Coke formation and deactivation during catalytic reforming

of biomass and waste pyrolysis products: A review

Item Type Article

Authors Ochoa, Aitor; Bilbao, Javier; Gayubo, Ana G.; Castaño, Pedro

Citation Ochoa, A., Bilbao, J., Gayubo, A. G., & Castaño, P. (2019).
Coke formation and deactivation during catalytic reforming of
biomass and waste pyrolysis products: A review. Renewable
and Sustainable Energy Reviews, 109600. doi:10.1016/
j.rser.2019.109600

Eprint version Post-print

DOI 10.1016/j.rser.2019.109600

Publisher Elsevier BV

Journal Renewable and Sustainable Energy Reviews

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Energy Reviews, [[Volume], [Issue], (2019-12-02)] DOI: 10.1016/
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Link to Item http://hdl.handle.net/10754/660570

Coke formation and deactivation during catalytic reforming of
biomass and waste pyrolysis products: a review
Aitor Ochoaa, Javier Bilbaoa, Ana G. Gayuboa, Pedro Castañoa,b*

a. Department of Chemical Engineering, University of the Basque Country (UPV/EHU), P.O.

Box 644-48080, Bilbao, Spain. * E-mail: pedro.castano@ehu.eus

b. Multiscale Reaction Engineering, KAUST Catalysis Center (KCC), King Abdullah University
of Science and Technology (KAUST), Thuwal, 23955-6900, Saudi Arabia. * E-mail:
pedro.castano@kaust.edu.sa

Abstract

Undoubtedly, hydrogen (H2) is a clean feedstock and energy carrier whose sustainable
production should be anticipated. The pyrolysis of biomass or waste plastics and the
subsequent reforming over catalysts supported on base or noble transition metals allows
reaching elevated H2 yields. However, the catalyst used in the reforming step undergoes
a rapid and severe deactivation by means of a series of physicochemical phenomena,
including metal sintering, metallic phase oxidation, thermal degradation of the support
and, more notoriously, coke deposition. This review deals with the currently existing
alternatives at the catalyst and reactor level to cope with catalyst deactivation and increase
process stability, and then delves with the fundamental phenomena occurring during this
catalyst deactivation. An emphasis is placed on coke deposition and its influence on
deactivation, which depends on its location, chemical nature, morphology, precursors or
formation mechanism, among others. We also discuss the challenges for increasing the
value of the carbon materials formed and therefore, enhance process viability.

Keywords: reforming, sustainable refinery, catalyst deactivation, carbon, characterization

1
1. Introduction

The near- and mid-term world energy market is expected to embrace a wide spectrum of

coexisting possibilities toward the clean and sustainable energy production [1]. In this

transition scenario, the so-called ‘hydrogen economy’ is envisioned as a progressively

developing framework for a sustainable H2 production, with the coexisting use of fossil

fuels together with an increasing relevance of alternative and renewable sources. On the

one hand, in this current transition scenario toward sustainability, lignocellulosic biomass

is presented as a near- and mid-term promising feedstock for H2 production, envisioned

within a large-scale bio-refinery framework. Considering it is one of the most abundant

renewable energy sources and its usage implies a null CO2 net generation, its valorization

technologies show a noticeable development degree [2,3]. On the other hand, recycling

of wastes from fossil fuels derivatives, such as plastic wastes, has aroused a great deal of

interest in H2 production within a waste refinery framework, considering the following

facts: (1) the world plastic production shows a continuous increasing trend, with a global

production of 335·106 t in 2016 [4]; (2) their dumping involves a severe environmental

issue due to their slow biodegradability [5]; and (3) their chemical composition is

favorable toward the production of H2 and carbon materials [6,7].

H2 plays an important role as feedstock, with a world market greater than 35 million euros,

distributed in the following sectors [8]: ammonia production for the fertilizer industry (51

wt%), refining (hydrotreating and hydrocracking) of petroleum fractions (31 wt%),

methanol synthesis (10 wt%) and applications in food industry, electronic industry and

metallurgic industry, among others (8 wt%). The world H2 consumption at the beginning

of the current decade (400-500·109 Nm3) corresponds to the 3 % of the total energy

consumption, and an annual increase of 5-10 % is expected, mainly due to the future H2

market as a sustainable energy source [9,10]. Whereas in 2008 the 80 % of the total energy

2
consumption (500 EJ) came from fossil fuels (petroleum, natural gas and carbon), in 2050

the fossil fuel consumption is estimated to be the 40 %, together with a 30 % for H2, for

a total consumption of 1000 EJ [11].

The importance of H2 within a sustainable refining scenario is noteworthy, as it plays a

key role in the fate of refineries, as well as considering its economic relevance [12]. H2

requirements show an increasing trend because it is used to improve the fuel quality and

meet the increasingly severe environmental requirements. An important sector of

hydrogen consumption within the petrochemical industry consists on its use as feedstock

in the synthesis of methanol and hydrocarbons (Fischer-Tropsch synthesis), these being

processes subjected to significant breakthroughs and an increasing industrial

implementation [13].

Nevertheless, the future of the H2 market is mainly framed in its use as a fuel and as an

energy carrier [12]. Throughout history, a progressive transition has taken place from

solid fuels to liquid and gas fuels as the main energy sources, in parallel with the

technological development of the energy production and transformation systems, as well

as for the sake of operational simplicity and convenience for the users. Moreover, the

environmental requirements call for an increasing demand of the decarbonation of the

energy sources [14]. These trends and requirements justify the increase of the funding of

R&D projects for the H2 production, distribution, storage and use, especially in the USA,

the European Union and Japan [15,16]. In this regard, the transition to a globalized

hydrogen economy pursues a progressive development of technologies and policies,

expansion of markets and infrastructures, and a social institutionalization scenario [17].

Although H2 is considered the future substitute for the petroleum derivatives, a more

realistic vision of the future development of the energy market is thought to be demanding

the coexistence of the consumption of conventional fossil fuels derived from petroleum,

3
together with the consumption of H2 and other renewable energy sources. The main

alternatives for the application of H2 as a fuel are: i) internal combustion engines fed by

H2 or blends, such as Hythane (20/80 of H2/methane); ii) fuel cells for transport; iii)

portable power generators; iv) as a storage medium and transport vector of energy

obtained from renewable sources (solar, wind, hydraulic or tidal power, among others)

[18].

The use of H2 as an automotive fuel shows several benefits, since the energy efficiency

of fuel cells is three times that of the vehicles with internal combustion engines, without

pollutant emission [19]. Nevertheless, the consideration of H2 as an energy solution has

also aroused uncertainties, since the current technology for the H2 production as an energy

vector is still too expensive and not efficient enough. According to several authors,

hydrogen economy lies on two main key points [20,21]: i) pollutant-free sources for H2

production, and ii) an increased efficiency in the transformation of H2 into useful energy

in fuel cells.

Beyond taking into account the economic aspects within the current energy market, the

consideration of H2 as a fuel of the future is based on the need of decreasing the

environmental contamination, minimizing the greenhouse effect and the emission of gas

pollutants. Moreover, its production is considered feasible in most worldwide economies,

due to both the wide range of alternative feedstock and the different existing production

technologies [20,22].

The H2 production methods are usually classified in terms of the employed feedstock: (i)

reforming of fossil fuels (natural gas, petroleum derivatives, carbon), (ii) routes from

biomass, and (iii) electrochemical water splitting or electrolysis [23]. The current H2

production is mainly produced from non-renewable sources (96 %), comprising steam

4
reforming of natural gas (48 %) and petroleum derivatives such as naphtha (30 %), and

coal gasification (18 %), together with a 4 % corresponding to water electrolysis [11].

Thus, the challenges to attain a steady and sustainable energy economy based on H2

include the decrease of CO2 emissions and the use of renewable energy sources for its

production, which includes the development of new sustainable processes based on these

sources, together with the improvement of the process efficiency and decrease of the

related costs. The so-called hydrogen economy is framed in a future scenario in which

this gas is produced in a cleaner and more economical way, from a wide range of sources

and an increasing relevance of renewable energy alternatives, biomass being one of the

most promising (Figure 1). This scenario is envisioned in order to satisfy the energy

demands of the society and diversify the energy system, leading to the decrease in the

current dependence on fossil fuels and the environmental pollution [24].

Figure 1.

H2 production from a fossil source (such as natural gas) is not sustainable, considering

the CO2 emitted during its steam reforming. If the avoidance of CO2 generation is

pursued, water electrolysis can be presented as the best alternative; however, this process

still has great costs related to technological limitations, for which no solutions are

expected to assure the feasibility for a large-scale H2 production in the next decades.

Accordingly, it is estimated that until 2100 a transition scenario will be taking place,

between the H2 production from natural gas (steam reforming) and from water

(electrolysis) [16]. In this current transition scenario toward sustainability, lignocellulosic

biomass is presented as a promising feedstock for H2 production in a large scale in near

and medium term (Figure 1). It is one of the most abundant renewable energy sources, its

usage implies a null CO2 net generation and its valorization technologies show a

noticeable development degree [10,20].

5
Some authors, considering the increasing CO2 emission rates, together with an optimistic

outreach of the development of the electrolysis technology with solar power, move

forward the transition period between the petroleum economy and the economy of H2

obtained from renewable sources. This transition has an estimated cost of 4.5 euros·GJ-1,

similar to that corresponding to the natural gas reforming [25]. Nevertheless, these

estimations are being affected by socioeconomic factors, such as the current decrease in

the petroleum cost, which delay the implantation of technologies for the valorization of

alternative sources. Moreover, the current commercial technologies capable of the

production of H2 from biomass in a large scale still have important hurdles.

All in all, the near- and mid-term energy market is expected to embrace a wide spectrum

of coexisting possibilities. This involves not only the transformation of fossil fuels, H2

and other alternative and renewable sources into useful energy and/or chemicals, but also

the coexisting use of fossil fuels and alternative and renewable sources for H2 production.

Moreover, the economic viability of H2 production processes involving hydrocarbon and

oxygenate feedstock (both fossil or renewable) may be enhanced by the valorization of

carbon materials generated as by-products (Figure 1), and thus the study of their

properties and formation/growth is receiving increasing interest within the H2 market.

The most common catalytic thermochemical process intended for H2 production from

hydrocarbons (CaHb, such as plastic wastes) and oxygenated hydrocarbons (CnHmOk, such

as biomass-derived compounds) is the reforming process [9,26,27]. This may be

conducted under several operating conditions, the most extensively studied being that

performed with steam cofeeding, namely steam reforming, since it gives the maximum

theoretical yield of hydrogen and is responsible for 78 % of the world H2 production [11].

Considering it is a strongly endothermic reaction, it requires external heat source, with

temperatures up to ca. 800 ºC in the case of bio-oil reforming.

6
 m
Cn Hm Ok + (n-k)H2 O → nCO + (n + - k) H2 ΔH0 ≫ 0 (1)
2

In addition to the main reaction displayed in Eq. (1), the mechanism of the steam

reforming of hydrocarbons and/or oxygenates involves other reactions [28], such as the

water gas shift (WGS) reaction (Eq. (2)), and thus the overall equation for the steam

reforming reaction is defined by Eq. (3). Under the usual operating conditions, the H2

yield obtained is lower than the stoichiometric maximum due to a series of side reactions,

including cracking of oxygenates (Eq. (4)), Boudouard reaction (Eq. (5)), steam

reforming of CH4 (Eqs. (6) and (7)) and light hydrocarbons (CaHb) (Eq. (8)), methanation

(inverse of Eqs. (6) and (7)), or interconversion reactions (Eq. (9)).

ΔH0 (kJ·mol-1)

Water gas shift

CO + H2 O ↔ H2 + CO2 -41.2 (2)
(WGS):
Overall steam m
Cn Hm Ok + (2n-k)H2 O → nCO2 + (2n + - k) H2 >0 (3)
reforming reaction: 2

Cracking of Cn Hm Ok →
>0 (4)
oxygenates: Cx Hy Oz + Ca Hb + CO + CO2 + H2 + C

Boudouard
2CO ↔ C + CO2 -172.5 (5)
reaction:

Methane steam CH4 + H2 O ↔ CO + 3H2 206.3 (6)

reforming: CH4 + 2H2 O ↔ CO2 + 3H2 165.0 (7)

Steam reforming of b
Ca Hb + aH2 O → aCO + (a + ) H2 >0 (8)
hydrocarbons: 2

Interconversion: Cn Hm Ok → Cx Hy Oz (9)

The oxydative steam reforming implies simultaneous air/oxygen and steam feeding,

resulting in a combination between endothermic steam reforming and exothermic partial

oxidation. Thus, this strategy lowers the heat requirements compared to steam reforming,

and the hydrogen yield is higher than that of partial oxidation. The net heat balance of the

reaction is endothermic, but an adequate tuning of steam and air/oxygen flows may reach

a thermodynamically neutral state (ΔH˚ = 0), which is known as autothermal reforming.

7
 m
Cn Hm Ok + (n-2-k)H2 O + O2 → nCO + (n + - 1- k) H2 ΔH0 > 0 (10)
2

In the case of reforming bio-oil, the issue of coke deposition may be more difficult to face

than in other lighter oxygenates (such as ethanol or dimethyl ether), and thus another

technology developed to face it consists on a two stage reforming, which comprises bio-

oil conversion into syngas without water feeding, followed by catalytic steam reforming

of produced gases. This arrangement turns out advantageous for catalyst regeneration due

to coke deposition. However, attains lower hydrogen production compared to steam

reforming. Other studied technologies require high pressures, such as in aqueous phase

reforming (ca. 15-50 bar) [29] or supercritical water reforming (ca. 220 bar) [30,31],

making them economically less viable compared to the aforementioned conventional

reforming strategies, performed at ambient pressure. As a result, the majority of the

studies for hydrogen production from biomass-derived hydrocarbons (CnHm) and/or

oxygenates (CnHmOk) are focused on steam reforming.

Pyrolysis is considered the most attractive strategy to produce a reforming feedstock from

plastic and biomass wastes on a large scale. In the case of addition polymers, the pyrolysis

products are very interesting from the reforming point of view. This is added to the fact

that they are the main fraction in municipal solid waste (MSW) [32-34]. Furthermore,

pyrolysis units are technologically simple, involve a reduced emission of pollutants and

may be placed next to the collection and classification points of municipal solid waste.

The main pyrolysis processes for waste polyolefins comprise thermal cracking [35] and

catalytic cracking [36-38], targeting the monomer recovery [39,40] or the production of

gasoline and/or diesel [41,42]. Pyrolysis does not pursue H2 production, but the pyrolysis

volatiles can be subsequently valorized towards H2 in another step, and thus H2

production can benefit from the advances made in studies on the technology of plastics

pyrolysis [43]. Pyrolysis of polyolefins at low temperature (500 ºC) allows the selective

8
production of pyrolysis waxes (C21+) which can be fed into refinery units such as the

catalytic cracker or the catalytic reformer, alone or together with the regular feed [36,44-

46]. The flexibility of pyrolysis processes also allows the co-treatment of plastic blends

together with other materials, such as biomass [47]. The requirements of scaling-up and

continuous operation have led to the proposal of a variety of technologies and reactors

under development [48]. In this regard, the fluidized bed reactor (with sand as a fluidizing

agent) is been widely employed, since its satisfactory heat and mass transfer leads to a

better thermal control [48].

A main constraint in plastic pyrolysis is the low thermal conductivity and high viscosity

of plastic, leading to mass and heat transfer issues, and subsequent melting and

agglomeration of plastic particles, blockage in fixed bed reactors and defluidization in

fluidized bed reactors [5]. In this regard, the conical spouted bed reactor technology, with

a cyclic and vigorous movement of sand particles covered by plastic, has shown a good

performance below 500 ºC without defluidization issues [49]. These breakthroughs in the

pyrolysis technology are attractive for H2 production from the volatiles produced in

pyrolysis of plastics, by means of an in-line strategy comprising a pyrolysis step followed

by catalytic reforming of the pyrolysis volatiles.

The following sections review the steam reforming catalysts and reactor configurations

studied in the literature for H2 production from biomass and/or its derivatives and waste

plastics, since these factors are crucial for their implantation within bio- and waste

refinery.

1.1. Catalysts

When talking about reforming catalyst, two subsegments should be considered: (i)

reforming of methane to produce hydrogen or (ii) reforming of hydrocarbons (mainly

9
naphtha fractions) for producing high octane reformate and hydrogen. The most relevant

commercial catalyst used industrially for (i) are Ni based [50] while for (ii) are Pt based

(ca. 0.5 wt%) supported on Al2O3 (normally ) [51,52], both promoted with other metals

such as Re or Ir. At the research level, the number of catalysts tested and used in reforming

is so overwhelmingly high that is better to indicate the mainstreams in the area.

1.1.1. Active phases

Transition metals are reported as the most common active phases in reforming catalysts,

including base transition metals (Ni, Co, Fe, Cu) and noble transition metals (Pt, Pd, Rh,

Ru, Ir) [19,31,53-57]. As a general trend, the highest activity is observed for noble metals.

However, the high cost of noble metals shifts the interest toward base transition metals as

a more accessible and economic alternative, among which Ni is the most promising active

phase. In this regard, Figure 2 shows the evolution until the end of 2017 of the scientific

papers citing the use of several transition metals for reforming. Until the early 1990s,

platinum was the most employed active phase, mainly due to its potential use in the

reforming of hydrocarbon streams, as the typically used ones in the refinery reforming

process. Nowadays, the reforming studies pursue H2 production from a wide range of

hydrocarbon and oxygenate feedstock and catalysts, Ni being the most noticeably studied

active phase.

Figure 2.

The progressively increasing interest in Ni is justified considering its high activity for

breaking C−C, C−H, C−O and O−H bonds, as well as for hydrogenation, facilitating H

atoms to form molecular H2 [58], leading to a comparable activity to that of noble metals

[59,60]. In contrast, other base transition metals have attracted much less attention, since

Fe and Cu are active for breaking C−C and C−H bonds, respectively, whereas Co may

10
show comparable bond-breaking activity to Ni, but suffers from a faster coke deposition,

which lowers its activity [54,61]. In general, the main drawback of base metals compared

to noble metals is the more rapid deactivation undergone during the reforming process,

mainly due to the coke formation and growth [55,62], as well as to the faster aggregation

of metal particles or sintering [63,64]. The irreversible nature of the latter further

motivates the use of noble metals. Moreover, base transition metals have a higher

tendency to oxidation than noble metals, which is usually ascribed as a reforming

deactivation cause, claiming that prior catalyst reduction is needed since the reduced state

of the metal attains the highest activity. However, metallic active phases in oxide state

are also widely employed in spinel-type (NiAl2O4, CuFe2O4) and/or perovskite-type

(LaNiO3, LaFeO3) bulk catalysts [54], in which active phase atoms are located within a

defined structure, instead of forming metal crystallites as in supported metal catalysts.

The combination of two metals as the active phase has shown an increased catalyst

performance by density functional theory (DFT) studies [65], since it may promote the

WGS reaction (Eq. (2)), while increasing metal dispersion and coke resistance. Besides,

the combination of two metals may lead to a weak metal-support interaction and

promotion of metal sintering [53,54]. Another interesting strategy to increase the

dispersion, active surface area and strength of metal-support interactions implies the

reduction of the metal particle size down to the atomic level, i.e. supported single-atom

catalysts [66].

1.1.2. Promoters

Although not being the active phase of the catalyst, they can enhance or promote a series

of features for a better catalyst performance. For instance, several basic oxides such as

MgO, La2O3, CeO2 or ZrO2 are commonly used in order to minimize and/or neutralize

the acidic nature of some supports (such as Al2O3), since catalyst acidity is widely known
11
to favor unwanted decomposition and polymerization reactions in reforming, yielding

more coke and less H2 [54,55]. The addition of alkali metals and alkaline earths (K, Ca,

Mg) and carbonates (such as K2CO3) have also been reported to reduce coke formation

and increase the conversion and/or WGS reaction, as well as to increase the resistance to

sintering in Ni-based catalysts [67]. Other studied methods to decrease coke formation

are the addition of sulfur compounds (such as K2SO4) leading to selective poisoning of

active sites, although it may lead to a considerable decrease in H2 production [68], or the

addition of promoters with oxygen storage/release capacity (such as CeO2), as the WGS

reaction is favored and coke and its precursors (such as CO) are combusted [69]. La2O3

has also been reported to promote active phase dispersion and coke gasification, the latter

by means of the formation of metal-promoter species [70]. Additionally, CO2 adsorbents

such as CaO or dolomite are widely known to promote the WGS reaction, and are used

both in situ (in the reforming reactor) [71] or in a sequential step [72], although they

undergo a rapid and partially irreversible deactivation.

1.1.3. Supports

Choosing an appropriate support may be crucial for the catalyst performance in reforming

reactions. For instance, reducible metal oxides (such as CeO2 or ZrO2) may imply a poorer

metal-support interaction, whereas the use of irreducible metal oxides (such as Al2O3) as

a support and/or perovskite-type catalysts (such as LaNiO3 or LaFeO3) lead to a higher

resistance to metal sintering and activity, due to a higher metal-support interaction

[53,73,74]. Mechanical and chemical resistance is another important feature to take into

account in supports, among which Al2O3-based supports are often used in reforming

catalysts [75]. Considering the higher tendency to coking and metal sintering of base

transition metals with respect to noble metals, the use of meso- and microporous supports

may also be beneficial to favor metal dispersion and thus resistance to both sintering and
12
coking, such as activated carbon [76]. Another closely related strategy which is gaining

an increasing attention to suppress these two phenomena consists on the encapsulation of

the metal sites by means of different support structures [13], as depicted in Figure 3. The

core-shell system involves the metal particles encapsulated by a support overlayer (Figure

3a-c), the latter being commonly a metal oxide, such as SiO2, Al2O3, MgO, ZrO2 and TiO2

[77-79]. Another system consists on the anchoring of metal particles (mostly Fe, Co and

Ni) inside and/or outside well-defined channels of nanotubes (Figure 3d-f), among which

CNTs are the most commonly employed [80-82]. Metal crystallites have also been

embedded inside highly porous structures, such as zeolites, thus limiting the space for

carbon growth [83], but zeolite requires its acidity to be lowered (for instance, by means

of dealumination) for submitting it to reforming [84]. The use of mesoporous silica

structures with a highly homogeneous pore diameter (including MCM-41 and SBA-15)

(Figure 3g-i) allows the tuning of the latter, high enough to prevent pore plugging by

metal particles and low enough to prevent their sintering [85-88]. Additionally, the

lamellar or layered structures of supported catalysts (Figure 3j-l) consists on the covering

of metal particles by a controlled layered deposition of the support (metal oxide).

Compared to the other encapsulating methods in Figure 3, this method allows tuning the

thick of the support layer by sequential molecular or atomic layers, which allows the

confinement of metal particles with an acceptable support porosity [89-92].

Figure 3.

Although methods in Figure 3d-l increase stability towards deactivation, it also results in

a lower activity due to diffusion limitations, somehow hindering their large-scale interest.

In this sense, several authors have proposed solutions for ensuring both a correct diffusion

and a satisfactory metal dispersion on catalyst surface. Thus, Lovell et al. [93] proposed

a simple method of reduction-oxidation-reduction pretreatment to decrease metal particle

13
size and increase dispersion. Moreover, Danghyan et al. [94] established a novel and

simple catalyst preparation method, consisting on Ni/fumed SiO2 preparation by wet

impregnation, followed by pressure dilution of additional fumed SiO2, the latter step

leading to a significant increase in Ni dispersion (from 19% to 61%), activity and stability

toward carbon formation.

1.2. Reactor configurations

The main reactor configurations developed in the literature for H2 production from

hydrocarbons (such as plastic wastes) and oxygenates (such as biomass-derived

compounds) should be classified into two main strategies [26,95]: (i) off-line reforming

or (ii) pyrolysis with in-line (sequenced) reforming.

1.2.1. Off-line reforming

This overall strategy involves the production of storable intermediates in delocalized

units, transportation of these intimidates and the off-line reforming in big scale units.

Thus, the off-line reforming reactor configuration delves with the intrinsic reforming step

alone and can be summarized in the ones shown in Figure 4 [26], divided into one-step

(Figure 4a-c) and two-step processes (Figure 4d,e).

Figure 4.

The reforming of hydrocarbons has been studied extensively in fixed bed reactors (Figure

4a). Owing to this experience, the same configuration has been studied in the reforming

of methanol [96,97], ethanol [98,99], acetic acid [100], butanol [101], glycerol [102,103],

bio-oil aqueous fraction [104-107] and raw bio-oil [108-110], among others. Fixed bed

reactors are widely reported to be limited by heat and mass transfer, and in this regard,

the fluidized bed technology has potential in interphase mass/heat transfer and mitigating

14
catalyst deactivation [55]. This is particularly interesting for heavier feeds since they are

more prone to thermal decomposition, being deposited high amounts of coke on the

catalyst and thus causing its severe deactivation. Fluidized bed technology (Figure 4b)

has been studied, besides other hydrocarbons, in the steam reforming of ethanol

[111,112], dimethyl ether [113,114], butanol [115], glycerol [116], phenol [117], toluene

[118], bio-oil aqueous fraction [119-121] and raw bio-oil [122-124].

A comparison between fixed bed and fluidized bed technologies for the steam reforming

of bio-oil aqueous fraction evidenced a higher initial activity with the fixed bed reactor,

obtaining a conversion of 80 % and H2 yield of 13.8 wt% at 2 h on stream on a Ni-based

catalyst, although lower overall deactivation was attained in the fluidized bed reactor

[125]. A higher conversion and H2 yield were also obtained in a fixed bed reactor

compared to fluidized bed reactor in the steam reforming of bio-oil [126], but the latter

showed a lower coke deposition (0.3 wt% with respect to 2.3 wt% in the fixed bed), at

650 ºC during 60 min on stream [127]. These attributes of fluidized bed reactor may be

related with the enhanced heat and mass transfer, while short residence time of the contact

reactants-products with the catalyst, of this system as compared with fixed bed reactor.

To enhance these attributes even further, some other new technologies include

microreactors, some of which use foam-like porous catalysts, in the steam reforming of

ethanol [128,129], dimethyl ether [130,131] or phenol [132]; and membrane reactors, for

the steam reforming of methanol [133], ethanol [134] or glycerol [135]. However, in

general terms these approaches are not as efficient as traditional systems, in terms of

conversion, H2 yield and future scaling-up [136].

Although the fluidized bed technology for the steam reforming of oxygenates can achieve

full conversion and high H2 yields (above 80 % of the stoichiometric maximum), catalyst

deactivation by coke deposition is still a severe problem [55]. In this regard, spouted bed

15
technology (Figure 4c) was tested for the steam reforming on bio-oil aqueous fraction and

no coke deposits were observed [137], although fluidized bed reactor showed higher

conversion (maximum of 96.5 %) and H2 production (maximum of 18.2 wt%), in the

steam reforming of bio-oil aqueous fraction of pine and poplar wood [107].

Aiming the mitigation of coke deposition and thus catalyst deactivation in bio-oil

reforming, some authors used two-stage systems (Figure 4d,e). The steam reforming of

bio-oil aqueous fraction [71,138,139], raw bio-oil [140-142] and bio-oil/ethanol mixtures

[143,144] was studied using a two-stage thermal-catalytic process (Figure 4d), in which

“pyrolytic lignin” was deposited by repolymerization of certain bio-oil compounds in the

first stage, and the treated bio-oil (in the form of volatiles) together with the gases formed

in the first stage were reformed in-line in a fluidized bed reactor. It is worth indicating

that the term pyrolytic lignin is not a unified one as other names have been used, such as

thermal lignin or thermal pyrolytic lignin. Yao et al. [145] used a two-stage fixed bed

reactor (Figure 3e), where firstly the bio-oil aqueous fraction was volatilized at 400 ºC

and subsequently the reforming step was carried out on modified Ni-Al catalysts.

Moreover, Wu et al. [146] used a two-stage fixed bed reactor system in order to avoid the

direct contact between the bio-oil and the catalyst. Thus, the bio-oil was reformed in the

first stage using dolomite as catalyst and, subsequently, the volatiles were purified using

a Ni/MgO catalyst in the second stage.

1.2.2. Pyrolysis and in-line reforming

The valorization of solid waste hydrocarbon and oxygenate materials (such as plastics

and biomass) for H2 production may be performed by a two-stage in-line pyrolysis-

reforming process, whose recent interest lies, among other reasons, on the higher

versatility of having two separated stages. Figure 5 shows the main reactor configurations

16
designed for biomass and plastic wastes, mainly studied in bench and laboratory scale

units [26,147].

Figure 5.

Some authors carried out the process in a two-stage fixed bed reactor (Figure 5a), both (i)

in discontinuous mode for the pyrolysis-reforming of polypropylene and polystyrene

[148,149] or biomass/plastics mixtures [150,151], and (ii) in continuous mode for

biomass feedstock, mainly for wood sawdust [152,153], as well as for cellulose [154],

rice husk [155,156], sugar cane bagasse and wheat straw [157], or pig manure compost

and sewage sludge [158,159]. Similarly, some authors employed two separated fixed bed

reactors connected in-line with several plastics as feedstock, both (i) in discontinuous

mode by the group of Williams [160-163], and (ii) in continuous mode by the group of

Yoshikawa [148,149].

In order to enhance mass and heat transfer in the pyrolysis step, some authors employed

a fluidized – fixed bed configuration (Figure 5b), with a continuous biomass feed to the

pyrolysis step (fluidized by sand) at the lower section of the unit, followed by the

reforming step in a fixed bed [164,165]. Other authors studied the implementation of a

conical spouted bed reactor in the continuous HDPE pyrolysis step (0.05 kg·h -1) [49], as

well as the addition of a catalyst to the pyrolysis step, followed by the fixed bed reforming

step with a secondary catalyst [166,167]. Another developed configuration consists on a

screw-kiln reactor for the continuous biomass pyrolysis and a fixed bed reactor for the

reforming of the pyrolysis volatiles (Figure 5c), which was employed both for biomass

[168] and MSW [169], the latter operating continuously (2 kg·h-1) in a pilot plant. The

two-step configuration was enhanced by introducing an intermediate gasification step

17
(Figure 5d), thus resulting on a first fluidized pyrolysis step, followed by entrained flow

gasification and a subsequent reforming step in a fixed bed reactor [170].

Although the use of fixed bed reactor in the reforming step is more extended, it leads to

severe bed blockage by coke deposition, which may imply serious limitations for its

scaling [49]. Aiming the mitigation of these operational problems, some authors have

employed a fluidized bed reactor in the reforming step, with a mention to the pioneer

work of Czernik and French [171], who employed a continuous pyrolysis-reforming of

polypropylene in separated fluidized beds. Some other authors have improved the system

performance, operating with (i) a conical spouted bed in the pyrolysis step, since the

vigorous cyclic movement avoids bed defluidization and enhances mass and heat

transport [49], (ii) followed by a fluidized bed in the reforming step (Figure 5e), for

plastics [172,173], biomass [174,175] and biomass/plastic mixtures [176]. This

configuration allows working continuously for a higher period of time without

operational problems, and thus involves a notorious improvement aiming a near-future

scaling-up [26].

2. Causes and mechanisms of reforming catalyst deactivation

Reforming and particularly, steam reforming, using the aforementioned catalysts and

reactor configurations, allows reaching full conversion of hydrocarbons and/or

oxygenates and high H2 yields, for instance, ca. 85 % of the stoichiometric maximum in

the case of steam reforming of bio-oil up to ca. 800 ºC [55,177]. However, the steam

reforming catalyst undergoes rapid and severe deactivation by means of a series of

physicochemical phenomena, including metal sintering, metallic phase oxidation, thermal

degradation of the support and, more notoriously, coke deposition. The relevance of each

18
deactivation cause depends on catalyst composition and structure and operating

conditions.

2.1. Metal sintering

Sintering of metals, both in supported or unsupported catalysts, is a thermally activated

physical phenomenon in which the growth of the surface metal particles takes place,

leading to the loss of active surface area [178,179]. An increase in the metal crystallite

size or sintering decrease the activity per gram of catalyst (less accessible active sites) but

may not affect the catalyst activity per exposed active site (normally used as turn over

frequency or TOF), in the case of structure-insensitive reactions (such as CO

hydrogenation). However, it may affect activity per exposed active site (increasing or

decreasing it), in the case of structure-sensitive reactions, such as hydrogenolysis or steam

reforming, in which sintering leads to a loss of activity [180]. Thus, this deactivation

cause has been widely studied in supported catalysts for steam reforming processes,

concluding that the main sintering mechanisms are based on (i) migration of atoms

adsorbed on smaller metal particles (adatoms) to larger particles, known as Ostwald

ripening (Figure 6a), and (ii) migration of small particles and coalescence to larger

particles aiming thermodynamic stability (Figure 6b) [64,181]. Hence, both sintering

mechanisms in Figure 6 imply the growth of larger particles at the expense of the decrease

and/or disappearance of smaller particles, and in this regard Monte Carlo simulations are

performed in order to advance in particle size predictions and thus the understanding of

sintering kinetics [182,183].

Figure 6.

Several factors have been found to influence on metal sintering during steam reforming

processes, temperature being pointed as most common. This is based on the fact that

19
sintering takes place above the Tamman temperature (half of the melting point

temperature), above which metal atoms start showing mobility [55,64]. Although noble

metals show higher sintering resistance due to their higher Tamman temperature (Ru,

1089 ºC; Rh, 856 ºC; Pt, 741 ºC; Pd, 641 ºC), Ni is the most studied metal for reforming

catalysts due to its lower cost, but its Tamman temperature (590 ºC) leads to inevitable

sintering in typical reforming conditions (above 600 ºC). Accordingly, Ochoa et al. [184]

monitored a sintering rate of ca. 20 nm·h-1 of a Ni-supported catalyst at 700 ºC of

reforming, in the in-line pyrolysis-reforming system of HDPE. Similarly, metal sintering

was the main responsible of the faster deactivation of a Ni supported catalyst compared

to a Rh supported catalyst in the oxidative steam reforming of raw bio-oil [185].

Moreover, sintering is accelerated by larger metal particles [186], as well as by a higher

steam content in steam reforming [28,186]. Indeed, operating above ca. 700 °C, steam/H2

atmospheres, high pressures (above 40 bar) and the presence of certain promoters (Pb, Cl,

S) favors the sintering of Ni particles in reforming catalysts [63,187]. Additionally, a low

dispersion of metal particles on the catalyst support, as well as a weak metal-support

interaction, favors particle migration (Figure 6b), whereas a strong metal-support

interaction hinders particle migration, favoring ripening (Figure 6a) as the governing

sintering route.

Sintering is routinely analyzed measuring the particle surface area (or dispersion) or the

particle size distribution in catalyst samples before and after its aging, by X-ray

diffraction (XRD), scanning and transmission electron microscopy (SEM and TEM), or

scanning transmission electron microscopy (STEM). However, these ex situ techniques

are not conclusive for establishing the governing sintering mechanism, and in this regard

in situ TEM allows the monitoring of detailed sintering dynamics with time on stream.

Some authors proved with this technique, together with phase field model predictions

20
[188], that early stages of Ni sintering are usually driven by Ostwald ripening of the

smallest particles (Figure 6a), leading to a drastic decrease of the particle dispersion,

whereas particle coalescence (Figure 6b) preferably takes place in subsequent sintering

stages [182,189]. This study turns out interesting as the smallest metal particles in

heterogeneous catalysts are in many cases the most active and selective. Moreover, the

laboratory-scale studies on sintering and disappearance or growth of individual particles

may be useful to estimate long-term sintering processes in industrial catalysts.

Several approaches aim to minimize metal sintering at reforming conditions, mainly for

Ni. For instance, K and Cu addition to Ni catalysts has proved to prevent sintering at 650

ºC in steam reforming, forming a Ni-Cu alloy in the latter case [190-192]. The addition

of noble metals, such as Ir and Rh, was also reported to improve the sintering resistance

of Ni-based steam reforming catalysts at 800 ºC and a steam pressure of 23 bar, by means

of the formation of Ni-Rh and Ni-Ir alloys [193]. Some other promoters, such as CeO2 or

CaO, also decrease atom mobility, as well as the use of porous supports, in order to favor

metal dispersion, and a strong metal-support interaction, such as oxide supports (α- and

γ-Al2O3, MgO, MgAl2O4, SiO2, ZrO2, and TiO2) or carbon nanofibers (CNFs) [194].

Additionally, coke deposition may prevent sintering by covering of the metal particles by

coke [195].

2.2. Metal oxidation

Another phenomenon leading to a decrease in the catalyst activity is the oxidation of

metal particles in the catalyst surface, since metallic phase is in most cases the active one.

Among the most employed metals in reforming catalysts (noble metals and Ni), whereas

noble metals are generally less prone to oxidation, Ni catalysts are the most susceptible

to this deactivation cause in typical reforming conditions. Nevertheless, an increase in the

21
calcination temperature of Ni-based catalysts may allow an increased resistance to

oxidation up to 700 ºC [144]. Regarding noble metals, although having a higher sintering

resistance, some authors pointed in Rh-based catalysts that depending on the reaction

medium composition, Rh oxide may be formed, leading to a decrease in activity, and thus

preserving Rh in its reduced state turns out relevant [196]. Typical oxidizing agents in

reforming reactions include oxygen in partial oxidation (i.e. reforming with oxygen

cofeeding) and oxidative steam reforming (i.e. with oxygen and steam cofeeding), CO2

in dry reforming and steam in steam reforming (Eq. (3)), and thus oxidation may be

favored by their high presence in the reaction medium. Conversely, the reducing capacity

of H2 and CO produced in reforming, together with the coverage of metal particles by

coke deposited during the reaction, is presumably able to maintain Ni in its reduced phase

even when the catalyst is extracted to the oxidant atmosphere [111,197].

2.3. Support aging

In addition to metal sintering, thermal degradation or aging of the catalyst may also lead

to a loss of support area by (i) support sintering, favoring metal sintering and changing

the metal-support interaction, (ii) and/or collapse of its porous structure, hindering the

access of reactants to metal particles within pores [64]. Among the most studied and/or

used support in reforming catalysts (Al2O3, MgO, MgAl2O4, SiO2, ZrO2 and TiO2, among

others), γ-Al2O3 and SiO2 are reported to be the most thermally stable supports in

oxidizing atmospheres, and carbons (such as CNFs) in the case of reducing atmospheres

[179]. Moreover, the presence of some promoters may form thermally stable spinel

phases, inhibiting support sintering, such as that form from the addition of Ca, Ba, Ni and

La oxides to Al2O3 [198]. Conversely, the presence of halogen atoms may favor support

sintering, such as Cl in MgO and TiO2, as well as the presence of steam, forming mobile

22
surface hydroxides (such as Si(OH)2) which are subsequently volatilized and condensate

into agglomerated particles [199].

Support degradation can also take place by phase transformations during its heating,

particularly in the case of Al2O3 [198], whose phase variety includes γ-Al2O3 (formed at

300-450 ºC), δ-Al2O3 (ca. 850 ºC), θ-Al2O3 (ca. 1000 ºC) and α-Al2O3 (ca. 1125 ºC), with

a drastic drop in the surface area from 400 m2·g-1 (γ-Al2O3) to 1 m2·g-1 (α-Al2O3). Thus,

the calcination temperature of the support plays a crucial role in its subsequent reforming

performance and resistance to degradation.

2.4. Coke deposition

Coke fouling is the physical deposition of unwanted carbonaceous species from the fluid

phase onto the catalyst surface, leading to activity loss due to blockage of active sites

and/or pores [64]. In catalytic processes with hydrocarbon and oxygenate feedstock, such

as reforming, unavoidable coke deposition and thus catalyst deactivation takes place by

means of several procedures, as shown in Figure 7: (i) strong chemisorption as monolayer

(carbide formation) or physisorption in multilayers hindering the access to active sites;

(ii) total covering (encapsulation) of the active site making it inaccessible to the reactants

(such as CnHmOk oxygenates or steam, in the case of steam reforming); (iii) plugging of

micropores and/or mesopores of the catalyst, blocking the access to active sites in inner

pores; (iv) changes and/or disintegration of catalyst structure and reactor plugging, in

advanced coke growth stages.

Figure 7.

A few sources established a distinction between two types of carbonaceous deposits based

on their origin, considering (i) carbon as that formed by CO disproportionation, whereas

(ii) coke is formed through condensation or decomposition of hydrocarbons and consists

23
of heavy hydrocarbons [200-202]. However, the vast majority of metal-catalyzed studies

in the literature indistinctly name ‘coke’ to refer to any unwanted carbonaceous solid

physically deposited on the catalyst surface, and thus the same nomenclature will be used

hereinafter in this work, for the sake of uniformity.

The range of reactions affected by this phenomenon includes, among others, oxidative

dehydrogenation, isomerization, hydrogenation, Fischer-Tropsch synthesis and

reforming, for which coke deposition is the main cause of catalytic activity loss [55,203].

Since coke deposition is unavoidable in these processes with hydrocarbons and/or

oxygenates as feedstock, many studies are focused on its minimization, as well as the

study of its features and their contribution to deactivation. Consequently, it is crucial to

study the coke formation with the aim of: (i) improving catalyst properties to minimize

activity decay; (ii) establishing optimal reaction conditions to minimize coke deposition;

and (iii) designing the reactor and the reaction-regeneration strategies for large-scale

operations.

2.4.1. Features of coke deposits

In processes affected by coke deposition (such as reforming), coke properties and their

effect on catalytic activity are usually explained in the literature in terms of four main

features, namely (i) content, (ii) location on the catalyst surface, (iii) morphology and (iv)

chemical nature, as depicted in Figure 8. The content of coke deposited is determined,

among others, by the employed operating conditions. In reforming reactions, too low

temperatures favor coke deposition since secondary reactions are promoted instead of

reforming and coke gasification is not promoted (ca. < 550 ºC in the case of bio-oil steam

reforming) [56], whereas a higher space time (higher proportion of catalyst mass with

respect to the fed reactants flow) is reported to lower the content of coke deposited, since

24
secondary reactions are minimized [138,141,142]. Moreover, an increasing steam and/or

oxygen presence (in the case of steam or oxidative steam reforming, respectively) favors

the gasification and/or combustion (respectively) of coke precursors and coke itself in

case of been formed [141,185]. On the other hand, an increase in the aromatic nature of

the feed subjected to reforming is reported to promote coke deposition, due to

polymerization reactions of aromatics [204]. The effect of catalyst composition is being

widely studied in the literature, since acid supports favor cracking reactions that yield a

higher coke content. The addition of metal oxides that offer high oxygen storage and

mobility through their redox behavior, such as CeO2, ZrO2 or CeO2-ZrO2 [205,206], also

help controlling coke deposition, by its combustion with oxygen atoms from the metal

oxide lattice. The presence of Fe oxide species in Ni-based reforming catalysts, forming

Ni-Fe alloys, also provides redox functionality and removes the carbon species deposited

on the surface [207]. Thus, catalyst structure also plays an important role in coke

deposition, such as metal-support interaction or metal particle size, since an increase in

the latter is known to promote coke formation [203,208].

Figure 8.

Regarding coke location, in metal-catalyzed reforming catalysts the proximity of coke to

metal sites influences on its nature, since these sites activate coke combustion and

gasification. Thus, the coke fraction which is proximate to metal sites is prone to be easily

combusted and/or gasified, impeding its evolution toward more condensed structures,

resulting in a (i) more hydrogenated composition (higher proportion of aliphatics with

respect to aromatics, i.e., higher H/C relationship); and/or (ii) more oxygenated

composition (higher O/C relationship) [111,209-211]. Conversely, that deposited further

from active sites evolves into more complex and “graphitic” structures, i.e. higher

proportion of aromatics with respect to aliphatics, and lower H/C and O/C relationship.

25
It is worth mentioning that the term of “graphitic” coke has been widely used for highly

developed aromatic structures, avoiding a more quantitative comparison with graphitic

materials. Some authors have established several types of coke deposited in the steam

reforming of oxygenates in terms of their location, distinguishing between

[71,121,138,212]: (i) coke deposited on metal particles, which is easily accessible to

gasification during the steam reforming and to oxygen during its combustion, both

activated by metal particles; (ii) coke deposited on metal-promoter interface and/or metal-

support interface; (iii) coke deposited on support, whose combustion is not catalytically

activated, and oxygen accessibility may be hampered by the porous structure of the

support. Interestingly, catalyst structure, such as the size of the metal particles, also may

play an important role in coke location [213], subsequently explained in Section 4 in this

work. Some works have evidenced a sequential and selective deposition in the steam

reforming of biomass pyrolysis volatiles [214,215], as depicted in Figure 9: (i) at low

values of time on stream, coke is deposited both on metal particles (coke I) and metal-

support or support (coke II), (ii) at higher values of time on stream, when the

encapsulation of metal particles by coke is significant (i.e. covering of metal particles is

reaching saturation point), coke deposition on metal particles (coke I) is decreased and

thus deposition on support (coke II) is promoted.

Figure 9.

Additionally, other reforming studies have identified three differentiated coke types based

on their morphology or structure (Figure 8) [111,201,216-220]:

i. Encapsulating coke. This coke is deposited on metal particles, and its formation

temperature is relatively low (ca. < 500 ºC). It is formed from the (i) adsorption on

metal sites of the compounds in the feed to be reformed (CnHmOk), as well as of the

26
 oxygenated and/or non-oxygenated compounds formed by secondary reactions of the

feed (CxHyOz and CaHb, respectively), followed by (ii) subsequent condensation or

polymerization of these precursors all over the metal particle surface, resulting in a

coke film which covers or encapsulates the metal particle. These precursors have

been identified, for instance, in the steam reforming of ethanol, including ethanol

(adsorbed as ethoxy ions) and decomposition byproducts (ethylene, acetone and/or

acetaldehyde) [218]; or in the steam reforming of bio-oil, including oxygenates in

bio-oil and their decomposition products, among which aromatic compounds are

potential precursors [221-223].

ii. Filamentous coke. This coke type is formed at higher temperatures (ca. > 450 ºC),

and generally concerns the formation of carbon nanotubes (CNTs) and/or carbon

nanofibers (CNFs), due to their filament-like morphology. The generally accepted

potential precursors of filamentous coke are: (i) CO by the Boudouard reaction (Eq.

(5)) or reduction (Eq. (11)), (ii) CH4 by its decomposition (Eq. (12)), and (iii) light

hydrocarbons, such as ethylene, by their decomposition (Eq. (13)) (Figure 8). Since

the first three reactions (Eqs. (5), (11) and (12)) are reversible, consideration of

thermodynamics turns out crucial aiming coke removal by gasification. The widely

accepted formation mechanism will be subsequently explained in more detail

(Section 4), and involves the (i) adsorption of coke precursors on metal sites and

dissociation to give atomic carbon, (ii) diffusion of carbon through the bulk and/or

surface of the metal particle, (iii) nucleation and (iv) precipitation on the basis or the

surface of the metal particle. In the former case (deposition on the basis), this

continuous process physically separates the metal crystal from the surface in which

it is supported, lifting it as the carbon filament grows, with the metal particle on its

top [57,224-227]. This phenomenon attracts much attention since it may be beneficial

27
 in order to prevent metal sintering, but may at the same time cause loss of active

phase if coke filaments are fractured by catalyst attrition in a fluidized bed, for

instance. Since carbon does not dissolve into noble metals, the formation of

filamentous coke is ascribed as a general rule to base transition metals, such as Ni,

Co and Fe [199], although a few studies have reported its formation on noble metals,

such Rh [228], Pt [229] and Ru [230].

ΔH0 (kJ·mol-1)

CO reduction: CO + H2 ↔ C + H2 O -131.3 (11)

Methane
CH4 ↔ C + 2H2 75 (12)
decomposition:

Decomposition of b
Ca Hb → aC + H2 >0 (13)
hydrocarbons: 2

iii. Pyrolytic coke. This is formed by thermal cracking of hydrocarbons or oxygenates in

the reaction medium at high temperatures (ca. > 600 ºC, Figure 8), and mainly occurs

at severe deactivation stages of the catalyst, when reforming reactions are almost

fully disfavored [111]. These cracking products (i.e. coke precursors) are deposited

indistinctly all over the catalyst surface (non-selective deposition) and form a coke

layer which causes its total encapsulation, even filling the voids created by

filamentous coke [111], and thus implies a drastic decrease of the catalyst activity.

Hence, its formation is generally not reported in reforming deactivation studies, since

it is avoided by the development of highly active catalysts, as well as by the catalyst

regeneration (coke combustion) before reaching a severe deactivation degree.

Interestingly, although coke content is routinely pointed as a crucial factor influencing on

catalyst performance, coke structure is reported to have a higher incidence on

deactivation, rather than its content, unless the latter becomes severe [218,219,231]. Thus,

28
encapsulating coke is pointed as the responsible for a significant catalyst deactivation,

since it blocks the access of reactants to the metallic sites. Conversely, the contribution

to deactivation of this coke morphology is reported as being hardly noticeable, unless (i)

a massive growth of filaments takes place, thus hindering the access of reactants through

the catalyst pores or even catalyst breakdown [217-219], (ii) growth in the form of clumps

of entangled filaments takes place, which encapsulates metal particles and thus causes

deactivation (later discussed in Figure 11) [94], and/or (iii) loss of metal occurs as

filaments are removed during catalyst regeneration [111,141,142]. Moreover, coke

morphology influences on its chemical nature, based on its location with respect to metal

particles (Figure 8). In this regard, (i) encapsulating coke has a less evolved structure

(higher H/C and/or O/C ratio), since it is proximate to metal sites which catalyze its

combustion and/or gasification, whereas (ii) filamentous and (iii) pyrolytic coke, due to

their further location with respect metal sites, have a more condensed and graphitic nature

(higher aromatics-to-aliphatics ratio) and thus require higher temperatures for their

elimination by gasification/combustion. Additionally, several authors claim that a change

in the metal particle size involves a change in the coke formation mechanism, favoring

the growth of filamentous coke with larger particles, whereas smaller particles favor the

growth of non-filamentous coke [55,232,233]. Furthermore, a highly porous catalyst

structure is recommended, in order to facilitate the growth of filaments to the outside the

particles and thus to avoid total pore plugging and/or structure disintegration (Figure 7(iii)

and (iv)).

2.4.2. Mechanisms of coke formation

Some authors proposed a few mechanisms in which coke formation in steam reforming

reactions takes place by means of formation and transformation of several intermediate

and stable carbonaceous species [201,224]. These mechanisms have been summarized
29
and reformulated in Figure 10, and include the following species, varying in morphology

and reactivity: (i) Cα or atomic carbon adsorbed on the metal surface (surface metal

carbide), formed at ca. 200-400 ºC; (ii) Cγ or bulk metal carbide (ca. 150-250 ºC); (iii) Cβ

or polymeric amorphous films (ca. 250-500 ºC); (iv) Cv or filamentous coke (300-1000

ºC); (v) Cc or graphitic platelets or films (ca. 500-550 ºC). This mechanism suggests that

the most reactive and amorphous carbonaceous species adsorbed on metal sites at lower

temperatures, such as Cα and Cβ, are converted at higher temperatures into less reactive,

graphitic and condensed species, such as Cv and Cc [64]. Thus, at high temperatures

employed in reforming reactions (600-850 °C), Cv and Cc are the main stable forms of

carbonaceous species present on the catalyst surface, the formation of the latter being

driven by diffusion of graphitic layers through the metal particle and their subsequent

development [234].

Figure 10.

Overall, the classification into three coke morphologies (encapsulating, filamentous and

pyrolytic) is supported by a great number of studies on the reforming of methane,

hydrocarbons and biomass-derived oxygenates. The most studied coke formation

mechanism is that of methane reforming, since (i) it is the hydrocarbon with the highest

H/C ratio and thus attains the highest H2 yield, (ii) it is the most simple hydrocarbon and

thus its coke formation mechanism is better understood [235], and (iii) it produces carbon

nanotubes (Figure 11), whose properties have attracted a great deal of interest in several

mechanical, thermal and electronic applications, triggering a better comprehension of

coke formation mechanism, as subsequently discussed in Section 4. Even though the

formation and growth of filaments/CNTs in methane reforming is commonly stated to

preserve a considerable active surface area and does not drastically affect catalyst

30
deactivation, a massive growth and entanglement of these CNTs may end up with metal

particle encapsulation, leading to significant deactivation (Figure 11) [94].

Figure 11.

In the case of larger hydrocarbons, they possess a lower H/C ratio and thus involve a

higher coke yield. Steam reforming takes place by means of decomposition of the fed

hydrocarbon into lower molecular weight hydrocarbons (by dealkylation or aromatic ring

opening, among others), and these intermediate decomposition products act as coke

precursors [236,237], together with the aforementioned CO (Eqs. (5) and (10)) and CH4

(Eq. (12)). Among these decomposition reactions during steam reforming, dehydration of

hydrocarbons gives olefins, such as ethylene, which is acknowledged as active in

oligomerization for the formation of amorphous and encapsulating coke [111,238], as

displayed in Figure 12. Moreover, this coke morphology may evolve into filamentous

structures, by means of metal carbides as reactive intermediates [200,239]. Conversely,

other authors claim that the mechanism of filamentous coke from ethylene takes place by

means of consecutive reactions of free radicals [240].

Figure 12.

In this regard, some authors observed by TEM that the coke deposited on Ni catalysts in

the H2 production by in-line pyrolysis-reforming of several plastic feedstock (HDPE,

LDPE, PP) comprises both amorphous (or encapsulating) and filamentous coke, the

former being presumably favored by the olefinic nature of the stream entering into the

reforming step [6,7,95,160,241]. Some of these authors aimed a co-production of H2 and

filamentous coke in the form of CNTs due to their commercial interest. In this respect, it

is worth noting that the presence of steam is reported to act as a weak oxidant, reacting

31
with amorphous and encapsulating coke, and leading to a slower and more ordered growth

of nanotubes, whose crystallinity is increased [242,243].

Coke deposition in steam reforming of oxygenates has also been widely studied in the

literature, identifying the aforementioned three morphologies, but the approach of a

detailed formation mechanism shows a somehow increased difficulty with respect to

hydrocarbons, as the formation and transformation of a series of oxygenated compounds

need to be considered in the reaction scheme. For instance, in steam reforming of ethanol,

whose interest lies on the fact that it may have a biomass-based origin, the evolution of

the coke formation with time on stream shows an initially amorphous coke that evolves

into filamentous coke, which is progressively graphitized [218] and may resemble carbon

nanotubes or graphene, depending on its graphitization degree [227]. In this regard,

several authors made some approaches in order to understand the formation routes of the

coke deposited [129,244]. Vicente et al. [218] took a step forward (Figure 13), proposing

a mechanism for the steam reforming of ethanol on a Ni/SiO2 catalyst, in which the

precursors of encapsulating and filamentous coke are identified, based on the product

distribution and catalyst characterization for a wide range of operating conditions. The

main precursors of encapsulating coke were ascribed to (i) products from secondary

reactions (ethylene, acetaldehyde and acetone), and (ii) ethanol, adsorbed as ethoxy ions

which subsequently dehydrate and condense into coke deposits. Thus, this encapsulating

coke is favored in conditions in which ethanol concentration in the reaction medium is

high (low conversion). On the other hand, CO and CH4 are assigned as the main

precursors of the filamentous coke, by means of the Boudouard reaction (Eq. (5)) and

CH4 decomposition (Eq. (12)), respectively, where the former route prevails.

Figure 13.

32
Thus, this identification of the coke precursors is considered to be crucial, aiming the

minimization of encapsulating coke, which is responsible for severe catalyst deactivation.

The monitoring with time on stream of the concentration of these coke precursors in the

reaction medium during the steam reforming of ethanol turns out useful to explain the

coke formation rate and its nature, and thus, deactivation dynamics. In this regard, a three-

stage deactivation mechanism was established performing the reaction on a Ni/La2O3-

αAl2O3 catalyst [111], as depicted in Figure 14. In a first reaction stage, a significant

increase of filamentous coke deposits (from CH4 and CO) lifts Ni particles on top of the

filaments and decreases the Ni particle size, without blocking the active sites and thus

implying a scarce contribution to catalyst deactivation. In a second stage, the decrease in

the Ni particle size continues, and the decrease of CH4 and CO yields, together with the

increase of acetaldehyde and unconverted ethanol yields, suggest a change in the coke

nature. Thus, the growth of filamentous coke decreases and undergoes progressive

condensation and graphitization, whereas the formation of a non-filamentous coke

increases (mainly from the evolution of the filamentous fraction), which is deposited in

multilayers both on Ni particles (blocking them) and on support (plugging pores and

filling the voids between coke filaments in multilayers). In a third stage, catalyst

deactivation is severe and ethanol conversion decreases, whereas non-filamentous coke

increases both in content and graphitization degree, deposited in multilayers both from

thermal decomposition of oxygenates in the reaction medium and aging of filamentous

coke. Thus, it may be ascribed to the pyrolytic coke previously described in Figure 8.

Figure 14.

Similarly, reaction and coke formation pathways have also been proposed for the steam

reforming of other oxygenates as bio-oil model compounds, such as acetic acid

33
[62,69,245], methanol [246], acetone [247], n-butanol [248] or phenol [58]. Nevertheless,

the complexity and heterogeneity in the composition of bio-oil (acids, ketones, esters,

alcohols, phenols and guaiacols, among others) makes it difficult to advance in the

understanding of coke formation mechanisms during the steam reforming of bio-oil, due

to (i) the different reactivity of the oxygenates, (ii) the synergy of their corresponding

reforming reactions and, particularly, (iii) the rapid catalyst deactivation [55]. According

to Wang et al. [249], decomposition steps of reactants take place during the steam

reforming of bio-oil, with the formation and adsorption of CH* and CH3C* species,

pointed out as key coke precursors, which are subsequently reformed. Hence, the control

of the formation of coke precursors and the enhancement of their reforming and

gasification reactions is a suitable strategy for minimizing deactivation [180].

2.4.3. Factors affecting catalyst deactivation by coke deposition

Considering the difficulty of identifying the main coke precursors and thus establishing

coke formation mechanisms in the steam reforming of bio-oil, most efforts are directed

toward the study of operating conditions and their effect on coke formation and thus

deactivation. Temperature has been pointed out as a key factor for minimizing

deactivation of Ni-based catalysts during the steam reforming of raw bio-oil [142], bio-

oil aqueous fraction [104,138] and bio-oil/bio-ethanol blends [143], with 650-700 ºC

being the suitable range, since reforming reactions are favored and coke gasification is

enhanced without Ni sintering. However, a higher attention should be paid to coke

morphology, nature and location, rather than its content.

Regarding coke morphology and composition, a higher deactivation is usually attained

with an increasing amount of amorphous and encapsulating coke. In the case of steam

reforming of bio-oil, the amount of encapsulating coke is related to the concentration of

34
bio-oil oxygenates in the reaction medium [141], and thus this coke type usually

comprises a more hydrogenated and/or oxygenated nature (coke I in Figure 14). This

observation evidences the autocatalytic effect of deactivation during the steam reforming

of biomass-derived oxygenates, since the catalyst deactivation leads to an increase of the

non-reacted oxygenates, which in fact are the precursors of encapsulating coke formation,

and this in turn promotes a higher deactivation [174,214].

In this sense, Ochoa et al. [220] (Figure 15) found that coke morphology in the steam

reforming of bio-oil causes a deep impact on deactivation and is mainly affected by

temperature, since at lower temperatures (550 ºC) a highly deactivating encapsulating

coke is formed from the oxygenates in the reaction medium, whereas a more filamentous

coke deposited at higher temperatures (700 ºC) does not significantly affect catalyst

activity. Moreover, they concluded that coke content (mainly affected by steam-to-carbon

ratio) does not influence on deactivation as significantly as its composition and

morphology (mainly affected by temperature) (Figure 15). Space time has also been found

to influence of the nature of coke deposited, since at low values the content of

encapsulating and filamentous fractions are increased, whereas at high space time values

the formation of encapsulating coke is attenuated [142]. Moreover, since the presence of

steam is known to favor gasification of coke and its precursors [138,250], Valle et al.

[141] set a steam-to-carbon molar feed ratio above 4 as suitable at high temperature (700

ºC) and high space time (0.38 gcatalyst·h·gbio-oil-1), obtaining an initial H2 yield of 87 % and

70 % after 5 h of time on stream.

Contact time is not a process parameter that can be tuned in order to minimize coke

deposition. What normally happen is that the intention is always to extend the lifetime of

the catalyst and operate for the longer contact time possible. However, form the research

point of view, analyzing the dynamics of coke evolution is of paramount importance for

35
understanding the effects of coke deposition. In this sense, some works dealing with the

effect of contact time in coke deposition during the reforming of pyrolysis products

should be highlighted [111,184,214,215].

Figure 15.

Furthermore, the catalytic performance during the steam reforming of bio-oil under

certain operating conditions is highly influenced by (and influences on) the composition

of the reaction medium (Figure 15), which in turn depends on composition of the bio-oil

fed. Rennard et al. [222] claimed that coke deposition during the steam reforming of bio-

oil is mainly ascribed to polymerization of aromatic and unsaturated components in the

lignin-derived fraction of bio-oil, due to its high thermal instability. Ortiz-Toral et al.

[223] found that bio-oil fractions that were richer in low-molecular-weight species, such

as acetic acid and acetol, were beneficial for H2 production, whereas the presence of

heavier molecules, such as levoglucosan and furfural, had a deep impact on deactivation.

However, no direct correlation was established between the molecular weight of the

molecules reformed, selectivity toward reforming and amount of coke deposited, due to

the complexity in composition of bio-oil fractions. Gayubo et al. [221] ascribed phenols

and aldehydes to the main contributors of deactivating coke formation, whereas Li et al.

[204] assigned phenols as the main coke formation responsibles, which undergo

polymerization reactions into polycyclic aromatic hydrocarbons, leading to coke

formation on the catalyst surface. Remón et al. [107] concluded that levoglucosan

posseses the fastest coking rate among other functional groups such as furfural, guaiacol

and phenol. In line with previous observations, Ochoa et al. [220] found a linear

correlation between the oxygenated composition of the reaction medium and the

composition of coke measured by Fourier transform infrared (FTIR) spectroscopy (Figure

15), and concluded that the presence of phenols with highly oxygen moieties (such as

36
methoxyphenols) and polyols (such as levoglucosan) play an important role in coke

formation, rather than acids, ketones and aldehydes. As a representative polyol, the steam

reforming of glycerol has been found interesting for the co-production of CNT-like

filamentous coke, together with H2 production [251].

Therefore, considering the impact of bio-oil composition on deactivation and in order to

reduce coke deposition, some authors (i) operated with the bio-oil aqueous fraction

[104,138], (ii) studied the co-feeding of bio-oil with methanol [122,252] or bio-ethanol

[143], or (iii) implemented a thermal treatment step of the raw bio-oil prior to its steam

reforming [253], so that a controlled and continuous deposition of carbon solids (thermal

pyrolytic lignin) takes place in this thermal step. These solids are formed from the

polymerization of phenolic compounds in bio-oil, thus minimizing pipe plugging or

catalyst deactivation in the subsequent reforming step. However, catalyst deactivation

during the reforming of biomass pyrolysis oxygenates or bio-oil is still severe, the process

requires challenging operating conditions (high temperatures and steam and catalyst

content) and may last for a few hours, hindering its scaling-up for industrial H2

production.

At the catalyst level, many attempts have been performed to control the deposition of

coke in these reactions or minimize its impact. Changing the morphology of the metal

(Ni) has recurrently been used to control catalyst deactivation, either by decreasing the

particle size [254,255], changing the chemical environment of Ni [256], using a different

synthetic pathway [257], using different calcination/reduction methods [144], or using

other metals such as the incorporation of Co [258,259], the use of Fe-Zn [260] or other

metals all together [261]. On the other side, several attempts have been made to control

the catalyst deactivation trough support modification, either by changing porosity or

metal placement on the support [28], or by using other conventional supports such as

37
ZrO2, SiO2, MgO, TiO2 [262] or unconventional ones [263]. A very well-known effect of

deactivation quenching is by increasing the basicity of the support and/or decrease its

acidity [56]. Kumar et al. [264] have indicated some of the trends within the use of basic

support in the reforming of acetic acid: CeO2, and ZrO2 have interesting redox features

together with basic character. The incorporation of La2O3 [265] or Ca and Mg [266] also

exhibits enhanced coke resistance.

Last but not least, at the reactor level many approaches have also intend the control of

catalyst deactivation. These approaches have been described in the Section 1.2.

3. Characterization techniques for deactivated reforming catalysts

An interesting procedure in order to register catalyst (and coke) properties during the

deactivation process consists on an in situ monitoring of the reaction dynamics by

characterization techniques [267-269]. However, the high temperatures used in steam

reforming (especially for heavy feedstock such as bio-oil, up to ca. 850-900 ºC), do not

allow this in situ analysis, due to the thermal limitation (usually up to ca. 600 ºC) of the

characterization units. Thus, the most widespread catalyst (and coke) characterization

procedure consists on extracting the spent catalyst at several values of time on stream or

several operating conditions, and subsequently performing a series of characterization

techniques (ex situ analysis). A review of the mostly employed characterization

techniques for reforming catalysts is shown below (Section 3.1), followed by a more

detailed section on coke characterization (Section 3.2), since some of its features are not

often studied enough and may give valuable insights.

3.1. Characterization of catalyst deterioration

38
The mainly analyzed catalyst features related with its deterioration may be classified into

the following:

Morphology. Catalyst morphology may be analyzed by means of N 2 adsorption-

desorption, and scanning and transmission electron microscopy (SEM and TEM,

respectively). N2 adsorption-desorption provides information about changes in the

catalyst surface porosity due to coke deposition (such as pore plugging, Figure 7(iii)), or

due to disintegration of the catalyst structure (Section 2.3 and Figure 7(iv)), among others,

in terms of surface area (per mass unit), total pore volume (per mass unit) and average

pore diameter. On the other hand, electron microscopy gives a visual idea of the physical

properties of the catalyst surface. In this regard, scanning electron microscopy (SEM)

provides 3-dimensional images and focuses on the surface morphology, mainly by means

of secondary electron images (SEI), which have a high resolution. On the other hand,

transmission electron microscopy (TEM) gives 2-dimensional pictures and provides a

more detailed identification of compounds at different depths, since their different atomic

number causes differences in their brightness (Figure 16a). For instance, the metal particle

size may be measured from a number of TEM images, in order to determine whether

metal sintering takes place (Section 2.1), and the identification of certain crystalline

phases is possible, by measuring the distance between layers (Figure 16a). The three

mentioned techniques provide complementary information on quantitative (N2

adsorption-desorption) and qualitative (SEM and TEM) properties of catalyst

morphology; however, N2 adsorption-desorption may not be as useful as microscopic

images in the case of catalyst surfaces with low porosity.

Figure 16.

39
Phase location. SEM analysis may give insights on the location of different phases or

elements on the catalyst surface, mainly by means of backscattered electron images (BEI),

which are employed in order to distinguish between different compounds in the surface,

due to the fact that brightness in BEI depends of the atomic number of the compound.

Complementarily, TEM analysis also differentiate compounds (of different atomic

number) in terms of their brightness within the image. Moreover, energy-dispersive X-

ray (EDX) spectroscopy allows the identification of elements in a specific area within a

SEM or TEM image.

Composition. The aforementioned EDX analysis gives a semiquantitative composition of

elements in a certain region of a SEM or TEM image. Additionally, X-ray diffraction

(XRD) quantifies the crystalline phases within the catalyst structure, and may be useful,

among others, in order to determine the average size of crystalline phases (such as

metallic phase), which determines the presence of sintering (Section 2.1), or whether the

metallic sites are in reduced or oxidized state (Section 2.2). A more detailed study of the

oxidation state of metallic sites on the catalyst is provided by X-ray photoelectron

spectroscopy (XPS), which gives a semiquantitative determination of the different phases

present in the outermost layers of the catalyst surface (2-10 nm from the surface). This

turns out interesting in order to corroborate XRD results whether metal oxidation takes

place or not, which may be a deactivation cause (Section 2.2).

3.2. Coke characterization

The unavoidable and severely deactivating nature of coke deposition in steam reforming

reactions calls for a further understanding of, among others, (i) the effect of operating

conditions and the reaction medium composition on the content, nature and location of

coke, (ii) the effect of these coke properties on deactivation, and (iii) the relative

40
importance of different compounds (in the reaction medium) in the formation of coke

and, consequently, in the catalyst deactivation. Although these features are more

commonly studied and better understood in the case of simple feedstock (such as

methane), an increasing attention is being focused on more complex and heterogeneous

feedstock, such as bio-oil or pyrolysis volatiles of waste plastics, aiming to enhance their

feasibility in a large-scale H2 production framework in near-mid future.

Table 1 summarizes the main ex situ techniques used for the characterization of the coke

deposited on reforming catalysts. Each technique is more useful to study one certain coke

feature, and their complementation provides a complete and detailed characterization.

Morphology. N2 adsorption-desorption provides quantitative information about the

porous structure created by the coke deposited, for instance, in the case of carbon

filaments. Moreover, SEM images allows identifying the overall morphology of the coke

deposited on the surface (Figure 16b), whereas TEM images shows a more detailed

morphology and internal features of the coke deposited, such as number of walls, wall

width and diameter of CNTs and CNFs, or distance between graphene layers (Figure 16

and Figure 19a-c). Thus, the most detailed information about coke growth dynamics may

be obtained from TEM analysis, although the other two techniques provide

complementary information.

Table 1.

Location. Electron microscopic analysis (SEM and TEM) can also be complementarily

used in order to determine the location of the coke deposited within the catalyst surface.

Nevertheless, considering the 3-dimensional and superficial nature of SEM images, some

phenomena such as pore plugging by coke may not be adequately visualized by this

technique. Conversely, since TEM images show inner regions of the coked catalyst, it

41
may be more useful to precisely locate the coke deposits, as well as to approximately

determine the layer thickness in amorphous and metal-encapsulating coke deposits or the

diameter and wall thickness in CNTs. Moreover, EDX spectroscopy allows the

identification of coke (as C element) in certain catalyst regions in SEM and TEM images,

and thus its location can be approximately set. Additionally, thermogravimetric analysis

(TG) by means of temperature-programmed oxidation (TPO) of the catalyst (TG-TPO)

gives the temperature in which mass loss takes place and thus coke (or different coke

fractions) is combusted, which may give an approximate idea of its location [270,271].

This is based on the criterion that metal particles catalyze coke combustion, and thus coke

deposited next to metal particles are burned at lower temperatures during TPO analysis

[111]. In this way, some authors have differentiated between three coke fractions with an

increasing combustion temperature, namely deposited (i) on metal particles, (ii) on metal-

promoter interface and/or metal-support interface, and (iii) on support

[71,121,138,212,214,215]. However, combustion temperature in TG-TPO analysis also

depends on more factors (such as coke composition), and thus this technique cannot be

exclusively used for determining coke location, but it gives qualitative complementary

information to that gained from SEM and TEM images.

Content. The amount of coke deposited on the catalyst surface is routinely determined

from the mass loss undergone by the coked catalyst subjected to combustion (TG-TPO)

[272]. This procedure is valid as long as no (or negligible) metal oxidation takes place

during the process (for instance, in noble metal catalysts), and thus the mass loss totally

corresponds to the coke deposited. Nevertheless, in base transition metal catalysts (Ni,

Fe, Co), metal oxidation during TPO is considerable and leads to a mass gain, which

masks the mass loss by combustion and thus the coke content cannot be directly

determined. In this regard, an interesting solution consists on coupling TG-TPO with the

42
analysis of the combustion exhausts with mass spectrometry (MS) (TG-MS/TPO)

[71,111,138-143,215,218,219,273,274], and determining the coke content from the

quantified CO2 signal in MS. This procedure involves O2 in excess in the reaction

medium, in order to assure complete combustion and negligible CO concentration.

Moreover, a qualitative approach of the coke content in a certain region of the catalyst

surface in a SEM or TEM image is possible by EDX spectroscopy, which may be useful

for the sake of comparison between certain regions of an image.

Composition. TG-TPO analysis is the most common method used for a qualitative

characterization of coke fractions with different composition, based on the general

criterion that coke fractions burning at lower temperatures have a (i) more hydrogenated

composition (higher proportion of aliphatics with respect to aromatics) [209,275], (ii)

more oxygenated composition [209], and (iii) higher accessibility of coke within catalyst

porous structure [276-278]. However, this qualitative study does not provide much

information on detailed chemical nature, and it may be complemented by a series of other

techniques. For instance, the semiquantitative composition of a given coke region in a

SEM or TEM image can be analyzed by EDX spectroscopy. Moreover, since XRD detects

the crystalline phases within the catalyst structure, coke may be identified in case of being

present in the graphitic form (diffraction peak at 2θ = 26º). Furthermore, X-ray

13
photoelectron, C nuclear magnetic resonance and infrared spectroscopic techniques

(XPS, 13C NMR and IR, respectively) provide information about the functional groups

(including oxygenated moieties) within coke. On the one hand, XPS is recommended for

the analysis of the outermost layers of the catalyst surface (2-10 nm from the surface),

where coke is mainly present in catalysts with a low porosity [215,220]. On the other
13
hand, C NMR and IR are intended for the bulk sample structure [184,279,280], thus

being more adequate for the study of coke in highly porous catalysts. However, since

43
coke in reforming catalysts is routinely analyzed together with the catalyst on which it is
13
deposited, C NMR analysis is not recommended due to the ferromagnetic nature of

some base transition metals (Fe, Ni, Co) used in reforming catalysts, and, to a lesser

extent, the paramagnetic nature of noble transition metals (Pt, Pd and Rh, among others).

This issue would be solved by extraction of a soluble coke fraction (with a solvent, such

as CH2Cl2) and its subsequent 13C NMR analysis, but the extraction technique is usually

found ineffective in reforming, since the relatively condensed coke structures formed on

the catalyst are hardly soluble.

The oxygen presence within coke structure evidences a considerable complexity for the

interpretation of results by some of these techniques, particularly by IR [209,214,220],

and its complementation by other techniques turns out beneficial and/or necessary. Thus,

Raman spectroscopy provides insights into the coke structure and aromaticity of

carbonaceous structures containing sp2 C atoms, such as graphite, disordered

carbonaceous or diamond-like structures, carbon nanotubes or graphene, among others

[281-283]. Complementarily, matrix-assisted or not-assisted laser desorption/ionization

coupled with time-of-flight mass spectrometry ((MA)LDI-TOF MS) allows the

determination of molecular fractions that comprise the coke structure, which gives an idea

of the approximate nature of the coke precursors. By means of this technique, Ochoa et

al. [184] found that, the coke deposited on the catalyst during the reforming of HDPE

pyrolysis volatiles, underwent carbonization with time on stream, from napthenes and

long chain olefins (resembling the feed into reforming) to highly polyaromatic structures.

The coupling of techniques during the coke combustion (TPO) may give additional

insights on the composition of coke fractions, with the analysis of the combustion

exhausts by mass spectrometry (MS) or the solid by Raman and/or infrared (IR)

spectroscopy or differential scanning calorimetry (DSC) [209]. Some authors have

44
employed the FTIR-TPO technique to study the combustion properties of several

carbonaceous solids by monitoring the FTIR spectra of the evolved products, for instance,

in the co-combustion of oil shale and semi-coke formed during its refining [284], co-

combustion of coal, lignite and petcoke blends [285] or co-combustion of blends of

hydrothermally carbonized oil palm biomass and coal [286]. More advanced methods

involve the direct FTIR analysis of the solid during the TPO. In this regard, and combined

with MS (FTIR-MS/TPO), some authors observed differences in chemical nature of

several coke fractions deposited on microporous shape-selective catalysts

[275,276,287,288].

Additionally, the registration of Raman spectra during a heating program (Raman-TPO)

turns out interesting in order to observe the evolution with temperature in structure of

carbon solids, although few studies are reported in the literature in this regard. Pardanaud

et al. [283] studied the thermal stability of amorphous carbon layers, registering Raman

spectra during a linear heating program. The evolution of several Raman parameters

obtained from the spectra revealed structuring of the samples under heating. Duzynska et

al. [289] studied the phonon properties (understood as vibrational energy that arises from

oscillating atoms within a lattice) of single-walled carbon nanotube thin films, monitoring

the Raman spectra under a linear heating program, aiming the understanding of thermal

properties and heat dissipation of the materials.

Complementarily, differential scanning calorimetry during coke combustion (DSC-TPO)

allows calculating the combustion heat released, which in fact is related to the elemental

analysis of coke [209,279]. At the same time, the higher heating value (HHV) of a coke

sample can be estimated from its elemental composition using the following equations

[290]:

45
 WO
HHV (MJ·kg-1) = [338.8·WC + 1442.8· (WH - ) + 94.2·WS ] · 10-3 (14)
8

HHV (MJ·kg-1) = 34.91·WC + 117.83·WH - 10.34·WO - 1.51·WN + 10.05·WS (15)

From these equations one may conclude that an increase in HHV is given by an increase

in carbon and hydrogen concentration and decrease in oxygen concentration within coke

structure. Moreover, since the heat released from coke combustion during catalyst

regeneration is envisioned to be provided to the reforming endothermic reaction [64,270],

coke composition and, particularly, oxygen content, will have a considerable impact on

the total heat balance. Thus, the consideration of these coke features are thought to be

crucial for the minimization of the heat requirements in a reforming-regeneration strategy

[209].

Combustion kinetics. Thermogravimetric analysis during coke combustion (TG-TPO,

TG/MS-TPO) allows the determination of combustion kinetics required for the design of

the catalyst regeneration step [280]. The most common procedure consists on the

assumption of a mathematical expression describing the combustion rate, i.e. a kinetic

model, but this method reports two main inconveniences: (i) only one set of kinetic

parameters is obtained for each coke fraction from the deconvolution of the TPO profile,

and (ii) the selection of the kinetic model to describe the process has been found to

influence strongly the resulting kinetic parameters [291]. In this sense, since assuming a

reaction model raises uncertainties [292], the development of modulated

thermogravimetric analysis (MTG) turns out advantageous (for instance, MTG/MS-

TPO), as no kinetic model assumption is needed, requires a single heating program

perturbed by a sinusoidal modulation and calculates the evolution of the activation energy

during the whole combustion process [292-294]. In a previous work, the most suitable

46
practices to properly obtain the activation energy were established, studying the effect of

heating rate, amplitude and frequency of the modulation [295]. These results were useful

for a subsequent study of kinetics and their dynamics for the combustion of several coke

fractions deposited on the catalyst in the steam reforming of bio-oil [209].

4. Production of carbon-structured materials in reforming processes

The valorization of hydrocarbons and oxygenates (regardless of being derived from fossil

or renewable sources) in the H2 production inevitably involves the generation of carbon

deposits on the catalyst and/or the reaction system, which leads to a decrease in their

performance and thus, limits the H2 yield. This may take place by means of covering of

the active sites in the catalyst or pipe plugging, among other causes, and hence, these

carbon deposits are often pointed as a non-desired product or residue during H2

production. These solid deposits include, among others, pyrolysis char [296-299],

gasification char [300,301], pyrolytic lignin generated in the thermal treatment of bio-oil

[253,279], or coke deposited on the catalyst during catalytic pyrolysis [302-304] or during

reforming [111,112,141,142,172-174] processes (Figure 17).

Figure 17.

Considering the unwanted nature of the generation of these carbon deposits, the economic

throughput of the H2 production process from hydrocarbons may be enhanced by means

of the production of value-added carbon materials (Figure 17). For instance, char is

reported in the literature as a promising precursor for graphene production [305,306],

whereas the coke deposited on the catalyst (catalytic routes) may be in the form of carbon

nanotubes [307,308], whose morphology shows multiple favorable applications [309].

47
The valorization routes of carbon materials have been reported to mainly depend on their

morphology (Figure 17), composition and structure (Figure 18), and may include: (i)

combustion (for heat and/or electricity), (ii) catalytic valorization (such as reforming,

catalytic cracking or oxidative catalysis for obtaining functionalized aromatics or acids),

(iii) thermal valorization (such as pyrolysis, coking, visbreaking, steam cracking, or

gasification) and (iv) activation (production of activated carbons) [279,310,311].

Figure 18.

Concerning reforming of hydrocarbons, a simultaneous production of H 2 and carbon

deposits with filamentous morphology is gaining interest in the nanotechnological

research field, due to the potential use of these carbon materials (such as carbon

nanotubes) in a number of mechanical, thermal and electronic applications. In this regard,

the group of Williams in the University of Leeds (UK) has envisioned applications for

the filamentous coke deposited on the catalyst during the steam reforming/gasification of

the volatiles from the pyrolysis of waste plastics, such as low density polyethylene

[6,312,313], polypropylene [241,314], tires [315] or real-world waste plastics [7,316], as

well as in bio-oil reforming [317], based on the fact that this filamentous coke resembles

high-value CNTs. Nevertheless, the feasibility of a co-production of coke with

filamentous morphology together with H2 production during the reforming of

hydrocarbons needs further study on the properties and formation/growth mechanism of

the coke, aiming to advance in their understanding and thus to enhance the economical

throughput of the reforming process within refinery. In this sense, Ochoa et al. [184]

observed an increase with time on stream in size and stacking of graphene layers in the

filamentous coke deposited on the catalyst during the steam reforming of high density

polyethylene pyrolysis volatiles, although they concluded the deposited coke would

48
require further carbonization and graphitization in order to lead to proper features as in

CNTs.

Many studies in the early literature (mostly until the 1990s) regarding steam reforming of

hydrocarbons used to refer to carbon deposits with filamentous morphology as ‘carbon

whiskers’ [224], ‘whisker-like carbonaceous species’ [201] or ‘filamentous carbon’

[318], whose formation mechanism is not fully understood. Conversely, the studies in the

last decades tend to employ a more defining terminology, differentiating between carbon

nanofibers (CNFs) and carbon nanotubes (CNTs), although still some confusion is found

in the literature between them, as they are closely related in terms of structure and

properties. Their physical, mechanical, and chemical properties, as well as their low

production cost, have received much attention for the fabrication of absorbent materials,

gas storage components, field emitters, or composite materials, among others, in

aerospace and automotive, construction, sports, electronic device and biosensor

applications [319-322]. Moreover, applications in tissue engineering also show promising

results, such as the treatment of cancer tumours by photothermal therapy studied in the

University of Oklahoma [323,324].

Their main differences, measured by techniques such as high-resolution transmission

electron microscopy (HRTEM) and Raman spectroscopy [325-327], are due to their size

and stacking of carbon atoms, and thus, disorder degree. Figure 19 shows a schematic

comparison of several morphologies. CNTs are hollow cylinders with the structure of a

wrapped graphene layer (single-walled carbon nanotube, SWCNT, Figure 19a) or several

layers coaxially disposed (multi-walled carbon nanotube, MWCNT, Figure 19b) [319].

CNFs consist of graphene sheets disposed in different stacking arrangements (for

instance, that shown in Figure 19c), which conform a fiber-like structure. CNTs are

smaller than CNFs (with a diameter of ca. 5-50 nm and ca. 50-200 nm, respectively),

49
possess a higher thermal conductivity (3000-6000 W·m-1·K-1 and 1950 W·m-1·K-1,

respectively) and better mechanical properties than CNFs, due to their highly ordered

structure [322]. As in CNFs, carbon fibers (CF) also have a variety of stacking

arrangements of graphene sheets (Figure 19d,e), but forming considerably larger

structures than in CNFs.

Figure 19.

Chemical vapor deposition (CVD) has shown to be the most promising technique for the

large-scale and low-cost production of CNFs and CNTs [321,327,328]. This process

involves the dissociation and/or chemical reactions of gaseous reactants in an activated

(heat, light, plasma) environment, followed by the formation of a stable solid product

[329]. The CVD process intended to the production of graphitic structures is based on the

thermal decomposition (pyrolysis) on a metal catalyst of a hydrocarbon gas, such as

methane, ethylene or acetylene [328,330], and has been employed to understand their

formation and growth mechanisms.

Considering that transition metal (mostly Fe, Co and Ni) nanoparticles are employed as

catalysts in the CVD process [243,328], the results on CVD may turn out helpful to

advance in the study of the formation of CNTs and/or CNFs in reforming processes, as

they are commonly conducted on supported catalysts with similar nature of the active

sites (transition metals) than those of CVD. The growth of CNFs and CNTs by CVD is

commonly reported to take place by means of (i) dissociative adsorption of carbonaceous

precursors onto the metallic particle surface, (ii) diffusion of carbon atoms and (iii)

incorporation of carbon atoms and formation of a graphitic fibrillar or tubular structure

around the metallic particle [213,331]. However, it is still not clear whether the diffusion

of the carbon atoms takes place through the particle bulk (Figure 20a) [200,318,332,333],

50
on the particle surface (Figure 20b) [334,335] or a combination of both. A simulation of

molecular dynamics was performed by Gomez-Gualdron and Balbuena [233] to study the

role and mechanism of carbon diffusion during single-walled carbon nanotubes

(SWCNTs) formation on supported metal nanoparticles by CVD. These authors

considered that both bulk and surface diffusion of carbon atoms take place, together with

another fraction of carbon atoms potentially involved in carbide formation. Abild-

Pedersen et al. [331] also considered the growth of graphene layers via surface and

subsurface (bulk) diffusion of carbon atoms, performing an ab initio DFT study for

methane decomposition over Ni nanoclusters. The last authors concluded that the energy

barrier for carbon diffusion through the particle bulk was significantly higher than that

for surface diffusion. Some other controversial aspects in the growth of CNTs and CNFs

include whether the metal is in solid or liquid state, or whether it is in pure state or in the

form of metal carbide [336]. However, the formation of metal carbide is unstable under

steam reforming conditions (above 300 ºC in the case of Ni carbide), and thus is

considered an intermediate in the process of dissolving carbon in the metal [224,227].

Figure 20.

Additionally, the final step of the mentioned mechanism, i.e. the incorporation of carbon

atoms around the metallic surface, may lead to different growth mechanisms, the most

accepted in the literature being: (i) ‘tip-growth’ (Figure 20 and Figure 21a), in which the

CNT or CNF grows from the support with the metal particle on its tip [337,338], and (ii)

‘base-growth’ (Figure 21b), in which the CNT or CNF grows from the supported metal

particle [339]. Interestingly, Gohier et al. [213] found that the catalyst particle size

influences on the growth mechanism of CNTs by CVD, concluding that a ‘tip-growth’

mechanism takes place for large particles (>> 5 nm), and a ‘base-growth’ for smaller ones

51
(< 5 nm), as depicted in Figure 21. This phenomenon was explained based on the

consideration that small particles are chemically more reactive due to their higher surface-

to-volume ratio, and that carbonaceous structures are absorbed with a stronger binding

energy on small particles. Thus, it was suggested that in larger particles (Figure 21a), as

absorbed carbonaceous structures (graphitic sections or reticulated carbon chains) have a

weaker binding with metal particles, their diffusion to the metal-support interface is

favored (step 2 in Figure 21a), and leaves the top surface of the metal particle for further

adsorption of carbonaceous compounds. This continuous process of carbon deposition in

the interface elongates the metal particle (step 3 in Figure 21a) until the particle is

separated from the surface, and CNTs (usually multi-walled or MWCNTs, with > 10

walls) grow with the metallic particle on its tip (step 4 in Figure 21a). Conversely, smaller

particles (Figure 21b), owing to their higher reactivity and a stronger interaction with

absorbed carbonaceous structures, lead to the formation of a graphene layer that

encapsulates the particle surface, in the way that the access of carbonaceous structures to

the particle surface is limited to the metal - support interface (steps 2-3 in Figure 21b).

Thus, the incorporation of carbon in the interface leads to the formation of single- or few-

walled CNTs (SWCNTs in Figure 21b4-5, or FWCNTs in Figure 21b4’-5’, respectively).

Figure 21.

Moreover, Baker [340] claimed that the growth rate of carbon filaments is inversely

proportional to the square root of the diameter of the metal catalyst particles, and thus

concluded that the growth mechanism is diffusion-controlled. Besides the metal particle

size, other aspects such as crystallographic plane types and their orientation [341,342],

strength of the metal-support interaction [343,344], temperature [318] or the composition

and content of reactants adsorbed on the catalyst surface, have been proved to cause a

52
deep impact on the nucleation and growth mechanism of the carbonaceous deposits, and

thus need to be taken into account. For instance, the use of higher temperatures (600-1150

ºC) has shown to favor the formation of SWCNTs, whereas at 300-800 ºC MWCNTs are

preferentially generated [328]. Moreover, the controlled presence of steam was found to

be optimal for producing CNTs with high crystallinity [345], whereas a high partial

pressure of hydrogen could hinder the dissociation of the hydrocarbons subjected to

reforming [225]. However, the effect of hydrogen on the surface elementary reaction

steps and the formation of fibrillar or nanotubular coke remains unclear.

In order to advance in the mechanistic and kinetic study of the growth dynamics of CNTs

or CNFs on supported metal particles, in situ TEM analysis is considerably useful

[332,340,346-348]. Helveg et al. [349] monitored the growth of CNFs by in situ HRTEM

in methane decomposition on Ni crystals, concluding that nucleation and formation of

graphene layers are associated with the restructuring and formation of Ni step-edge sites.

Based on these HRTEM results and by means of a DFT study, Abild-Pedersen et al. [331]

concluded that these step-edge sites are preferential for the growth of graphene layers.

Moreover, they established three mechanisms in which graphene growth takes place

(front growth at Ni facet sites, base growth by carbon incorporation, and base growth by

atom exchange), depending on the termination of the graphene perimeter at the nickel

surface.

5. Catalyst regeneration

If the carbon materials produced as coke are not interesting from any commercial

viewpoint, catalyst regeneration is inevitably the following concern once we are able to

operate for long reaction times (days to years) or in continuous reaction/regeneration

mode. The most extended way to regenerate and rejuvenate the reforming catalyst
53
involves oxidative environments at high temperatures to burn off the coke. This strategy

has been compared with gasification by Wu et al. [350] in the reforming of bio-oil.

However, combustion offers technological easiness at the expense of carbon loss.

Ni supported catalyst typically do not fully recover the activity in biomass [351] or plastic

[352] reforming/regeneration cycles. This is true for the first reforming/regeneration

cycles. However, they reach a more stable behavior once the Ni particles do not sinter

significantly during the reforming, which happens after several reforming/regeneration

cycles. Similar results have been observed in the reforming of naphthalene [353], which

is potentially a pyrolysis product from plastics. Other authors have found that by using

bio-oils with lower water content, the Ni/Al2O3 catalyst can be fully regenerated [232].

Nevertheless, a more stable behavior and better renderability of Ni catalyst can be

achieved by using Ni-spinel, such as NiAl2O4 [354], bulk Ni [355] or alloys of Ni-Fe

[356]. Li et al. [357] have found that incorporating CeO2 (or MnO), traces Pt, and MgO

to the Ni supported catalyst has a positive impact for having a more stable behavior trough

reforming/regeneration cycles.

Noble metal supported catalyst use relatively milder conditions of reaction than Ni

supported catalyst and it has been found that the formers can be regenerated in the

reforming of biomass-derived pyrolysis oil [358]. However, Wang et al. [359] have found

that the noble metal supported catalyst does not fully recover the activity when a more

“realistic” feed is used, even with the presence of promotors.

Valle et al. [360] have solved the regeneration issue with a complete new approach

involving the removal of phenols, which have the leading role in the catalyst deactivation

during bio-oil reforming [220]. By removing the phenols, the performance of the catalyst

and its stability in reforming/regeneration cycles are significantly enhanced.

54
6. Final remarks

Near- and mid-term energy market calls for the co-use of a wide range of sources for H2

production, including fossil fuels and alternative and renewable sources. Among the

studied processes for H2 production, thermochemical routes from hydrocarbon and

oxygenate feedstock (both fossil or renewable) are gaining much attention, for which a

great deal of laboratory-scale catalytic studies are being carried out, mainly based on the

reforming technology. Moreover, within the sustainable economy framework, the

utilization of waste materials and biomass-derived materials for their reforming is

attracting increasing scientific interest, as well as a change in perspective of unwanted

coke deposits toward their valorization (Figure 22).

Figure 22.

First of all, an increase in the complexity of the feedstock into reforming poses a challenge

in the study of catalyst deactivation, with respect to previous studies in the reforming of

pure and model compounds. However, this study involves a step forward for the large-

scale valorization of these complex feedstock within the waste- or bio-refinery

frameworks.

Some of the most interesting thermochemical reaction systems for H2 production from

these complex feedstock show a series of advantages for their large-scaling, including: (i)

the reforming of storable oxygenates, with a decentralized production of storable

oxygenates and its subsequent centralized reforming in biorefinery, and (ii) in-line

pyrolysis reforming, whose two-stage strategy allows the minimization of the energy

requirements, aiming the optimization of the catalyst performance.

55
However, the feasibility of reforming toward its scaling-up still needs to be further studied

and enhanced, since the catalyst used in the process undergoes a progressive and

sometimes severe activity loss, thus hindering the economic viability of H2 production.

Catalyst activity during reforming may be affected by two main phenomena: (i)

deterioration of the catalyst structure, by means of metal sintering, metal oxidation and/or

thermal degradation of the support, and (ii) more notoriously, coke deposition on the

catalyst surface. On the one hand, the structure deterioration calls for a tuning in the

catalyst composition and preparation method, including the optimization of the catalyst

calcination conditions for a reproducible performance in subsequent reaction-

regeneration cycles, as well as a tuning of the reforming operating conditions, among

others.

On the other hand, since coke formation in reforming is unavoidable due to the carbon-

containing nature of the feedstock and employed operating conditions, one may easily

conclude that hydrocarbons with a higher H/C ratio implies higher H2 production and

lower coke deposition, thus catalyst being active for a longer period. In this regard,

methane is the most widely studied reforming feedstock, since it has the highest H/C ratio,

but as aforementioned, a feasible H2 economy calls for the availability of complementary

feedstock submitted to reforming. This unavoidably means the use of larger and more

complex hydrocarbons (with a lower H/C ratio), such as waste plastics derivatives (waste

refinery), as well as hydrocarbons with oxygenated moieties within their structure, such

as biomass-derived compounds (biorefinery). The use of these larger and more complex

feeds unavoidably decreases H2 production and increases catalyst deactivation (mainly

by coke deposition), compared to the reforming of pure compounds. In this regard, the

large-scale viability of these alternative feedstock for H2 production turns out to be

challenging and calls for further understanding of the coke deposited, including: (i) the

56
detailed nature and features of coke on spent catalysts, (ii) identification of coke

precursors and coke formation mechanism, and (iii) catalyst regeneration, among others.

Reasonably, the challenge of studying these coke features is considerable when the

reforming feedstock is not a pure compound, but a complex and highly heterogeneous

mixture of hydrocarbons (such as those from pyrolysis of waste plastics) or that of

oxygenates (such as bio-oil or biomass pyrolysis volatiles). This is of the utmost

relevance, due to rapid catalyst deactivation, challenging operating conditions (high

temperatures, high steam and catalyst contents), as well as the different reactivity of the

compounds in the reaction medium and the synergy of their corresponding reforming

and/or secondary reactions.

Considering the difficulty of identifying the coke precursors in the reforming of large

hydrocarbons and oxygenates, and thus establishing coke formation mechanisms, most

efforts in the literature are directed toward the study of catalyst selection, operating

conditions and their effect on coke formation. Moreover, unlike coke content, not enough

attention is often paid to coke composition, location on the surface and morphology,

which is demonstrated to have a higher impact on catalyst deactivation. These coke

features have been found to be strongly affected by the reforming operating conditions,

since temperature and space time show a higher influence on the composition of the

medium and coke, coke morphology and location, which in turn is more influential on

deactivation than coke content (mainly affected by the steam-to-carbon ratio).

7. Conclusions

The viability of the reforming of complex feedstock calls for a further understanding of,

among others, the effect of operating conditions on the content, nature and location of

57
coke, the impact of different compounds (in the reaction medium) in these coke

properties, and the impact of these coke properties on deactivation. Aiming the study of

these coke properties, another challenge encountered in the reforming of complex

mixtures of hydrocarbons and oxygenates is the limitation of catalyst (and coke)

characterization techniques by means of an in situ monitoring of the reaction dynamics,

due to the severe conditions for their reforming, such as high temperatures and fluidized

regime on the catalyst bed. Thus, the most common procedure is the ex situ coke analysis

after catalyst extraction at several values of time on stream or operating conditions.

However, and particularly in the reforming of complex feedstock, in the literature it

consists routinely on a temperature programmed oxidation (TPO) for a rapid

determination of coke content and/or nature, often complemented with electron

microscopy (SEM, TEM) for analyzing coke morphology, and thus few efforts in coke

properties and formation mechanisms are found. In this regard, in a limited number of

studies, the main progress in the understanding of reforming catalyst deactivation has

been done by (i) spectroscopic techniques (such as Raman, IR or XPS), (ii) technique

coupling, (iii) and particularly, in situ techniques during coke combustion, which turned

out useful to gain more detailed insights into properties of several coke fractions,

determination of coke precursors and/or kinetics of coke combustion, aiming catalyst

regeneration. In this sense, one of the main challenges in near-future would be the use of

in situ techniques during reforming reactions under severe conditions.

These results open an interesting field into the versatile use of these techniques in other

reforming or coke-depositing processes, particularly with feeds with a complex chemical

nature, like those fed within waste- and biorefinery frameworks. Furthermore, owing to

the fact that coke deposition is usually non-desired and with a limited economic interest,

a significant step forward involves the consideration that coke nature and its combustion

58
(during catalyst regeneration) may play an important role in the energy balance in the

reforming-regeneration system, thus minimizing the heat requirements in the reforming

step. Moreover, since coke with a filamentous nature (and particularly carbon nanotubes,

CNTs) has attracted a great deal of interest in several commercial applications, some

authors do not envision CNT-like coke as an unwanted deposition, but they pursue a co-

production of H2 and CNTs during reforming, which in fact triggers a better

comprehension of CNT formation mechanism. These considerations aim at enhancing the

economical throughput of the process for its promising large-scaling.

Acknowledgments

This work was carried out with the support of the Ministry of Economy and

Competitiveness of the Spanish Government, some cofounded with ERDF funds

(CTQ2015-68883-R and CTQ2016-79646-P) and the Basque Government (IT748-13).

A. Ochoa is grateful for his predoctoral grant from the Department of Education,

Language Policy and Culture of the Basque Goverment (PRE_2016_2_0129). The

technical and human support provided by SGIker (UPV/EHU, MICINN, GV/EJ, ERDF

and ESF) is greatly acknowledged.

Abbreviations

BEI backscattered electron images

DFT density functional theory
Cα atomic carbon
Cβ polymeric amorphous films
Cγ bulk metal carbide
Cc graphitic platelets or films
Cv filamentous coke

59
CNFs carbon nanofibers
CNTs carbon nanotubes
CVD chemical vapor deposition
DSC differential scanning calorimetry
EDX energy-dispersive X-ray
FTIR Fourier transform infrared
H/C hydrogen to carbon ratio
HCs hydrocarbons
HDPE high density polyethylene
HHV higher heating value
IR infrared
LDI laser desorption/ionization
LDPE low density polyethylene
MALDI matrix-assisted laser desorption/ionization
MS mass spectrometry
MSW municipal solid waste
MTG modulated thermogravimetric analysis
MWCNT multi-walled carbon nanotube
NMR nuclear magnetic resonance
O/C oxygen to carbon ratio
PP polypropylene
SEI secondary electron images
SEM scanning electron microscopy
STEM scanning transmission electron microscopy
SWCNT single-walled carbon nanotube
TEM transmission electron microscopy
TG thermogravimetric analysis
TOF turn over frequency or time of flight
TPO temperature-programmed oxidation
XPS X-ray photoelectron spectroscopy
XRD X-ray diffraction
WGS water gas shift

60
 Environmental sustainability

Coal Petroleum derivatives Natural gas Biomass

Steam
Pyrolysis

Gasification Reforming Gasification Reforming

Carbon
H2 CO2, CO, CH4, light HCs (C2-C4)
materials
Current valorization interest

Figure 1. The main processes for H2 production from hydrocarbon and oxygenate
feedstock at present and in near future, and their typical product distribution.

61
 Total number of publications
1000
(until 2018)
Ni 5787

Number of publications
800 Cu 1435
Co 749
Fe 908
600 Ir 157
Ru 703
Rh 1109
400
Pd 1183
Pt 2257
200

0
1970 1980 1990 2000 2010
Year

Figure 2. Evolution of the number of scientific studies using several transition metals
for reforming. Source: Scopus®. Keywords: reforming and catalyst.

62
 (a) (b) (c)

(d) (e) (f)

(i)
(g) (h)

(k) (l)
(j)

Figure 3. Several support structures for the encapsulation of metal particles in

reforming catalysts: (a-c) core-shell [79], (d-f) core-tube [82], (g-i)
mesoporous structure [87,88], (j-l) lamellar structure [91,92]. Figures (a), (d),
(g) and (j) are taken from [13].

63
Figure 4. Reactor configurations for reforming of storable biomass-derived
oxygenates: (a) fixed bed reactor, (b) fluidized bed reactor, (c) spouted bed
reactor, (d) two-stage fixed-fluidized bed reactor, and (e) two-stage fixed bed
reactor. Adapted from [26].

64
Figure 5. Reactor configurations for pyrolysis and in-line catalytic steam reforming of
plastic wastes and biomass: (a) two-stage fixed bed reactor, (b) fluidized –
fixed bed reactor, (c) screw-kiln – fixed bed reactor, (d) fluidized bed,
entrained flow gasification and fixed bed reactor, and (e) spouted bed –
fluidized bed reactor. Adapted from [26,147].

65
 (a) (b)
Large Large
Adatoms particle particle
Small Small Small
particle particle particle

Support Support

Figure 6. Two main mechanisms of sintering of metal particles: (a) Ostwald ripening
and (b) particle migration and coalescence.

66
 CnHmOk
C Physisorption
C
H2O C C Chemisorption
C C
C Metal carbide
C
C
Metal
C
Support

(ii) (iv)
(ii) (i)

(iii)
(i)
Degradation

Figure 7. Deactivation pathways by coke deposition on a supported metal catalyst: (i)

carbon chemisorption or physisorption hindering the access to reactants; (ii)
metal particle encapsulation; (iii) pore plugging; (iv) degradation of catalyst
structure, for instance, by massive CNT growth.

67
 Space time ↓ Aromatic feed ↑
O2 ↓
Steam ↓ Catalyst acidity ↑
T ↓↓, T ↑↑ Coke Metal particle size ↑
Catalyst

(2)
(3)
(a) (b) (1)
(c)

Metal Metal
Support Support Support

Location (a) On metal (b) On metal-promoter / (c) On support

metal-support interface

Chemical H/C ↑
Aromatics ↑
nature O/C ↑

Morphology (1) Encapsulating (2) Filamentous (3) Pyrolytic

Precursors CO, CH4, light CaHb Thermal CxHyOz

CnHmOk CxHyOz CaHb CnHmOk
cracking CaHb
(i) Adsorption + dissociation
Formation (i) Adsorption (ii) C diffusion through metal
mechanism (ii) Condensation Non-selective
(iii) Nucleation
deposition
(iv) Precipitation
Formation
temperature 400 ºC 450 ºC 500 ºC 600 ºC

Figure 8. Main features of coke deposited on catalyst in reforming reactions.

68
Figure 9. Evolution with time on stream of location, deposition rate and estimated
molecular structures of coke deposited on a Ni-based catalyst in the reforming
of biomass pyrolysis volatiles [214].

69
 CnHmOk (a) Cα (a) + H (a) + CO (a) + CO2 (a) + CaHb (a) + CxHyOz (a)

Cγ (s) C dissolved Cβ (a)

in metal

Cv (s) Cc (s)

Figure 10. Formation and transformation of several coke species during reforming of
CnHmOk. Adapted from [201,224]. Note: ‘a’ and ‘s’ refer to adsorbed and
solid states, respectively.

70
Figure 11. CNT growth, metal particle encapsulation and CNT entanglement during dry
reforming of methane [94].

71
 H H
H H H H C=C
H H C=C C=C H H
C=C H H H H
H H

Metal
Support Support Support Support

Oligomerization Encapsulating coke Filamentous coke

Figure 12. Coke formation from ethylene oligomerization.

72
Figure 13. Kinetic scheme proposed for the steam reforming of ethanol on a Ni/SiO2
catalyst [218].

73
Figure 14. Evolution of Ni0 and coke and deactivation stages of the catalyst in the steam
reforming of ethanol [111].

74
 Correlation
Major
Operating conditions: Temperature S/C molar ratio Minor
(550-700 ºC) (1.5-6)

Gas-phase
Reaction medium:
composition

Catalyst: Coke Coke

Ni0 particle size Coke content
morphology composition

Deactivation: Product
Stability Conversion
yields

Figure 15. Correlation diagram between the factors influential on deactivation during the
steam reforming of bio-oil on a Ni/La2O3-αAl2O3 catalyst. Adapted from
[220].

75
 (a) 10 nm (b) (c)

5 nm 5 nm

Figure 16. (a) TEM image of a Ni particle [349]; (b) SEM image of synthetized CNTs
[309]; (c) TEM image of a conical CNF [361].

76
 Table 1. Techniques for the characterization of coke deposited on reforming catalysts.

Technique Morphology Location Content Composition Combustion Information provided

kinetics
N2 adsorption- × Surface area and porosity of coke and coked
desorption catalyst
SEM × × Coke morphology and location

TEM × × Coke morphology, dimensions and location

TG-TPO × × × × Content; qualitative location and composition;

model-based combustion kinetics
TG/MS-TPO × × Content; model-based combustion kinetics

EDX × × × Elemental composition and qualitative content

in an specific region; coke location
XRD × Crystallinity (diffraction peak at 2θ = 26º)

XPS × Surface atomic concentration

IR × Semiquantification of functional groups

Raman × Organization and aromaticity

(MA)LDI-TOF MS × Determination of molecular fractions

FTIR/MS-TPO × Semiquantification of functional groups of

coke fractions

Raman-TPO × Organization and aromatization of coke

fractions
DSC-TPO × Combustion heat

MTG/MS-TPO × Model-free combustion kinetics

77
 Coal Thermal routes Graphene
Gasification
Petroleum
Thermal Char
derivatives and
wastes pyrolysis Thermal
Bio-oil
pyrolytic
Natural Catalytic routes Thermal lignin
treatment
gas Catalytic
pyrolysis Coke
Biomass Reforming
Carbon
nanotubes

Figure 17. Production of carbon materials in the main H2 production processes from
hydrocarbon and oxygenate feedstock.

78
 36 Pychar (1.0)
Combustion O/C ratio Pyrolytic lignin
32 0.1 (0.7)
0.4
Lignite (3.0)
HHV (MJ kg )

28
-1

Bio-oil (0.7)

24 Thermal pyrolytic
lignin (1.2)
Catalytic
Thermal Bitumen (0.9)
20 valorization
valorization
Pine sawdust (0.7)
16 Activation Commercial lignin
(0.7)
0.00 0.04 0.08 0.12 0.16
-1
H/C ratio (wt% wt% )

Figure 18. Valorization routes of several carbon materials, based on their composition
(H/C and O/C ratios) and high heating value (HHV) [279]. For a better
visualization, the size of each bubble is linked with the O/C weight ratio
multiplied by a factor shown in the right legend.

79
 (a) 2 nm (b) 10 nm (c) 50 nm (d) 2 μm

direction
CNF
~ 0.34 nm
~ 0.34
nm
(e) 2 μm

SWCNT MWCNT CNF CF

Diameter
1 101 102 103 104 (nm)

Figure 19. SEM, TEM and HRTEM comparison in size and morphology of several
tubular and fiber-like carbon structures: (a) single-walled carbon nanotube
(SWCNT), (b) multi-walled carbon nanotube (MWCNT), (c) stacked-cup-
type carbon nanofiber (CNF), (d-e) carbon fibers (CF). Adapted images from
[362-364].

80
 H2 CnHmOk H2
(a) C C (b)

Metal C C Metal

CNF CNF

Figure 20. Growth mechanism of a CNF with carbon diffusion via (a) the metal particle
bulk and (b) the particle surface.

81
 (a) CnHmOk CnHmOk CnHmOk
CnHmOk
CnHmOk CnHmOk
C
CC C C
C
C C C

1 2 3 4

(b) CnHmOk
CnHmOk
CnHmOk CnHmOk CnHmOk CnHmOk CnHmOk
C CC

1 2 3

CnHmOk CnHmOk CnHmOk CnHmOk

4 5

CnHmOk CnHmOk CnHmOk CnHmOk

4’ 5’

Figure 21. CNT growth mechanism from large particles (typically >> 5 nm) (a) and from
small particles (typically < 5 nm) (b). Adapted from [213].

82
 Steps forward
Pure compounds Complex mixtures
Reforming CH4 CnHm CnHmOk CnHm CnHmOk
feedstock
Waste refinery Bio-refinery
Storable CnHmOk SR Decentralization
Reaction
system CnHm, CnHmOk Pyrolysis SR Energy saving

 Metal sintering
Structure Structure
 Metal oxidation Optimization of
deterioration  Support degradation
tuning
Catalyst catalyst
activity Coke Formation performance &
Properties Precursors regeneration
deposition mechanism
Combustion
Content Morphology Location Composition
kinetics

Temperature Coke composition

Operating & morphology Tuning of operating
Space time Deactivation
conditions conditions
S/C ratio Coke content

Ex-situ techniques
Catalyst and coke SEM/ Spectroscopy Technique In-situ
TPO techniques
characterization TEM (IR, Raman, XPS) coupling
Coke Energy Co-production
Unwanted deposition
balance
+ of CNTs
valorization

Figure 22. Roadmap of breakthroughs and challenges in the study on catalyst

performance and deactivation in the reforming of hydrocarbons and
oxygenates for H2 production.

83
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