ion o he composi e (50 w % zeoli e/32 w %
γ-Al
2
O
3
/18 w %
α
-Al
2
O
3
) is sui able o ob ain a high mechanical
s eng h, by almos keeping zeoli e p ope ies (P´
e ez-U ia e e al.,
2016). Thus, a highe con en o binde and ille gi es way o a sub-
s an ial dec ease in zeoli e p ope ies, due o he pa ial blockage o he
mic opo e mou hs.
The physical p ope ies (BET su ace a ea, mic o- and mesopo e
olume and dis ibu ion) and he acid p ope ies o he esh zeoli e, he
ma ix and ca alys a e shown in Table 1. The p ope ies o he ma ix
ga he ed in Table 1 co espond o a composi e o γ-Al
2
O
3
/
α
-Al
2
O
3
,
p epa ed by he o me p ocedu e o ca alys p epa a ion, bu in he
absence o zeoli e. The physical p ope ies we e de e mined by N
2
adso p ion-deso p ion (Fig. S1 in he Suppo ing In o ma ion) in a
Mic ome i ics ASAP 2010. The acid s eng h o he ca alys was de e -
mined by adso p ion-deso p ion o NH
3
in a calo ime e Se a am TG-
DSC 111, wi h a Ha a d injec ion pump, coupled o a mass spec om-
e e Balze s Ins umen s. P io o analysis, he samples we e swep wi h
He (80 cm
3
min
−1
) a 500 ◦C o 1 h. Then, he empe a u e was s abi-
lized a 150 ◦C wi h a low a e o He o 20 cm
3
min
−1
. A hese con-
di ions, he sa u a ion o he sample was ca ied ou by injec ion o NH
3
(50 cm
3
min
−1
). A e he sa u a ion o he sample, he physically
adso bed molecules we e emo ed wi h He (20 cm
3
min
−1
) a 150 ◦C.
Finally, a empe a u e-p og ammed deso p ion (TPD) was pe o med by
hea ing up he sample up o 550 ◦C wi h a hea ing a e o 5 ◦C min
−1
in a
low a e o He o 20 cm
3
min
−1
, eco ding a he same ime he signal o
NH
3
. The p ocedu e was also ep oduced in an Au ochem 2920 equip-
men o asce ain he NH
3
-TPD p o iles (Fig. S2).
In o de o deepen in he iden i ica ion o he ype o acid si es in he
samples (B øns ed and Lewis acid si es) py idine adso p ion was ca ied
ou a 150 ◦C using a Nicole 6700 appa a us equipped wi h a Specac
ca aly ic chambe . A able o ~10 mg o sample (zeoli e o ca alys ) was
p epa ed by g inding and p essing he g ains a 10–12 on cm
−2
o 15
min. The able was in oduced in he ca aly ic chambe and was sub-
mi ed o a hea p e ea men a 550 ◦C wi h a hea ing a e o 10 ◦C
min
−1
, unde acuum, o elimina e impu i ies. Then, empe a u e was
cooled down o 150 ◦C and he signal was eco ded wi h a equency o
2 min
−1
. The esul s a e ga he ed in Fig. S3.
Table 1
Physical and acid p ope ies o he ma ix, HZSM-5 zeoli e and ca alys .
Ma ix Zeoli e Ca alys
Physical p ope ies
S
BET
(m
2
g
−1
) 147 356 281
S
mic o
(m
2
g
−1
) 0 275 160
V
meso
(cm
3
g
−1
) 0.41 0.11 0.30
V
mic o
(cm
3
g
−1
) 0 0.11 0.07
Acid p ope ies
To al acidi y (
μ
mol
NH3
g
−1
) 107 686 362
Acid s eng h (kJ mol
NH3
−1
) 50 150 110
BAS/LAS a io 0 4.3 3.4
Z. Tabe nilla e al.
Jou nal o Cleane P oduc ion 441 (2024) 141072
3
As obse ed in Table 1, he p esence o he ma ix inc eases he po e
olume wi h espec o he zeoli e due o he con ibu ion o he ma ix
mesopo es. Fu he mo e, he impac o he ma ix on he acidi y is he
dec ease o he o al acidi y and he a e age acid s eng h o he si es,
due o he limi ed acidi y o he si es (weak only) o he γ-Al
2
O
3
in he
ma ix.
2.2. Reac ion equipmen and condi ions
E hylene oligome iza ion uns we e ca ied ou in a eac ion equip-
men shown in Fig. S4 and desc ibed in de ail elsewhe e (Tabe nilla
e al., 2023). The eac o is a 316 s ainless-s eel ixed-bed eac o (in-
e nal diame e o 9 mm and an e ec i e leng h o 100 mm). To ensu e a
cons an heigh o 1.5–2 cm, he ca aly ic bed is o med o ca alys and
ine solid (SiC). To a oid condensa ion p oblems, he gas p oduc
s eam is hea ed up o 110 ◦C and i is analyzed online in an Agilen
300A Mic oGC gas-ch oma og aph, which is equipped wi h he
ollowing columns: i) Molecula sie e (MS-5A) o quan i y O
2
, N
2
, H
2
,
CO, CH
4
, CO
2
; ii) Po apak Q (PPQ) o oxygena ed compounds, CO
2
,
ligh ole ins (C
2
=
-C
3
=
) and wa e ; iii) Alumina o ligh hyd oca bons up o
C
4
, and; i ) OV-1 ype column o highe hyd oca bons. Gas p oduc
s eam was analyzed e e y 4 min. Liquid p oduc s (C
5
–C
20,
wi h insig-
ni ican con en s o e ained C
3
and C
4
compounds) collec ed in di e en
pe iods o ime on s eam we e analyzed ex-si u in a GC ×GC/MS
(Agilen 5975C Se ies GC/MSD) equipmen coupled on-line wi h an XL
MSD mass spec ome e equipped wi h a FID de ec o , a non-pola col-
umn (DB-5MS, 30 m ×0.25 mm ×0.25
μ
m), and a pola column
(HP-INNOWAX, 5 m ×0.25 mm ×0.15
μ
m). Fo he analysis a 2 ◦C
min
−1
hea ing a e was used om 40 ◦C o 200 ◦C (cons an o 4 min).
De ailed in o ma ion on he analysis is desc ibed in Sec ion S3 in he
Suppo ing In o ma ion.
Typically, he eac ions we e ca ied ou a : 1.5 ba ; 325 ◦C; space
ime, 10.6 g
ca alys
h mol
C
−1
(co esponding o a ca alys mass o 1 g and
an e hylene mola low a e o 37 ml min
−1
); e hylene concen a ion in
he eed, 20–80 % (using 99.999 % e hylene, Ai Liquide); e hylene
pa ial p essu e in he eed, 0.33–1.18 ba , using as diluen s N
2
and
syngas (H
2
/CO mola a io o 3/1); and, ime on s eam (TOS), 5 h.
These condi ions ha e been es ablished based on he esul s ob ained in
a p io wo k whe e he same ca alys was used in he oligome iza ion o
pu e e hylene (Tabe nilla e al., 2023).
The esul s we e e alua ed in e ms o e hylene con e sion (X), yield
(Y
i
) and selec i i y (S
i
) o each lumped p oduc , which a e de ined in
Eqs. (1)–(3), espec i ely.
X=
F0−F
F0
⋅100 (1)
Yi=
Fi
F0
⋅100 (2)
Si=
Fi
F0−F⋅100 (3)
whe e F
0
and F, a e he mola low a e o e hylene in he eed and in he
ou le s eam, while F
i
is he low a e o i lump in he ou le s eam. All
low a es in Eqs. (1)–(3) a e exp essed in con en C uni s.
The ollowing main lumps ha e been de ined: C
3
=
and C
4
=
ole ins, C
4
pa a ins, C
5-7
alipha ics (mainly pa a ins) and C
5+
(gasoline) ac ion
(including ole ins, pa a ins and a oma ics). No me hane has been
de ec ed unde he ope a ing condi ions s udied.
2.3. Used ca alys cha ac e iza ion
A e each eac ion, he ca aly ic bed was swep wi h 30 cm
3
min
−1
o N
2
a he eac ion empe a u e (325 ◦C) o 30 min in o de o ensu e
he ep oducibili y o he used ca alys cha ac e iza ion analyses. The
con en and na u e o he di e en ypes o coke (so coke and ha d
coke) we e de e mined by empe a u e-p og ammed sweeping wi h N
2
(N
2
-TPS) ollowed by empe a u e-p og ammed oxida ion (TPO) anal-
ysis, espec i ely, using a TGA Q5000TA he mobalance (The mo Sci-
en i ic) equipmen .
Fo he N
2
-TPS analysis, he used ca alys samples (~15 mg) we e
ea ed wi h N
2
(50 cm
3
min
−1
) hea ing up he sample up o 350 ◦C wi h
a hea ing a e o 10 ◦C min
−1
and kep o 20 min, o sweep he so coke
con ined in he ca alys po es. Subsequen ly, he TPO analyses o he
emaining coke ac ion (ha d coke) we e ca ied ou wi h ai (50 cm
3
min
−1
), up o 700 ◦C (2 ◦C min
−1
) and kep o 1 h ( o ensu e he
comple e combus ion o he ha d coke o med inside he zeoli e
channels).
3. Resul s
3.1. Con e sion and p oduc yield
Fig. 1 shows he e ec o e hylene pa ial p essu e in he eac o inle
eed, dilu ed in N
2
(Fig. 1a) and in syngas (SG) (Fig. 1b), on e hylene
con e sion and p oduc yield (C
3
=
and C
4
=
ole ins, C
4
pa a ins, C
5-7
ali-
pha ics (mainly pa a ins), and C
5+
(gasoline) hyd oca bons) a ze o
ime on s eam ( i s sampling a 4 min). An inc ease in e hylene pa ial
p essu e in he eed up u ns he con e sion (abo e 80 % a all condi-
ions), which is cohe en wi h he li e a u e on he con e sion o ligh
ole ins on HZSM-5 ca alys s, by inc easing he same a iable (Lin e al.,
2009; Fe nandes e al., 2020), o he absolu e p essu e (Ding e al.,
2009). The inc ease o e hylene con e sion caused by a aise in e hylene
pa ial p essu e is associa ed wi h a g ea e amoun o eagen a ailable
a zeoli e ac i e si es. The main di e ence be ween he esul s wi h he
wo diluen s is ha wi h syngas dilu ion (Fig. 1b) he comple e con-
e sion is no eached and he yield o C
5+
hyd oca bons is no ably
lowe . Conside ing ha he yield o C
5-7
alipha ics is simila , he di -
e ence in he yield o C
5+
hyd oca bons is due o he a enua ion o
a oma ic o ma ion wi h syngas as diluen . The explana ion lies in he
a enua ion o he ex en o he dehyd ocycliza ion eac ions o
e hylene, p opylene and bu enes, he la e wo ha ing a ele an ole as
highly eac i e in e media es in he oligome iza ion o e hylene o e
HZSM-5 ca alys s (Fe nandes e al., 2020).
Fo bo h diluen s, he yield o bu enes (C
4
=
, o med by e hylene
dime iza ion and in e media es in he o ma ion o highe ole ins) and
p opylene (C
3
=
, p oduc o c acking by β-scission o highe oligome s)
dec eases wi h inc easing e hylene pa ial p essu e in he eac o inle
s eam. I should be no ed ha his e ec o e hylene pa ial p essu e is
used o maximize p opylene selec i i y om e hylene con e sion on
HZSM-5 ca alys s (Lin e al., 2009).
3.2. Ca alys deac i a ion
Unde kine ic egime condi ions (no excess o ca alys ), e hylene
con e sion dec eases wi h ime on s eam due o ca alys deac i a ion.
Inc easing e hylene pa ial p essu e in he eed, i is obse ed ha unde
hese condi ions he deac i a ion is as e , being his e ec mo e ele-
an in Fig. 2b (wi h syngas as diluen ) han in Fig. 2a (wi h N
2
). This
e ec canno be obse ed in Fig. 2 as he dec ease in con e sion is
insigni ican . Howe e , i is mo e e iden on he e olu ion o p oduc
dis ibu ion (Fig. 3) as la e commen ed. The inc ease in he deac i a-
ion a e is explained because an inc ease in e hylene pa ial p essu e
a o s he ex en o he o ma ion o oligome s ha a e e ained in he
po es o he ca alys , and hus, he ex en o eac ions o coke o ma ion,
as checked in Sec ion 3.4.
A sligh ly lowe deac i a ion was also obse ed wi h H
2
as diluen ,
which can be a ibu ed o he ole o H
2
in a enua ing he a e o
dehyd ocycliza ion eac ions o ole ins wi h o ma ion o coke. I should
be no ed ha And ei e al. (2020) obse ed a mo e impo an e ec o
deac i a ion a enua ion in he oligome iza ion o dilu ed e hylene by
he p esence o H
2
, bu wo king a 15 ba . In Sec ion 3.2 an explana ion
Z. Tabe nilla e al.
Jou nal o Cleane P oduc ion 441 (2024) 141072
4
on deac i a ion is gi en, in which he ole o occluded oligome s and
coke o ca aly ic o igin a e dis inguished.
I is ema kable in he dynamics o deac i a ion in Fig. 2 ha a e an
ini ial pe iod o apid deac i a ion he con e sion esul s in Fig. 1 a e
almos cons an . In he ini ial apid deac i a ion, he oligome s occluded
in he ca alys block he access o e hylene and o he eac ion in-
e media es o he zeoli e mic opo es, and so, hampe he o ma ion and
subsequen di usion o he oligome s owa ds he ex e io (Mlina e al.,
2012; Díaz e al., 2020a; Bickel and Gounde , 2022). Aiming o mini-
mize he deac i a ion in his ini ial pe iod, Co ma e al. (2013) checked
o he in e es o gene a ing mesopo es wi hin he zeoli e o a enua e
he blockage o he mic opo es. The p esence o a mesopo ous ma ix is
disclosed as an e icien s a egy o he di usion o he oligome s o-
wa ds he ex e io o he ca alys pa icle (Díaz e al., 2021). The esul s
in Fig. 2 show he e ec i eness o zeoli e agglome a ion in a mesopo ous
ma ix o minimize he ini ial deac i a ion by po e blockage, which
enables o each a pseudo-s eady s a e o he ca alys wi h a ema kable
emnan ac i i y. Unde his s a e, he deac i a ion o he ca alys is slow
and i is ela ed o he e olu ion o he e ained oligome s owa ds
polya oma ic condensed coke s uc u es h ough condensa ion eac ions
(Halmenschlage e al., 2016). These eac ions a e ca alyzed by acid
si es, whe e B øns ed si es play a key ole (Zhang e al., 2020), by he
well-es ablished mechanisms wi h a oma ics as main in e media es
(Guisne and Magnoux, 2001; Chung e al., 2011; Ib´
a˜
nez e al., 2017;
Co de o-Lanzac e al., 2018). In Fig. S5 he e olu ion o e hylene con-
e sion is compa ed o he zeoli e and he agglome a ed ca alys .
The e ec o e hylene dilu ion on he e olu ion wi h ime on s eam
o he main p oduc dis ibu ion is shown in Fig. 3 ( o N
2
as diluen ) and
Fig. 4 ( o syngas). As obse ed, his dilu ion a enua es ca alys
deac i a ion and i has an impac on p oduc dis ibu ion, due o: (i) he
lowe a ailabili y o ca alys acid si es o oligome iza ion and side e-
ac ions; and, (ii) he di usion limi a ions due o he p esence o coke in
he po ous s uc u e o he ca alys . Thus, he yields o highe molecula
weigh p oduc s (quan i ied as C
5-7
and C
5+
in Fig. 3d and e and 4d, e)
dec ease wi h ime on s eam, while he yields o he in e media e ole-
ins, bu enes (Fig. 3b and 4b) and p opylene (Fig. 3a and 4a) inc ease.
The g owing end in he yield o hese ole ins wi h ime on s eam in-
dica es ha ca alys deac i a ion a ec s in a majo ex en hei oligo-
me iza ion o highe ole ins han hei o ma ion, by e hylene
dime iza ion in he case o bu enes and by β-scission o highe ole ins in
case o p opylene (Fe nandes e al., 2020, 2021). Fo he highes dilu ion
(e hylene pa ial p essu e in he eed o 0.33 ba ), he cons an yield o
hese ole ins wi h ime on s eam can be a ibu ed o a balance be ween
he e ec o deac i a ion on he eac ions o hei o ma ion and con-
e sion. The a enua ion o he a e o hyd ogen ans e eac ions wi h
ca alys deac i a ion is e idenced by he dec ease o bu ane yield wi h
ime on s eam (Fig. 3c and 4c), which is conside ed an index o he
ex en o hese eac ions, ca alyzed by he acid si es o he HZSM-5
zeoli e (Zhang e al., 2020).
Compa ing he esul s wi h he wo diluen s in Figs. 3 and 4, he
di e ence in he e olu ion o C
5+
hyd oca bon yield wi h ime on s eam
is s iking. The lowe ini ial yield and he less p onounced dec ease o
his yield wi h ime on s eam when syngas is used o dilu ion (Fig. 4e)
in compa ison o N
2
(Fig. 3e), is a ibu able o he g ea e a enua ion o
he ex en o he eac ions o a oma ic o ma ion by he p esence o H
2
,
due o he shi o he dehyd ocycliza ion eac ions o ole ins (And ei
e al., 2020). This esul a i ies he ole a ibu ed o a oma ics as coke
p ecu so s, which a e esponsible o ca alys deac i a ion (Mlina e al.,
Fig. 1. E ec o e hylene pa ial p essu e in he eed on i s con e sion and on he yield o he main lumped p oduc s o di e en diluen s: a) N
2
and b) Syngas (SG).
Reac ion condi ions: 325 ◦C; 1.5 ba ; space ime, 10.6 g
ca alys
h mol
C
−1
(1 g o ca alys ); 0 h on s eam.
Fig. 2. E ec o e hylene pa ial p essu e in he eed on he e olu ion wi h ime on s eam o e hylene con e sion o di e en diluen s a) N
2
and b) Syngas (SG).
Reac ion condi ions: 325 ◦C; 1.5 ba ; space ime, 10.6 g
ca alys
h mol
C
−1
(1 g o ca alys ).
Z. Tabe nilla e al.
Jou nal o Cleane P oduc ion 441 (2024) 141072
5
2012). Fu he mo e, he ole o H
2
in a enua ing he eac ion ex en o
coke e olu ion owa ds condensed s uc u es on acid ca alys s is well
es ablished in some eac ions whe e ole ins pa icipa e as eac an s o
in e media es (A o a e al., 2018; Zhao e al., 2019).
3.3. Pseudo-s a e s eady o he ca alys
Fo p ocess scale-up, he esul s o p oduc dis ibu ion in he ca a-
lys pseudo-s eady s a e ( ime on s eam abo e o 3–4 h) a e pa icula ly
in e es ing. These esul s a e shown in Fig. 5, o he uns wi h N
2
(Fig. 5a) and syngas (Fig. 5b) as diluen s. The highe con e sion o
e hylene in he pseudo-s eady s a e wi h syngas as diluen is a conse-
quence o he a o emen ioned (Sec ion 3.2) lowe deac i a ion wi h
espec o he esul s wi h N
2
(Fig. 2), wi h a lowe coke con en in he
ca alys when he equilib ium o i s deposi ion is eached (as shown in
Sec ion 3.4). In addi ion, he p esence o H
2
also jus i ies he lowe yield
o C
5+
hyd oca bons, as he eac ions o a oma ic o ma ion, which
ake place by ole in dehyd ocycliza ion, a e hinde ed (And ei e al.,
2020).
Figs. 6 and 7, co esponding o he uns wi h N
2
and syngas as dil-
uen s, espec i ely, show he selec i i y o hyd oca bons (pa a ins,
ole ins and a oma ics) acco ding o hei ca bon numbe , in he pseudo-
s eady s a e o he ca alys . The di e ence in he esul s wi h he wo
diluen s is no ewo hy. Thus, when N
2
is used (Fig. 6), as e hylene
pa ial p essu e inc eases and due o he g ea e ex en o he eac ion,
he o ma ion o hyd oca bons o highe molecula weigh is a o ed,
wi h a no able p esence o C
8+
hyd oca bons a a pa ial p essu e o
1.18 ba . The highe selec i i y o pa a ins and a oma ics wi h
inc easing e hylene pa ial p essu e is also a consequence o he highe
ex en o hyd ogen ans e eac ions. Howe e , wi h syngas as diluen
(Fig. 7) he e ec o e hylene pa ial p essu e is smalle . The supp ession
o he o ma ion o C
8+
hyd oca bons is o be highligh ed, which can be
explained by he a enua ion o he ex en o ole in dehyd ocycliza ion,
esponsible o he o ma ion o a oma ics (And ei e al., 2020; Fe -
nandes e al., 2021). Conside ing he ole a ibu ed by Shi and Bhan
(2022, 2023) o H
2
in he dual cycle mechanism o he con e sion o
me hanol o ole ins, he lowe yield o a oma ics and he highe yield o
p opylene and bu enes wi h syngas dilu ion may be ela ed o he
pa icipa ion o H
2
limi ing he e olu ion o he a oma ic cycle and a-
o ing he o ma ion o p opylene and bu enes om he ole in cycle.
These au ho s also es ablished ha CO dilu ion only had an impac on
he mechanism ( o boos ing he p opaga ion o he a oma ic cycle) a
high p essu e, which is also in ag eemen wi h he a o emen ioned e-
sul s, ha can be explained by he ole o H
2
.
3.4. Coke deposi ion
In Fig. 8 (N
2
dilu ion) and in Fig. 9 (syngas dilu ion), he N
2
-TPS
(g aphs a) and TPO (g aphs b) p o iles o he co esponding used ca -
alys s a e shown. The con en s o so coke and ha d coke indica ed in
hese igu es ha e been calcula ed om he a ea de ined by he N
2
-TPS
and TPO p o iles, espec i ely. The analysis condi ions ha e been
desc ibed in Sec ion 2.3, and each p o ile co esponds o a ype o coke
(so coke in N
2
-TPS p o ile and ha d coke in TPO p o ile). The exis ence
o hese wo ypes o coke on he HZSM-5 zeoli e ca alys s in he olig-
ome iza ion o e hylene is well es ablished in he li e a u e (Co ma
e al., 2013; Fe nandes e al., 2020; Monama e al., 2020), whe e he
apid ini ial deac i a ion o he ca alys (obse ed in Fig. 2) is a ibu ed
Fig. 3. E ec o e hylene pa ial p essu e in he eed, using N
2
as diluen , on he e olu ion wi h ime on s eam o he main p oduc yields: a) C
3
=
, b) C
4
=
, c) C
4,
d) C
5-7
,
and e) C
5+
. Reac ion condi ions: 325 ◦C; 1.5 ba ; space ime, 10.6 g
ca alys
h mol
C
−1
(1 g o ca alys ).
Z. Tabe nilla e al.
Jou nal o Cleane P oduc ion 441 (2024) 141072
6
o he physical phenomenon o e en ion o he oligome s (so coke)
which pa ially block he zeoli e mic opo es. Bickel and Gounde (2022)
analyzed he di usion limi a ions o he oligome s e ained in he mi-
c opo es o HZSM-5 zeoli e and hei e ec on p oduc dis ibu ion in
he oligome iza ion o p opylene. As shown in Fig. 2, a e he ini ial
apid deac i a ion, he ca alys eaches a pseudo-s eady s a e, a which a
slow deac i a ion is obse ed, a ibu able o he o ma ion and e olu-
ion o ha d coke, wi h a lowe incidence on ca alys po e blockage han
so coke e en ion (Jan e al., 2018).
Fo bo h diluen s he con en o so coke is limi ed (Fig. 8a and 9a).
P esumably he compounds a e e ained in he ma ix o he ca alys ,
whose mesopo ous s uc u e allows hei ci cula ion h oughou he
eac ion. Thus, a high ac ion o so coke p esen du ing each un is
emo ed wi h he N
2
sweeping pe o med in si u a he end o each un
(30 min a 325 ◦C). I is obse ed ha he so coke con en inc eases
wi h inc easing e hylene pa ial p essu e and he highes so coke
con en o 1.8 w % is ob ained a an e hylene pa ial p essu e o 1.18
ba . This educed p esence o so coke jus i ies he ca alys o each a
pseudo-s eady s a e in Fig. 2, wi h a ema kable emnan ac i i y due o
he ac ha he access o e hylene and in e media es o he zeoli e
c ys als is only pa ially limi ed. This e ec o he hie a chical po ous
s uc u e o a enua ing he deposi ion o so coke and i s condensa ion
Fig. 4. E ec o e hylene pa ial p essu e, using syngas as diluen , on he e olu ion wi h ime on s eam o he main p oduc yields: a) C
3
=
, b) C
4
=
, c) C
4,
d) C
5-7
, and e)
C
5+
. Reac ion condi ions: 325 ◦C; 1.5 ba ; space ime, 10.6 g
ca alys
h mol
C
−1
(1 g o ca alys ).
Fig. 5. E ec o e hylene pa ial p essu e in he eed on i s con e sion and yields o he main lumped p oduc s in he pseudo-s eady s a e o he ca alys , using as
diluen s, a) N
2
and b) syngas (SG). Reac ion condi ions: 325 ◦C; 1.5 ba ; space ime, 10.6 g
ca alys
h mol
C
−1
(1 g o ca alys ); 3 h on s eam.
Z. Tabe nilla e al.
Jou nal o Cleane P oduc ion 441 (2024) 141072
7
eac ions o ha d coke has al eady been obse ed in he li e a u e on
ca alys s p epa ed wi h a HZSM-5 wi h mesopo es gene a ed by desili-
ca ion (Monama e al., 2020).
The mechanism o ha d coke o ma ion is slowe han he as
e en ion o so coke and akes place h ough eac ions ac i a ed by he
acid si es o he ca alys (Halmenschlage e al., 2016; Zhang e al.,
2020) whe e he dehyd ocycliza ion o ole ins and he hyd ogen ans e
eac ions play a ele an ole. The TPO p o iles o he used ca alys s
(Fig. 8b and 9b) gi e e idence o he no able e ec o inc easing
e hylene pa ial p essu e, as ha d coke con en is boos ed, whose
maximum con en is o 4.6 w % o an e hylene pa ial p essu e o 1.18
ba , wi h N
2
as diluen (Fig. 8b). Fo all he used ca alys s, he TPO is
decon olu ed in o wo cha ac e is ic peaks o he con e sion o ole ins
o e HZSM-5 zeoli e ca alys s, which a e a ibu ed o he combus ion o
wo ha d coke ac ions (Ib´
a˜
nez e al., 2017; Co de o-Lanzac e al., 2018;
Díaz e al., 2021). The ha d coke I, wi h he maximum combus ion a e
a ~460–480 ◦C, is likely deposi ed on he ma ix and on he ex e io o
he c ys als o he HZSM-5 zeoli e, which acili a es i s combus ion. Ha d
coke II will be deposi ed inside he zeoli e channels, by limi ing ai
di usion, which jus i ies he need o a highe combus ion empe a u e,
wi h a maximum a e a ~540–560 ◦C. The highe o al ha d coke
con en in he ca alys wi h inc easing e hylene pa ial p essu e is
explained by he ac ha he ex en o he eac ions o i s o ma ion a e
a o ed, in pa allel o he highe ex en o he eac ions o he o ma ion
o highe hyd oca bons. The simila esul ob ained o he di e en
diluen s, wi h a maximum coke con en o 5.3 w % o a pa ial p essu e
o e hylene o 1.18 ba , sugges s ha coke o ma ion does no occu
di ec ly om a oma ics (absen in he eac ion wi h syngas as diluen ),
bu ha i s o ma ion will ake place by dehyd ocycliza ion o poly-
condensed s uc u es o he ole inic oligome s e ained in he zeoli e
channels. This no able ex en o ole in dehyd ocycliza ion abo e 300 ◦C
is well es ablished (Bonnin e al., 2021). I is also no ewo hy ha he
na u e o he gaseous diluen shows a sca ce incidence on coke e olu-
ion, because he coke II/coke I a io (lowe han 1 in all cases, in he
0.3–0.9 ange) and he empe a u e o maximum combus ion a e o
hese cokes (457–503 ◦C o coke I and 543–561 ◦C o coke II) show
sligh di e ences o hese wo diluen s.
I should be highligh ed ha he coke ea u es a e sui able o acil-
i a e ca alys egene abili y (key condi ion o p ocess scale up). Thus,
he a o emen ioned esul s, wi h a high con en o so coke and a low
condensed ha d coke ( ega ding he empe a u e needed o i s com-
bus ion) ease i s emo al. The p ocedu e o ca alys egene a ion has
been es ablished in a p io wo k (Díaz e al., 2021) o he same ca alys
used in he oligome iza ion o 1-bu ene, which consis s o wo successi e
ea men s, a e which he ull eco e y o ac i i y is ob ained: i)
sweeping wi h N
2
(1 h a 400 ◦C), o he emo al o so coke ( apped
oligome s in he ma ix), and; ii) subsequen combus ion wi h ai o he
ha d coke (mainly deposi ed on he zeoli e mic opo es) ( amp o 10 ◦C
min
−1
be ween 400 and 500 ◦C and 0.5 h a 500 ◦C). Rega ding ha he
coke deposi ed on his wo k in he oligome iza ion o dilu ed e hylene is
less condensed, i s emo al wi h his ea men is also comple e. Hence,
he ca alys can be used in successi e eac ion- egene a ion cycles.
4. Conclusions
The low-p essu e oligome iza ion o e hylene dilu ed wi h N
2
o
syngas enables o ob ain a ema kable yield o highe hyd oca bons,
which jus i ies he in e es o de eloping a p ocess o he alo iza ion
wi h low cos o seconda y s eams con aining dilu ed e hylene. Thus,
o an e hylene pa ial p essu e o 0.33 ba he con e sion o e hylene is
g ea e han 80 % a 325 ◦C wi h ei he N
2
o syngas as diluen s, o a
mode a e space ime o 10.6 g
ca alys
h mol
C
−1
, wi h a C
5+
hyd oca bon
yield highe han 40 % wi h N
2
and o e 30 % wi h syngas. The educed
p esence o a oma ics wi h N
2
dilu ion, which is negligible wi h syngas,
is also a ac i e o he ob ained gasoline.
The p esence o a mesopo ous ma ix in he HZSM-5 ca alys acili-
a es he di usion o coke p ecu so s, minimizing he p oblems o zeoli e
coke deac i a ion as he e en ion o he oligome s is limi ed, which
acili a es he di usion o so coke (deposi ed in he ma ix) and a -
enua es he ha d coke o ma ion eac ions (mos ly in he mic opo es o
he HZSM-5 zeoli e). This a enua ion o coke deac i a ion is a o ed by
Fig. 6. P oduc dis ibu ion (selec i i y) in he pseudo-s eady s a e o he
ca alys acco ding o ca bon numbe and hyd oca bon amilies (pa a ins,
ole ins and a oma ics) using N
2
as diluen a di e en e hylene pa ial p essu e
in he eed: a) 0.33 ba , b) 0.74 ba and c) 1.18 ba . Reac ion condi ions:
325 ◦C; 1.5 ba ; space ime, 10.6 g
ca alys
h mol
C
−1
(1 g o ca alys ); 3 h on s eam.
Fig. 7. P oduc dis ibu ion (selec i i y) in he pseudo-s eady s a e o he
ca alys acco ding o ca bon numbe and hyd oca bon amilies (pa a ins,
ole ins and a oma ics) using syngas as diluen a di e en e hylene pa ial
p essu e in he eed: a) 0.33 ba , b) 0.74 ba and c) 1.18 ba . Reac ion condi-
ions: 325
◦C; 1.5 ba ; space ime, 10.6 g
ca alys
h mol
C
−1
(1 g o ca alys ); 3 h
on s eam.
Z. Tabe nilla e al.
Jou nal o Cleane P oduc ion 441 (2024) 141072
8
he dilu ion o e hylene as he ex en o coke o ma ion is limi ed and he
di usion o he p ecu so s (so coke) om he e ained coke is a o ed,
which e ol es in he c ys alline channels o he zeoli e (ha d coke).
Thus, he dilu ion o e hylene and he p esence o he ma ix in he
ca alys con ibu e o main aining a no able emnan ac i i y a e he
ini ial s age o oligome occlusion.
The esul s highligh he in e es o low-p essu e oligome iza ion o
dilu ed e hylene o in ensi y he alo iza ion o seconda y s eams om
sus ainable p oduc ion p ocesses o ole ins and o he hyd oca bons,
yielding gasoline ee o he e oa oms, and wi h a sui able composi ion o
be added in o he e ine y gasoline pool.
Sou ce o suppo
Any g an s/equipmen /d ugs, and/o o he suppo ha acili a ed
he conduc o esea ch/w i ing o he manusc ip (including AFMRC
p ojec de ails, i applicable).
⁃ Minis y o Science, Inno a ion and Uni e si ies o he Spanish
Go e nmen (P ojec PID2022-140584OB-I00)
⁃ Basque Go e nmen (P ojec IT1645-22)
⁃ Eu opean Regional De elopmen Funds (ERDF) and he Eu opean
Commission (HORIZON H2020-MSCA RISE, 2018. Con ac No.
823745)
⁃ Z. Tabe nilla is g a e ul o he PhD g an om he Depa men o
Educa ion, Uni e si y and Resea ch o he Basque Go e nmen
(PRE2023_2_0005)
CRediT au ho ship con ibu ion s a emen
Zu ia Tabe nilla: Da a cu a ion, In es iga ion, Me hodology,
W i ing – o iginal d a , Concep ualiza ion, W i ing – e iew & edi ing.
Aina a A eka: Valida ion, Visualiza ion, W i ing – o iginal d a ,
W i ing – e iew & edi ing, Concep ualiza ion, Funding acquisi ion,
P ojec adminis a ion. And ´
es T. Aguayo: Me hodology, Resou ces,
Supe ision, Da a cu a ion, In es iga ion, Valida ion. Ja ie Bilbao:
Concep ualiza ion, Da a cu a ion, W i ing – o iginal d a , W i ing –
e iew & edi ing, Supe ision, Valida ion. E a Epelde: Concep ualiza-
ion, Da a cu a ion, Supe ision, W i ing – o iginal d a , W i ing – e-
iew & edi ing.
Decla a ion o compe ing in e es
The au ho s decla e ha hey ha e no known compe ing inancial
in e es s o pe sonal ela ionships ha could ha e appea ed o in luence
he wo k epo ed in his pape .
Da a a ailabili y
The au ho s a e unable o ha e chosen no o speci y which da a has
been used.
Acknowledgmen s
This wo k has been ca ied ou wi h he inancial suppo o he
Minis y o Science, Inno a ion and Uni e si ies o he Spanish Go -
e nmen (PID2022-140584OB-I00); he Basque Go e nmen (P ojec
Fig. 8. E ec o e hylene pa ial p essu e in he eed, using N
2
as diluen , on (a) N
2
-TPS and (b) TPO p o iles o he used ca alys s. Reac ion condi ions: 325 ◦C; 1.5
ba ; space ime, 10.6 g
ca alys
h mol
C
−1
(1 g o ca alys ); 5 h on s eam.
Fig. 9. E ec o e hylene pa ial p essu e in he eed, using syngas as diluen , on (a) N
2
-TPS and (b) TPO p o iles o he used ca alys . Reac ion condi ions: 325 ◦C;
1.5 ba ; space ime, 10.6 g
ca alys
h mol
C
−1
(1 g o ca alys ); 5 h on s eam.
Z. Tabe nilla e al.
Jou nal o Cleane P oduc ion 441 (2024) 141072
9
IT1645-22); and he Eu opean Regional De elopmen Funds (ERDF) and
he Eu opean Commission (HORIZON H2020-MSCA RISE 2018. Con-
ac No. 823745). Z. Tabe nilla is g a e ul o he PhD g an om he
Depa men o Educa ion, Uni e si y and Resea ch o he Basque Go -
e nmen (PRE2023_2_0005).
Appendix A. Supplemen a y da a
Supplemen a y da a o his a icle can be ound online a h ps://doi.
o g/10.1016/j.jclep o.2024.141072.
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