Kine ic modeling o CO2 + CO hyd ogena ion o DME o e a CuO-
ZnO-Z O2@SAPO-11 co e-shell ca alys
Aina a A eka*, Miguel Sánchez-Con ado , Ande Po illo, Ja ie Bilbao, And es T.
Aguayo
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 . Tel.: 34-94-6015361. E-mail add ess: aina a.a [email protected]
ABSTRACT
A kine ic model o he CO2 + CO hyd ogena ion o dime hyl e he (DME) in a single
s ep o e an o iginal co e-shell s uc u ed CuO-ZnO-Z O2@SAPO-11 bi unc ional
ca alys (me allic in he co e and acid in shell) has been es ablished. The ca aly ic uns
ha e been ca ied ou in an iso he mal ixed bed eac o unde he ollowing condi ions:
250-320 ºC; 10-50 ba ; space ime, 1.25-15 gca ·h·molC-1; H2/COx mola ac ion in he
eed, 2.5-4, and CO2/COx, 0-1. The ca alys has a high ac i i y and s abili y as a esul
o he sepa a ion o eac ions in he wo unc ions.The model desc ibes he e ec o he
ope a ing condi ions ( empe a u e, p essu e and eed composi ion) o e he e olu ion o
p oduc dis ibu ion wi h ime on s eam. Fo his, he indi idual eac ions (CO2 and CO
hyd ogena ion o me hanol, i s dehyd a ion o DME, he WGS eac ion and he side
eac ion o hyd oca bons o ma ion) a e conside ed oge he wi h ca alys deac i a ion.
Using he model, simula ion s udies allow o es ablishing sui able ope a ing condi ions
(305 ºC,70 ba , CO2/COx o 0.75 and H2/COx o 3) o a ain a good comp omise
be ween DME yield and CO2 con e sion, eaching a alue o 23 % o bo h objec i es.
This is he Accep ed Manusc ip e sion o a Published Wo k ha appea ed in inal o m in Fuel P ocessing Technology 206 : (2020) , 106434.
To access he inal edi ed and published wo k see h ps://doi.o g/10.1016/j. up oc.2020.106434
© 2020. This manusc ip e sion is made a ailable unde he CC-BY-NC-ND 4.0 license h ps://c ea i ecommons.o g/licenses/by-nc-nd/4.0/
KEYWORDS: Model; deac i a ion; co e-shell; CO2; alo iza ion; dime hyl e he
GRAPHICAL ABSTRACT
Yield (%)
HC
MeOH
H2O
DME
CO
Time on s eam (h)
CO2
CuO-ZnO-Z O2
SAPO-11
CO
H2
CO2
1. INTRODUCTION
The hal o clima e change equi es educing he consump ion o ossil sou ces and he
implemen a ion o new sus ainable p ocesses o he alo iza ion o CO2 and o he
al e na i e p oduc ion o uels and ene gy ec o s [1,2]. Among he ca aly ic p ocesses
unde s udy o he con e sion o CO2, he di ec syn hesis o dime hyl e he (DME)
ecei es g ea a en ion and has good p ospec s o i s la ge-scale indus ial
implemen a ion, due o he in e es o DME economy and he capaci y o he p ocess o
alo ize CO2 co- ed wi h syn hesis gas.
DME is a good domes ic and diesel engine uel because i s p ope ies a e simila o
hose o he Lique ied Pe oleum Gases (LPG) and i has a high ce ane numbe , which
acili a es i s s o age and dis ibu ion [3,4]. I s u iliza ion o powe p oduc ion in
u bines is also in e es ing [5]. In addi ion, he iabili y o he selec i e con e sion o
DME in o ligh ole ins [6,7], a oma ics o gasoline [8,9] is well es ablished. Besides,
DME has o he applica ions, as o example, i s use as e ige an o g een sol en
[10,11], o in he enhanced oil eco e y [12].
The syn hesis o DME comp ises he ollowing eac ions:
Me hanol syn hesis om CO: CO + 2H2 ↔ CH3OH (1)
Me hanol dehyd a ion o DME: 2CH3OH ↔ CH3OCH3 + H2O (2)
Re e se wa e gas shi ( WGS): CO2 + H2 ↔ CO + H2O (3)
Besides, he di ec hyd ogena ion o CO2 o me hanol (MeOH) also ake place, and is
desc ibed acco ding o he ollowing eac ion:
CO2 + 3H2 ↔ CH3OH+ H2O (4)
Mo eo e , he undesi ed side eac ion o pa a ins o ma ion may also akes place,
gi ing way mainly o me hane:
OnHHCH)1n2(OCn 22n2n2
(n=1-3) (5)
The di ec syn hesis o DME is ca ied ou wi h bi unc ional ca alys s unde p essu e
and empe a u e condi ions in e media e o hose co esponding o he indi idual
eac ions o me hanol syn hesis (Eqs. 1 and 4) and i s dehyd a ion o DME (Eq. 2).
Concep ually, he in eg a ion o he wo eac ions in a single eac o has lowe
equipmen cos s and also acili a es he displacemen o he he modynamic equilib ium
o me hanol syn hesis eac ions, since i is in si u dehyd a ed o DME. The
he modynamic ad an ages o di ec syn hesis o DME wi h espec o wo-s age
syn hesis and o he syn hesis o me hanol ha e been compa ed in he li e a u e [13,14].
Among he p ac ical consequences o hese ad an ages, he ollowing a e o be
men ioned: i) he g ea e con e sion o CO2 when i is co- ed oge he wi h syngas, and;
ii) he lowe H2/CO a io equi ed, which acili a es he alo iza ion o he syngas
de i ed om biomass and om di e en sou ces (coal, na u al gas, biomass, plas ics,
i es). These ad an ages and he a ailabili y o na u al gas and he impo an
de elopmen o gasi ica ion and e o ming echnologies jus i y he a en ion ecei ed in
he li e a u e by he di ec syn hesis o DME [15,16]. This a en ion has ocused mainly
on he de elopmen o new ca alys s [17] and new eac o s [18]. The mos s udied
eac o s a e ixed-bed eac o s. Mo adi e al. ca ied ou a h ee dimensional dynamic
CFD simula ion o he di ec DME p oduc ion om CO and CO2 hyd ogena ion in a
ixed bed eac o . [19,20]. Slu y eac o s ha e also been used o DME syn hesis om
CO hyd ogena ion. Papa i e al. de eloped an axial dispe sion ma hema ical model o
simula e a slu y bubble column eac o o his eac ion [21,22]. This model has been
ex ended o o he eac o ypes [23]. The iso he mici y o he luidized bed eac o is
in e es ing o con ol he empe a u e in di e en ca aly ic p ocesses, in which he gas
low is conside ed wi h a wo-phase model [24]. In his ega d, Abasha e al. desc ibed
a model o simula e a wo-phase luidized bed eac o o DME syn hesis. [25].
T adi ionally, in he bi unc ional ca alys s used in he di ec syn hesis o DME he
me allic ( o me hanol syn hesis) and acid ( o i s dehyd a ion o DME) unc ions a e
in eg a ed in o he same pa icle by pelle iza ion, in o de o achie e he equi ed
mechanical s eng h o i s use in he eac o and also o a o he syne gy o he
ca aly ic ac i i y o he wo unc ions. As acid unc ion, HZSM-5 zeoli e (less
hyd ophilic) has eplaced he -Al2O3 ini ially used oge he wi h he CuO-ZnO me allic
unc ion (wi h di e en p omo e s). Despi e he mode a e-medium acidi y o HZSM-5
zeoli e, in o de o limi he o ma ion o hyd oca bons (coke p ecu so s) in me hanol
dehyd a ion, he inco po a ion o me als is used o passi a e he s ong acid si es [26].
This s a egy and he pa ial dealumina ion a e e ec i e o minimizing side eac ions
ac i i y and s abilizing zeoli es [27].
Howe e , he close con ac o he me allic and acid si es also a o s he syne gy o he
coke o ma ion mechanisms in each ype o si es and he mig a ion o componen s,
which causes he i e e sible deac i a ion o hese si es [28-30].
The use o ca alys pa icles wi h co e-shell s uc u e is an a ac i e ini ia i e o
p ese e he p ope ies o he me allic ca alys s and a enua e hei sin e ing [31-33],
poisoning [34] o he o ma ion o coke h ough side eac ions [35]. In addi ion, he
sepa a ion o he indi idual eac ions in di e en egions o he ca alys pa icle
imp o es he selec i i y in complex eac ions such as Fische -T opsch [36]. Thus, he
di ec syn hesis o DME by CO and CO2 hyd ogena ion has been s udied in he
li e a u e, wi h co e-shell ca alys s o di e en composi ion such as
Cu-ZnO-Al2O3@HZSM-5 [37-39], CuO-ZnO@HZSM-5 [40], C -ZnO@HZSM-5 [41],
CuO-ZnO-Al2O3@SiO2-Al2O3 [42] o Al2O3@Cu [43]. In p e ious wo ks, he
p epa a ion and he ad an ages o a bi unc ional CuO-ZnO-Z O2@SAPO-11
(CZZ @S-11) co e-shell ca alys o he di ec syn hesis o DME ha e been s udied,
and i s pe o mance has been compa ed wi h ha o a ca alys wi h con en ional
con igu a ion (p epa ed by pelle iza ion o he me allic and acid unc ions) [44]. Among
hese ad an ages, he g ea e ac i i y and s abili y (lowe deac i a ion) o he
CZZ @S-11 ca alys a e o be highligh ed. The sepa a ion o me hanol syn hesis and
dehyd a ion eac ions in wo egions acili a es he sepa a ion o wa e om he i s ,
a o ing he ac i i y o he ca alys o me hanol syn hesis, which explains he highe
ac i i y o he ca alys . The sepa a ion o he wo eac ions also p e en s he
deac i a ion phenomena p e iously s a ed [28-30]. Consequen ly, he CZZ @S-11 co e-
shell ca alys is e y s able below 325 ºC, and only su e s a slow deac i a ion by coke
[44,45].
The implemen a ion o he CZZ @S-11 ca alys on a la ge scale equi es ha ing a
kine ic model sui able o he design o he eac o , which allows assessing he e ec s o
he p ocess condi ions on p oduc s yields and dis ibu ion. Gi en he indus ial
ele ance o he main eac ions in ol ed, he mechanisms and kine ic models o
me hanol syn hesis [46-50]; i s dehyd a ion [51-54] and WGS eac ion [55-59] a e well
es ablished in he li e a u e. Howe e , hese kine ic equa ions ha e been ob ained unde
he sui able condi ions (p essu e, empe a u e) o each o hese eac ions and wi h a
composi ion o he eac ion medium ha is also di e en om ha in he di ec
syn hesis o DME. I is also no ewo hy ha ca alys deac i a ion is no quan i ied. As
o he di ec syn hesis o DME ega ds, kine ic models ha e been p e iously epo ed
o di e en con en ional bi unc ional ca alys s (hyb id) such as
CuO-ZnO-Al2O3/γ-Al2O3 [60] o CuO-ZnO-MnO/SAPO-18 [61], bu no kine ic
equa ion has been es ablished o a ca alys wi h co e-shell con igu a ion.
In he p esen wo k, a kine ic model has been es ablished o he di ec syn hesis o
DME wi h he CZZ @S-11 co e-shell ca alys , in a wide ange o eac ion condi ions
( empe a u e, p essu e, space ime, CO2/(CO+CO2) and H2/(CO+CO2) mola a ios in
he eed).
2. EXPERIMENTAL
2.1. Ca alys p epa a ion and cha ac e iza ion
The CZZ @S-11co e-shell-like ca alys , has been p epa ed by physically coa ing he
CZZ me allic unc ion wi h he S-11 acid unc ion, in a mass a io o 1/2 as desc ibed
in de ail in p e ious wo ks [44,45]. The good pe o mance o he CuO-ZnO-Z O2
(CZZ ) unc ion and i s adequa e composi ion o he syn hesis o me hanol we e
s udied in a p e ious wo k [62]. SAPO-11 (S-11) has a s uc u e made up o ellip ical
one-dimensional channels o 0.4x0.6 nm. In addi ion, i has a high o al acidi y, bu wi h
si es o weak acid s eng h. These p ope ies lead o high ac i i y o he s age o
me hanol dehyd a ion o DME, bu a low ac i i y o he side eac ions o hyd oca bons
and coke o ma ion. This good beha io has been asce ained in a p e ious wo k [63].
As o he co e-shell p epa a ion me hodology espec s, o e he CZZ co es
(90-120 μm) he adhesion o he S-11 has been conduc ed by using a silica solu ion
(Ludox TMA-34, Ald ich) as adhesi e, ollowing p ocedu es desc ibed in he li e a u e
[64-66]. The esul ing pa icles ha e been d ied and calcined a 400 ºC o 2 h, and he
s eng hened co e-shell pa icles sie ed o 125-800 μm. Fo his pu pose, he CuO-Zn-
Z O2 me allic unc ion was p e iously p epa ed ollowing a con en ional me hod o co-
p ecipi a ion o he me allic ni a es in he desi ed p opo ions (Cu:Zn:Z = 2:1:1) wi h
Na2CO3 and calcined a 300 ºC o 10 h [62]; and he SAPO-11 c ys allized (a 195 ºC
o 24 h) in a Be gho Highp eac o BR-300 e lon coa ed au ocla e om H3PO4
(Me k), Ludox AS-40 (Ald ich) and Dispe al (Sasol) and di-p opylamine (Ald ich) as
o ganic empla e, and calcined a 575 ºC o 8 h [63].
The ex u al p ope ies o he ca alys we e cha ac e ized by N2 adso p ion–deso p ion
a -196 ºC, using a Mic ome i ics ASAP 2010. P io o he measu emen s, he sample
was degassed a 150 ºC o 8 h as o emo ing possible impu i ies. Using he
B unaue -Emme -Telle equa ion, he speci ic su ace a ea was de e mined om he
iso he m; and using he BJH me hod in he adso p ion b anch o he iso he m, he o al
po e olume and he mic opo e olume we e de e mined. The me allic con en
(Cu:Zn:Z ) has been analyzed by ICP-OES (Induc i ely Coupled Plasma Op ical
Emission Spec ome y) in a Pe kin Elme Op ima 8300 appa a us; whe eas he me allic
p ope ies (Cu su ace a ea and dispe sion) we e de e mined by selec i e N2O
chemiso p ion in a Mic ome i ics Au ochem 2920 Appa a us coupled on-line o a Mass
Spec ome e (P ei e -Vacuum Omnis a ). The acidi y and acid s eng h ha e been
measu ed by combining he mog a ime y and calo ime y o NH3 adso p ion a 150 ºC
and subsequen empe a u e p og ammed deso p ion (a 5 ºC·min-1 a e up o 550 ºC)
using a Se a am TG-DSC 111 equipmen coupled o a Balze s Ins umen s The mos a
Mass Spec ome e . Table 1 summa izes he mos ele an p ope ies o he ca alys .
Howe e , u he analyzes such as, Scanning Elec on Spec oscopy o assess he
in e nal s uc u e o he ca alys ; Ene gy Dispe si e X- ay spec oscopy o analyze each
sec ion o he ca alys ; XRD o s udy he s uc u al p ope ies, and; Tempe a u e
P og ammed Reduc ion (TPR) o ensu e he comple e educ ion o CuO o Cu0 [62]
ha e been ca ied ou . Fo he cha ac e iza ion o he coke con en deposi ed on he used
ca alys s, he CO2 signal esul ing om Tempe a u e P og ammed Oxida ion analyzes
(conduc ed in a TA Ins umen s TGA Q5000 appa a us) has been egis e ed in a Mass
Spec ome e (Balze s Ins umen s). Fo he quan i a i e measu emen o CO2 in he
combus ion gases, CaCO3 has been added o each sample as in e nal s anda d
(decomposes a highe empe a u e han he combus ion compounds) [67].
Table 1. Tex u al, me allic and acid p ope ies o he CZZ @S-11 ca alys .
Tex u al p ope ies
SBET (m2·g-1)
Vm (cm3·g-1)
Vp (cm3·g-1)
123
0.031
0.300
Me allic p ope ies
SCu (m2·gCu-1)
SCu (m2·gca -1)
Dispe sion (%)
33.3
3.9
5.1
Acid p ope ies
Acid s eng h (kJ·molNH3-1)
To al acidi y (mmolNH3·gca -1)
85
0.186
2.2. Reac ion equipmen and ca aly ic uns
The eac ion uns ha e been ca ied ou in an au oma ed eac ion equipmen
(Mic oac i i y e e ence, PID Eng. Tech. Mic ome i ics) p o ided wi h a high p essu e
packed bed s ainless s eel 316 eac o , o 9 mm o in e nal diame e and 100 mm o
e ec i e leng h. The used equipmen is capable o ope a ing up o 100 a m and 700 ºC,
and has been desc ibed in de ail in p e ious wo ks [45,68]. In o de o asce ain ha he
kine ics is no a ec ed by he limi a ions o he s ages o di usion inside and ou side he
pa icles, heo e ical and expe imen al c i e ia o he li e a u e ha e been adop ed [69].
Thus, he absence o di usion limi a ions o ca alys pa icles in he 0.1-0.5 mm ange
and eeding a o al gas low a e o 60 cm3·min-1 o he eac o has been de e mined.
Consequen ly, hose ha e been selec ed as un condi ions.
and p og essi e coke deposi ion on he acid si es, which equi es an induc ion pe iod,
and has been ela ed o he ou es o he hyd oca bon pool mechanism, side p oduc s
also con aining me hoxy ions (p oduced om he me hanol and DME adso bed on he
si es o he acid unc ion) as in e media es. These mechanisms o coke o ma ion a e
well es ablished o he MTO (me hanol o ole ins) and DTO (DME o ole ins)
p ocesses [76]. Howe e , he high H2 p essu e in he s udied condi ions and he limi ed
acid s eng h o he si es o he SAPO-11 in he ca alys a e key ea u es o a enua e he
o ma ion o coke. Gi ing he complexi y o conside ing bo h ou es, due o hei
di e en kine ics and bea ing in mind ha he i s one only occu s du ing he i s hou
o eac ion, special a en ion has been paid o he second ou e as his cause o
deac i a ion p og esses slowly wi h ime on s eam. Consequen ly, a deac i a ion
kine ic equa ion has been es ablished dependen on he concen a ion o he oxygena es
(me hanol and DME) in he eac ion medium, due o i s ole in he gene a ion o
me hoxy ions and subsequen o ma ion o hyd oca bons p ecu so s o coke [77,63]:
a·· k
d
da dDMEMeOHd
(28)
whe e kd is he kine ic cons an o deac i a ion.
In Eq. (28) a e m θd has been conside ed o quan i ying he a enua ing e ec o H2O
and CO2 concen a ions on he deposi ion o coke due o he limi a ion o he me hoxy
ions o ma ion [77] and o he compe i ion o hese componen s wi h coke p ecu so
hyd oca bons o hei adso p ion on he ac i e si es (bo h on me allic and on acid si es).
As men ioned, e m θd ga he s he a enua ing e ec o H2O and CO2 adso p ion;
anyhow, di e en exp essions ha e been used in he kine ic models p e iously
desc ibed. Thus, in Models 1-3 his e ec has no been conside ed, and he e o e, θd = 1
has been es ablished in Eq. (28). In Models 4 and 5 e m θd has been conside ed
acco ding o he exp essions desc ibed in Eqs. (29) and (30), espec i ely.
dOH,adsOH
d
22 K· 1
1
(model 4) (29)
dCO,adsCO
dOH,adsOH
d
2222 K· K· 1
1
(model 5) (30)
whe e
dOH,ads 2
K
and
dCO,ads 2
K
co espond o he adso p ion cons an s o H2O and CO2 on
he ac i e si es in ol ed in he deac i a ion by coke.
The equa ions conside ed in he di e en models ha e been summa ized in Table 2.
Table 2. S udied kine ic models.
Model
Equa ions
MeOH
DME
WGS
HC
1
10
11
12
13
2
14
11
12
13
3A
14
11
12
15
3B
14
11
12
16
3C
14
11
12
17
4A
18
11
12
13
4B
14
19
12
13
4C
14
11
20
13
4D
14
11
12
21
5A
23
11
12
13
5B
18
11
24
13
5C
18
11
12
25
3.3. Disc imina ion o he kine ic models
Table 3 shows he main s a is ic pa ame e s (sum o squa es o he e o s, SSE; deg ees
o eedom, ν; a iances o he lack o i , s2) o each model and o he expe imen al
esul s, whe eas Table 4 ga he s he alues (Fische dis ibu ion, Fa-b; and he c i ical
alue o Fishe dis ibu ion, F1-α) used o model disc imina ion ( ollowing he
me hodology desc ibed in he Suppo ing In o ma ion).
Table 3. S a is ic pa ame e s o each model, and o he expe imen al e o .
Model
SSE
ν
s2
1
3.36E-01
11251
2.69·10-1
2
3.36E-01
11246
2.61·10-4
3A
3.26E-01
1248
2.61·10-4
3B
3.26E-01
1247
2.61·10-4
3C
3.26E-01
1246
2.61·10-4
4A
3.16E-01
1242
2.54·10-4
4B
3.26E-01
1242
2.63·10-4
4C
3.26E-01
1242
2.62·10-4
4D
3.26E-01
1242
2.62·10-4
5A
2.52E-01
1238
2.04·10-4
5B
2.46E-01
1238
1.99·10-4
5C
2.59E-01
1238
2.09·10-4
Expe imen al
1.35E-01
581
2.32·10-4
Table 4. S a is ic compa ison o model disc imina ion.
Fa-b
Fa-b
F1-α
Imp o emen
Selec ed
F1-2
18.67
3.001
Yes
2
F2-3A
0.08
3.85
No
2
F2-3B
0.67
3.00
No
2
F2-3C
0.59
2.61
No
2
F2-4A
5.70
2.02
Yes
4A
F2-4B
0.08
2.02
No
2
F2-4C
0.17
2.02
No
2
F2-4D
0.20
2.02
No
2
F4A-5A
78.08
2.38
Yes
5A
F4A-5B
87.89
2.38
Yes
5B
F4A-5C
69.09
2.38
Yes
5C
F om he esul s in Tables 3 and 4, i is e iden ha conside ing successi ely me hanol
o ma ion om CO2 (Model 2), he a enua ing e ec o H2O adso p ion on he eac ion
and deac i a ion a es (Model 4) and he a enua ing e ec o CO2 adso p ion (Model 5)
lead o ele an imp o emen s on he i ing. On he o he hand, gi en he low pa a in
amoun epo ed, using mo e kine ic pa ame e s o analyze he o igin o hei o ma ion
is no wo h i (Model 3). Fo compa ing models 5A-5C, as hey ha e equal deg ees o
eedom, a a iance analysis has been ca ied ou . Thus, ha o lowe a iance has been
selec ed (5B) since any o hem implies an imp o emen o e he o he on i ing he
expe imen al da a. Finally i has been asce ained ha he selec ed Model 5B sa is ies
he signi icance es in Eq. (S5) (Fs= 0.86), which means ha he e o associa ed o he
lack o i is lowe han he expe imen al e o , and so, ha he model ep esen s
sa is ac o ily he expe imen al esul s.
The kine ic pa ame e s o bes i (kine ic and adso p ion cons an s a e e ence
empe a u e, k* and K*, espec i ely, and ac i a ion ene gies and eac ion hea s, E and
H, espec i ely) o he selec ed model (5B) ha e been lis ed in Table 5. I is
no ewo hy ha he ac i a ion ene gy o me hanol syn hesis om CO (12.8 kJ·mol-1) is
no ably lowe han ha co esponding o i s syn hesis om CO2 (84.5 kJ·mol-1).
Fu he mo e, he kine ic cons an a he e e ence empe a u e is g ea e o he
syn hesis om CO (1.14 10-5 molMeOH·g-1·h-1·ba -3) han om CO2 (9.47 10-7
molMeOH·g-1·h-1·ba -4). These esul s, ob ained by i ing he esul s o an empi ical
kine ic model, a e consis en wi h he molecula simula ion esul s o he DME
syn hesis by Qin e al. [78]. These au ho s de e mined by densi y unc ional heo y
(DFT) ha me hanol syn hesis mechanism akes place h ough o ma e ions, wi h a
lowe ene gy ba ie o he syn hesis om CO han om CO2. Consequen ly, hey
conside in hei in insic eac ion model ha -WGS (Eq. (3)) is key o he syn hesis o
me hanol. In Table 5, he alue o he kine ic cons an a he e e ence empe a u e o
me hanol dehyd a ion is e y high (25.6 molDME·g-1·h-1·ba -2), which is also in
acco dance wi h he conside a ion o Qin e al. ha he s age o me hanol syn hesis is
slowe han ha o me hanol dehyd a ion and condi ions he hyd ogena ion o CO2 o
DME [78]. On he o he hand, he eac ion hea s co esponding o he cons an s ela ed
o de adso p ion o H2O and CO2 on he me allic and acid si es (Kads,H2O and Kads,CO2)
a e small, as co espond o physical adso p ion. An in e p e a ion o he alues o he
adso p ion hea s o H2O and CO2 canno be made o he cons an s ha quan i y
deac i a ion due o hei empi ical meaning.
Table 5. Kine ic pa ame e s o Model 5B conside ing deac i a ion.
Pa ame e
uni s
k* o K*
(a 275 ºC)
E o ∆H
(kJ·mol-1)
k1
(molMeOH·g-1·h-1·ba -3)
1.14·10-5
1.28·101
k2
(molDME·g-1·h-1·ba -2)
2.56·101
2.07·102
k3
(mol·g-1·h-1·ba -2)
4.63·101
9.33·101
k4
(molMeOH·g-1·h-1·ba -4)
9.47·10-7
8.45·101
k5
(molHC·g-1·h-1)
1.30·10-3
-
Kads,H2O
(ba -1)
3.17·100
8.70·10-2
Kads, CO2
(ba -1)
1.16·10-1
1.56·10-1
kd
(h-1·ba -1)
1.31·10-1
5.73·100
Kads,H2O,d
(ba -1)
1.37·10-2
9.12·10-1
Kads,CO2, d
(ba -1)
1.26·10-2
9.71·10-1
In o de o show isually he i ing o he es ed models o he expe imen al da a,
u he in o ma ion o he i ing ob ained wi h Models 1, 2, 4A and 5B can be ound in
he Suppo ing In o ma ion (Fig. S1) and in Fig. 1, whe e he i ing o all he
componen s in he eac ion medium is depic ed. Fo his and subsequen igu es p oduc
yield has been de ined as:
100·
F
F·n
Y0
COx
ii
i
(31)
whe e ni is he numbe o ca bon a oms in a molecule o componen i; Fi he mola
low a e o componen i a he eac o ou le , and
0
COx
F
he mola low a e o ca bon in
he eac o inle s eam ed as CO and/o CO2.
0 2 4 6 8 10 12 14 16
0
10
20
30
40
50
60
0 2 4 6 8 10 12 14 16
0
10
20
30
40
50
60
0 2 4 6 8 10 12 14 16
0
10
20
30
40
50
60
0 2 4 6 8 10 12 14 16
0
10
20
30
40
50
60
Yield (%)
Space ime (gca ·h·molC
-1)
a)
CO CO2 MeOH DME HC
Model
Model 1
Expe imen al
Yield (%)
Space ime (gca ·h·molC
-1)
Model 2
b)
Yield (%)
Space ime (gca ·h·molC
-1)
Model 4A
c)
Yield (%)
Space ime (gca ·h·molC
-1)
Model 5B
d)
Figu e 1. Fi ing o models 1 (a), 2 (b), 4A (c) and 5B (d) o he expe imen al alues
o CO, CO2, MeOH, DME and HC yields. Reac ion condi ions: 300 ºC,
30 ba , CO2/COx= 0.5, H2/COx= 3.
3.4. Fi ing o he model o he expe imen al alues
As an example, he i ing ob ained wi h Model 5B a di e en ope a ing condi ions is
depic ed in Figu e 2. The eac ion condi ions unless o he indica ed ha e been: 300 ºC;
30 ba ; 5 gca ·h·molC-1; H2/COx mola a io in he eed o 3, CO2/COx mola a io in he
eed o 0.5, and 5 h TOS. The s udy has been ex ended in he Supplemen a y
In o ma ion Sec ion, o o he ope a ing condi ions, Figu es S2-S6.
0 1 2 3 4 5
0
4
8
12
16
40
50
60
0 1 2 3 4 5
0
4
8
12
40
50
60
0 1 2 3 4 5
0
20
40
60
80
Yield (%)
Time on s eam (h)
a)
CO CO2 MeOH DME HC
Model
Expe imen al
Yield (%)
Time on s eam (h)
b)
Yield (%)
Time on s eam (h)
c)
0 1 2 3 4 5
0
4
8
12
16
40
50
60
0 1 2 3 4 5
0
4
8
12
40
50
60
0 1 2 3 4 5
0
20
40
60
80
Yield (%)
Time on s eam (h)
a)
CO CO2 MeOH DME HC
Model
Expe imen al
Yield (%)
Time on s eam (h)
b)
Yield (%)
Time on s eam (h)
c)
0 1 2 3 4 5
0
4
8
12
16
40
50
60
0 1 2 3 4 5
0
4
8
12
40
50
60
0 1 2 3 4 5
0
20
40
60
80
Yield (%)
Time on s eam (h)
a)
CO CO2 MeOH DME HC
Model
Expe imen al
Yield (%)
Time on s eam (h)
b)
Yield (%)
Time on s eam (h)
b)
0 1 2 3 4 5
0
10
20
60
80
100
0 1 2 3 4 5
0
10
20
30
60
80
100
0 1 2 3 4 5
0
4
8
20
40
60
80
100
Yield (%)
Time on s eam (h)
c)
CO CO2 MeOH DME HC
Model
Expe imen al
Yield (%)
Time on s eam (h)
b)b)b)b)
Yield (%)
Time on s eam (h)
c)c)c)
c)
0 1 2 3 4 5
0
4
8
40
60
80
0 1 2 3 4 5
0
4
8
40
50
60
0 1 2 3 4 5
0
4
8
40
60
80
0 1 2 3 4 5
0
1
2
3
4
40
60
Yield (%)
Time on s eam (h)
a)
CO CO2 MeOH DME HC
Model
Expe imen al
Yield (%)
Time on s eam (h)
b)b)b)b)
Yield (%)
Time on s eam (h)
d)
Yield (%)
Time on s eam (h)
d)
0 1 2 3 4 5
0
10
20
30
80
100
0 1 2 3 4 5
0
4
8
20
40
60
80
100
0 1 2 3 4 5
0
5
10
15
20
60
80
100
Yield (%)
Time on s eam (h)
a)
CO CO2 MeOH DME HC
Model
Expe imen al
Yield (%)
Time on s eam (h)
b)b)b)b)
Yield (%)
Time on s eam (h)
c)c)c)
e)
0 1 2 3 4 5
0
2
4
6
8
40
50
60
0 1 2 3 4 5
0
2
4
6
8
40
50
60
0 1 2 3 4 5
0
4
8
12
16
30
40
50
60
0 1 2 3 4 5
0
4
8
12
16
20
30
40
50
60
Yield (%)
Time on s eam (h)
)
CO CO2 MeOH DME HC
Model
Expe imen al
Yield (%)
Time on s eam (h)
b)b)b)b)
Yield (%)
Time on s eam (h)
c)
Yield (%)
Time on s eam (h)
d)
Figu e 2. Fi ing o he Model 5B o he expe imen al alues o CO, CO2, MeOH,
DME and HC yields e olu ion wi h ime on s eam. Reac ion condi ions: a)
300 ºC; 30 ba ; H2/COx, 2.5; CO2/COx, 0.5; space ime, 5 gca ·h·molC-1; b)
idem excep H2/COx, 4; c) idem excep H2/COx, 3 and CO2/COx, 0 (syngas);
d) idem excep 325 ºC and CO2/COx, 0.5; e) idem excep 300 ºC and 40 ba ;
) idem excep 30 ba and space ime 1.25 gca ·h·molC-1.
3.5. Reac o simula ion
Once p o ed in he p e ious Sec ion 3.4 ha he p oposed kine ic model is capable o
desc ibing he e olu ion o p oduc dis ibu ion wi h TOS wi hin he s udied ange o
ope a ing condi ions, i has been used o simula ing he ope a ion in a ixed-bed
iso he mal eac o . Figu e 3, shows he ope a ing maps o DME yield o wo di e en
eeds; syngas (CO+H2) and CO2+H2, as a unc ion o eac ion empe a u e and p essu e.
I can be obse ed ha he CO2 con en in he eed has a ema kable in luence on he
yield o DME (YDME), dec easing om a ound 50 % o CO+H2 eeds, o almos 10 %
o CO2+H2 eeds a he mos sui able condi ions. Fo bo h eed composi ions, YDME
inc eases no ewo hy upon inc easing eac ion p essu e, and he op imum is loca ed
wi hin he 280-300 ºC ange, he lowe limi co esponding o he maximum a highe
p essu e. Mo adi e al. ha e s udied by simula ion o a ixed bed eac o he impo ance
o p essu e and empe a u e in he con e sion o CO and selec i i y o DME, ob aining
as op imum a p essu e o 50 ba [19,20]. The op imal empe a u e o hese au ho s is
270 ºC in an adiaba ic egime and 260 ºC in an iso he mal egime. The di e ences in
he esul s o hese au ho s wi h hose shown in Figu e 3 o CO hyd ogena ion a e
mode a e and a e a consequence o he di e ences in he kine ic model (di e en
ca alys ). Fu he mo e, he esul s in Figu e 3 co espond o an H2/COx a io o 3, and
his a io (sui able o CO and CO2 hyd ogena ion) is o g ea ele ance in he esul s
[45], as also e i ied by Mo adi e al. in he hyd ogena ion o CO [20].
Figu e 3. E olu ion o DME yield wi h eac ion empe a u e and p essu e o
CO2/COx a ios in he eed o 0 (syngas, CO+H2) and 1 (CO2+H2). Reac ion
condi ions: H2+CO+CO2 eed; H2/COx, 3; space ime 5 gca ·h·molC-1; ime
on s eam, 1 h.
As a a o able ea u e, he e ec o eeding CO2 on he a enua ion o he deac i a ion is
ema kable. Thus, a e 1 h ime on s eam his deac i a ion is e y slow when eeding
CO2, as i can be obse ed in Figu es 2a, 2b, 2d, 2e and 1 , and in Figu es S2-S6, when
CO2 is ed wi h a CO2/COx a io o 0.5 o abo e. This esul is o g ea in e es o he
indus ial iabili y o he p ocess wi h his ca alys and is consis en wi h he
deac i a ion kine ic equa ion, Eq. (30), which conside s he compe ence o he
adso p ion o H2O and CO2 wi h coke p ecu so s. P esumably, hese p ecu so s a e
hyd oca bons o med in he me allic si es by Fische -T opsch syn hesis om CO, and in
he acidic si es om he oxygena es (me hanol and DME), by he gene a ion o me hoxy
ions in his case, which a e also ac i e o gene a e hyd oca bons h ough he well
es ablished hyd oca bon pool mechanism [79]. In addi ion, he ela ionship be ween he
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The ollowing Figu es S2-S6 show he i ing quali y o he selec ed model (5B) o he
expe imen al esul s a di e en ope a ing condi ions.
0 1 2 3 4 5
0
4
8
12
16
40
50
60
0 1 2 3 4 5
0
4
8
12
40
50
60
0 1 2 3 4 5
0
20
40
60
80
Yield (%)
Time on s eam (h)
a)
CO CO2 MeOH DME HC
Model
Expe imen al
Yield (%)
Time on s eam (h)
b)
Yield (%)
Time on s eam (h)
c)
Figu e S2. Fi ing o he model o he expe imen al alues o CO, CO2, MeOH, DME
and HC yields e olu ion wi h ime on s eam o di e en H2/COx a ios in
he eed: 2.5 (a), 3 (b) and 4 (c). Reac ion condi ions: 300 ºC, 30 ba ,
CO2/COx= 0.5, space ime 5 gca ·h·molC-1.
0 1 2 3 4 5
0
10
20
60
80
100
0 1 2 3 4 5
0
10
20
30
60
80
100
0 1 2 3 4 5
0
4
8
20
40
60
80
100
Yield (%)
Time on s eam (h)
a)
CO CO2 MeOH DME HC
Model
Expe imen al
Yield (%)
Time on s eam (h)
b)b)b)b)
Yield (%)
Time on s eam (h)
c)c)c)
c)
Figu e S3. Fi ing o he model o he expe imen al alues o CO, CO2, MeOH, DME
and HC yields e olu ion wi h ime on s eam o di e en CO2/COx a ios in
he eed: 0 (a), 0.75 (b) and 1 (c). Reac ion condi ions: 300 ºC, 30 ba ,
H2/COx= 3, space ime 5 gca ·h·molC-1.
0 1 2 3 4 5
0
4
8
40
60
80
0 1 2 3 4 5
0
4
8
40
50
60
0 1 2 3 4 5
0
4
8
40
60
80
Yield (%)
Time on s eam (h)
a)
CO CO2 MeOH DME HC
Model
Expe imen al
Yield (%)
Time on s eam (h)
b)b)b)b)
Yield (%)
Time on s eam (h)
c)
Figu e S4. Fi ing o he model o he expe imen al alues o CO, CO2, MeOH, DME
and HC yields e olu ion wi h ime on s eam o di e en eac ion
empe a u es: 250 ºC (a), 275 ºC (b) and 325 ºC (c). Reac ion condi ions:
30 ba , H2/COx= 3, CO2/COx= 0.5, space ime 5 gca ·h·molC-1.
0 1 2 3 4 5
0
10
20
30
80
100
0 1 2 3 4 5
0
4
8
20
40
60
80
100
0 1 2 3 4 5
0
5
10
15
20
60
80
100
Yield (%)
Time on s eam (h)
a)
CO CO2 MeOH DME HC
Model
Expe imen al
Yield (%)
Time on s eam (h)
b)b)b)b)
Yield (%)
Time on s eam (h)
c)c)c)
c)
Figu e S5. Fi ing o he model o he expe imen al alues o CO, CO2, MeOH, DME
and HC yields e olu ion wi h ime on s eam o di e en eac ion
p essu es: 20 ba (a), 30 ba (b) and 40 ba (c). Reac ion condi ions: 300 ºC,
H2/COx= 3, CO2/COx= 1, space ime 5 gca ·h·molC-1.
0 1 2 3 4 5
0
2
4
6
8
40
50
60
0 1 2 3 4 5
0
2
4
6
8
40
50
60
0 1 2 3 4 5
0
4
8
12
16
30
40
50
60
0 1 2 3 4 5
0
4
8
12
16
20
30
40
50
60
Yield (%)
Time on s eam (h)
a)
CO CO2 MeOH DME HC
Model
Expe imen al
Yield (%)
Time on s eam (h)
b)b)b)b)
Yield (%)
Time on s eam (h)
c)
Yield (%)
Time on s eam (h)
d)
Figu e S6. Fi ing o he model o he expe imen al alues o CO, CO2, MeOH, DME
and HC yields e olu ion wi h ime on s eam o di e en space ime alues:
1.25 (a), 2.5 (b), 10 (c) and 15 (d). Reac ion condi ions: 300 ºC, 30 ba ,
H2/COx= 3, CO2/COx= 0.5.
Re e ences
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Ind. Eng. Chem. Res. 39 (2000) 292–300. doi:10.1021/ie990188z.
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assessmen o he CO2 con e sion, Fuel P ocess. Technol. 181 (2018) 233–243.
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