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Carbon Deposition
Carbon deposition (coking) is the phenomena of organic compounds absorbed on
active sites being dehydrated or decarboxylated to fine solid carbon, which
accumulates and fouls the catalyst.
From: Recent Advances in Thermo-Chemical Conversion of Biomass, 2015

Related terms:
Methane, Hydrogen, Syngas, Anode, steam reforming, Deactivation

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Hydrogen Energy Engineering Applications and Products

Hirohisa Uchida, Makoto R. Harada, in Science and Engineering of Hydrogen-Based Energy Technologies, 2019

Carbon Formation
Carbon deposition is considered to be an inevitable phenomenon in hydrogen production reactions. Carbon
deposition occurs in the steam reforming reaction depending on operating conditions. Precipitated carbon is
classified into three types. Table 5.6 describes these carbons [12]. The most typical carbon deposition is called
whisker carbon and occurs on the surface of the Ni catalyst. Carbon deposition amount increases due to diffusion of
C in the fuel. In addition, there are carbon deposits in which carbon is generated as a core of the feedstock radical
called encapsulating polymers. This phenomenon is seen as the activity gradually decreases. It is a phenomenon
observed at a low temperature of 500°C or less. The third carbon deposition is called pyrolytic carbon, which is
generated by thermal decomposition of hydrocarbons as a feedstock. For this reason, this phenomenon occurs in a
temperature range of 600°C or more.

Table 5.6. Different Routes for Three Types of Carbon Formation in Hydrogen Production Reactions [15]

Whisker Carbon Encapsulating Polymers Pyrolytic Carbon

 Whisker Carbon Encapsulating Polymers Pyrolytic Carbon

Formation Diffusion of C through Ni-crystal: Slow polymerization of Thermal cracking of

nucleation and whisker growth with hydrocarbon radicals on Ni-surface hydrocarbon: deposition of C-
Ni crystal at top into encapsulating film precursors on catalysts

Temperature >300°C <500°C >600°C

Phenomenon Deactivation breakdown of catalyst Gradual deactivation Encapsulation of catalyst

and increasing ΔP particle: deactivation and
increasing ΔP

Critical Low steam/carbon Low temperature High temperature

parameters Low activity Low steam/carbon High void fraction
Aromatic feed in feedstock Low H2/carbon in feedstock Low steam/carbon high-
Abrupt temperature change Aromatic reed in feedstock pressure deactivation

Usually carbon deposition in hydrogen production utilizing steam reforming reaction generates whisker carbon. It
depends on contamination of unsaturated hydrocarbons in the feedstocks. Fig. 5.8 is a graph showing the time
course of the carbon precipitation amount when using a Ni catalyst as the feedstock of unsaturated hydrocarbon. It
is understood that carbon precipitates in a very short time.

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Figure 5.8. Carbon formation from different feedstock. Thermogravimetric studies. 0.7 g Ni/MgO/Al2O3 catalyst. S/C = 2, 0.1 MPa, 500°C.
Based on J.R. Rostrup-Nielsen, New aspects of syngas production and use, Catal. Today. 63 (2–4) (2000)159.

Fig. 5.9 is the scanning electron microscope (SEM) image of the surface of the Ni catalyst. (A) is a new catalyst. It is
evident that the Ni particles are highly dispersed on the alumina carrier. In this way, the Ni particles are initially in a
highly dispersed state on the surface of the carrier.
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Figure 5.9. SEM of the surface of the Ni catalyst. (A) New catalyst surface. (B) Sintered surface of the catalyst. Ni particles become large according
to reaction heat. (C) Surface of the carbon deposit. It is usually caused by a decrease in activity. Plant steam reforming catalyst. S/C = 2.5,
P = 0.1 MPa, Ni/Al2O3 catalyst. Feedstock gas is propane.

Normally, since the Ni catalyst is used at a high temperature of 450°C or higher, sintering occurs and the particle
diameter becomes coarse. That is, the Ni particles move on the surface of the carrier. Therefore, the activity
decreases as compared with the initial stage. Fig. 5.9(B) is a SEM image of this sintered surface. Ni particles present
a liquid-like behavior at high temperatures, 450°C or higher. Ni particles will coarsen by sintering because their
surface energy is decreased. For this reason, there is a phenomenon in which the activity decreases.
When the activity declines, carbon precipitates on the surface of the catalyst as shown in Fig. 5.9(C). The carbon
deposition shown in Fig. 5.9(C) is a typical whisker carbon, and filamentary nanotubes are observed. Also, Ni particles
acting as a catalyst exist at the tip of the filament. Carbon deposition is remarkable, especially when subjected to
sulfur poisoning described later. Usually, in a reformer of a fuel cell that is a hydrogen energy device, carbon
deposition often occurs on the inlet side of the catalyst layer, and most of it is whisker carbon. The cause is
considered to be due to low S/C (molar ratio of steam to carbon) at the start of the reformer, and when carbon is
generated, it cannot be removed and thus the reformer is replaced [13].

Natural Gas Conversion V

K. Tomishige, ... K. Fujimoto, in Studies in Surface Science and Catalysis, 1998

4 CONCLUSION
Ni0.03 Mg0.97O solid solution catalyst has high resistance to carbon deposition in CO2 reforming of methane, but the
deactivation due to oxidation of active nickel species was observed under some reaction condition. This deactivation
was able to be avoidable by the addition of hydrogen to reactant gas. On Ni0.03 Mg0.97O catalyst, nickel particles were
much more highly dispersed than that on 3 mol% Ni/MgO. And CO2 was adsorbed on Ni0.03 Mg0.97O similarly to
MgO. In addition, CO2 was activated on Ni0.03 Mg0.97O at 60 K lower temperature than on 3 mol% Ni/MgO. This is
suggested to be promoted by large interface between metal and support, and strong interaction of CO2 with support
surface. Combined with the results of reaction order, it is suggested that high resistance to carbon deposition in
methane reforming is closely related to high ability of CO2 activation and this causes rapid oxidation of carbon
species on nickel before converting to deposited carbon.

Carbon Nanofibers
R.T.K. Baker, in Encyclopedia of Materials: Science and Technology, 2001

4 Events Occurring at the Metal–Carbon Interface

The degree of crystalline perfection of the deposition carbon nanofiber is dictated by a number of factors including
the chemical nature of the catalyst particle, the composition of the reactant gas, and the reaction temperature. It has
been established that the graphitic nature of carbon nanofibers is controlled to a large degree by the wetting
properties that exist between the metal and deposit, i.e., a strong interaction must exist between the two
components. It has been demonstrated that in order for dissolved carbon to be precipitated in a highly crystalline
form, there must be a registry between the interstitial spacing of the metal atoms at this interface and atomic
spacing of carbon atoms in graphite (Yang and Chen 1985). Surface science studies have established that certain
crystallographic faces of a metal favor precipitation of dissolved carbon in the form of graphite, whereas less ordered
forms will be deposited from other faces (Goodman et al. 1980, Nakamura et al. 1989).
Investigations using controlled-atmosphere electron microscopy techniques have revealed that certain metals can
readily undergo a spreading action along the edge regions of graphite under reducing conditions (Baker 1995). On
the basis of these data it is possible to make predictions with regard to the structural perfection of nanofibers
generated from a given catalyst system with ethylene/hydrogen at a temperature between 500 °C and 650 °C.
Indeed, it is a detailed understanding of the properties exhibited by the two components at the interfacial region that
enables one to catalytically engineer the growth characteristics of these novel materials.

In addition to controlling the degree of crystalline order exhibited by the nanofibers, the orientation of the
crystallographic faces existing at the metal–carbon interface is responsible for imposing the particular geometric
arrangement of the graphite platelets adopted by these structures (Rodriguez et al. 1995). Transmission electron
microscopy studies have demonstrated that the nanofibers can exist in various conformations, some of which are
presented in Fig. 2. In Figs. 2(a) and 2(b) the nanofibers have been generated via a bidirectional mode where the
carbon precipitation process occurs from opposite faces of the catalyst particle, which remains embedded within the
structure during the entire growth period. The type of nanofiber shown in Fig. 2(c), however, is produced by a mode
in which carbon precipitation occurs at the sides of the particle, which is located at the growing tip of the structure.
These three types of structures share a number of common characteristics, including the fact that the width of the
nanofibers is the same as that of the associated catalyst particle. A further feature is that the nanofibers are relatively
straight, indicating that the carbon diffusion characteristics through the particle are symmetrical.
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Figure 2. Transmission electron micrographs of three different types of carbon nanofibers generated by (a, b) a bidirectional mode and (c) a
whisker-like process.

Figures 3 and 4 show the corresponding high-resolution micrographs and three-dimensional schematic renditions,
respectively, of the carbon nanofiber structures presented in Fig. 2. Detailed examination reveals that the graphite
platelets constituting the material shown in Fig. 4(b) are stacked in a direction that is perpendicular to the fiber axis,
adopting the arrangement of a ‘‘deck of cards.’’ This arrangement is to be contrasted with that presented in Fig. 4(c)
where the graphite sheets are aligned parallel to the fiber axis, adopting the structure of a ‘‘multiwalled faceted
nanotube.’’ Inspection of the structure shown in Fig. 4(a) indicates that in this case the graphite platelets are at an
angle to the fiber axis in a so-called ‘‘herring-bone’’ arrangement.
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Figure 3. High-resolution electron micrographs showing the arrangements of the graphite platelets of the respective materials shown in Fig. 2.

Si i t d l d f ll i i
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Figure 4. Schematic representation of metal catalyst particles and (a) the ‘‘herringbone’’, (b) the ‘‘deck of cards’’, and (c) the ‘‘parallel’’ arrangement
of platelets in graphite nanofibers. Marked sections correspond to the respective electron micrographs presented in Fig. 3.

The unusual spiral form of nanofiber, highlighted in Fig. 5, is believed to originate from a perturbation in the
diffusion characteristics of carbon species through the catalyst particle, brought about by the participation of either
sulfur or phosphorus compounds which introduce an element of asymmetry into the system (Motojima et al. 1991,
Owens et al. 1994). Such a condition could arise if the reconstruction of certain faces forced the particle to adopt an
irregular shape during the formation of the nanofiber, or if adsorption of the adatoms occurred at certain faces of the
particle and interfered with the carbon precipitation step, thus creating an anisotropic growth pattern.

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Figure 5. Transmission electron micrograph showing the spiral appearance of carbon nanofibers resulting from the interaction of Fe–Ni with
ethane containing H2S at 815 °C.

Reactivity of Heat-Treated Coals

O.P. Mahajan, P.L. WalkerJr., in Analytical Methods for Coal and Coal Products, Volume II, 1978

9 Carbon Deposition
Recently Kamishita et al. (1977) have studied the effect of carbon deposition (CD), resulting from the cracking of
methane, on a lignite char on subsequent reactivity to air (1 atm) at 375°C. Different amounts of carbon were
deposited at 855°C on raw and acid-washed chars prepared by the heat treatment in N2 of a North Dakota lignite (40
× 100 mesh) at 855 and 1000°C. It was found that the reactivity decreased progressively with increasing amounts of
CD. This was attributed to a decrease in ASA and deactivation of catalytic inorganic impurities due to coating with
carbon. The results indicated that the deposited carbon was much less reactive to air than the lignite char. It was also
found that surface area development in the char as a result of gasification was sharply reduced by prior CD. It was
concluded that in order to maximize surface area development and, hence, char reactivity to oxidizing gases, carbon
deposition from volatiles during the conversion of coal to char should be kept to a minimum.

THE FORMATION OF DEPOSITS IN OIL-FIRED SYSTEMS

Alan Williams BSc, PhD, CEng, FInstE, FRSC, FInstPet, FInstGasE, in Combustion of Liquid Fuel Sprays, 1990

8.4 Carbon Deposits in Diesel Engines

Carbon deposition can form in both automotive engines using a distillate diesel form or in larger engines, such as
marine diesels, which use a fuel containing residium. In the former case deposition occurs on the atomisers and is a
result of the deposition of larger droplets on the atomiser or as the result of fuel dribbling out before atomisation
commences properly (or when it ceases). This can be minimised by better atomiser design, reduction in aromatic
content of the fuel (which seems unlikely) or by the use of an anti-cracking additive. Varnish-like deposits can also
accumulate on the needle used in the hole or direct injectors causing needle sticking or irregular fuel flow.
These problems can be aggravated by the use of residual fuels although the presence of vanadium may assist in
burning out carbon deposits.

Methane synthesis
Martin Seemann, Henrik Thunman, in Substitute Natural Gas from Waste, 2019

Carbon deposition
Carbon deposition occurs in all catalytic transformations of hydrocarbons and can cause catalyst deactivation
(R t Ni l 1997) H th i l d t i t t f hh b f d th
(Rostrup-Nielsen, 1997). Hence the involved costs are massive; a vast amount of research has been performed on the
carbon formation on catalysts. Only some fundamental publications are cited here (Bartholomew, 1982; Bernardo
and Trimm, 1979; Bond, 1997; Rostrup-Nielsen and Sehested, 2001; Trimm, 1977).
There are manifold mechanisms of deactivation; by blockage of the active sites by adsorbed species, encapsulating of
metal crystals by polymeric carbon (1), plugging of the micro- and mesopores (2), and in the worst case destruction
of the catalysts structure by whisker formation (3) (see Fig. 9.3).

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Figure 9.3. Forms of permanent deactivation of catalytic surface by deposited carbon: (A) encapsulating carbon, (B) pore mouth poisoning, (C)
whisker formation.

The relevant reactions, sources, and mechanisms for deposition and removal of carbon on nickel catalysts are
presented in the following sections.

Computational fluid dynamics (CFD) analysis of membrane

reactors: simulation of a palladium-based membrane reactor
in fuel cell micro-cogenerator system
L. Roses, ... G. Manzolini, in Handbook of Membrane Reactors: Fundamental Materials Science, Design and
Optimisation, 2013

14.4.4 Carbon deposition

Carbon deposition deactivates the supported metal catalyst reducing its effectiveness and in extreme cases can even
block the reformer (Twigg, 1996). In steam methane reforming, the most likely mechanisms for carbon formation
are:
Methane decomposition (or methane cracking):

Boudouard reaction:

Carbon monoxide reduction:

Thermodynamically, the higher the H/C ratio in the mix, the lower the possibilities for carbon formation, therefore in
the membrane reactor in discussion, the extraction of H2 could raise a problem from this point of view. Methane
decomposition is likely to be the predominant mechanism for coking, because at the feed inlet, the hydrogen
content is initially nil, and along the reactor in the vicinity of the membrane the lower H2 partial pressure would also
favour this reaction.
Equations [14.44]–[14.46] show the kinetics for Reactions 4–6 which are obtained experimentally (Hou and Hughes,
2001).
[14.44]

[14.45]

[14.46]

Again one could analyse the equilibrium quotient for the reactions in consideration as follows:
[14.47]

[14.48]

[14.49]

Figure 14.11 plots the equilibrium quotient for Reactions 4 and 5 (the situation for Reaction 6 is very similar to the
plot of Reaction 5), for different S/C and a case with high permeance. The figures take the data for the partial
pressures in the vicinity to the membrane (r = 0.030 m), because in this region the occurrence of Reaction 4 is more
critical than in the bulk of the reforming section. For Reaction 5 the equilibrium quotient does not have an evident
preference in the radial direction, but the plot is also taken close to the membrane in order to study the possibility of
blockage over the membrane surface due to carbon deposition.
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14.11. Carbon deposition study for different S/C and permeance through equilibrium quotient analysis. Carbon deposition through (a) CH4
cracking and (b) Boudouard coking.

By means of the equilibrium quotient we can study the affinity of carbon formation in different cases; a quotient
below 1 means that the reaction is thermodynamically driven to convert towards carbon formation. As expected,
methane cracking is almost inevitable in the reactor inlet, and after some hydrogen is produced this effect is quickly
bypassed. The equilibrium quotient for methane cracking, after an initial peak begins to fall due to the extraction of
hydrogen from the reacting mix. With regards to Boudouard coking, the evolution of the quotient is towards lower
values, due to the fact that even though the partial pressure of both CO and CO2 rise, the quotient depends on the
square of CO partial pressure. As expected, in either of the mechanisms studied, low S/C ratios favour coke
formation. As already discussed, a system with very high permeance imposes stronger radial profiles for the species
and in particular H2, leading to higher affinity to carbon formation against the membrane. From the figure we can
see that for the same S/C of 3.0, the equilibrium quotient is closer to the critical value for the case having higher
permeance.
It must be added that carbon deposition cannot be entirely predicted by using equilibrium calculations; in practice,
carbon deposition can occur before reaching the thermodynamic limit (due to poisons, real temperature gradients,
etc.) (Rostrup-Nielsen, 1984; van Beurden, 2004). However, the analysis still provides reasonable guidelines or ‘rules
of thumb’ that allow identifying those conditions which are critical for carbon formation, therefore providing aid for
decision making about reactor design. An aspect of great importance is the selection of the catalyst, for instance,
compared to Nickel-based catalysts, the use of noble metals reduces the likelihood of coking because they do not
dissolve carbon.
From the analysis it is clear to see that some carbon formation is very likely to happen, at least at the reactor inlet by
methane cracking. However, this effect would be bypassed by the adoption of a pre–reforming section which could
be performed outside the membrane reactor using a small amount of catalyst or even at different temperature. The
catalyst of a small pre–reforming section could be replaced periodically. Another solution, being that a small amount
would be required, a noble based catalyst could be used for a pre–reformer, which in some cases could turn out to be
economically advantageous since, besides the higher capital cost, it would avoid more frequent replacement.

GTL Feed by Catalytic Oxidation of Methane in Plate Reactor

Mohamed A. Nakoua, Muftah H. El-Naas, in Proceedings of the 1st Annual Gas Processing Symposium, 2009

3.2 Coke Formation

The deactivation of Ni-based catalyst by carbon deposition is often a problem in POM reaction. There are three
possible mechanisms for carbon formation, purposely, formation via the catalytic methane decomposition
reaction (5), the boudouard reaction (6), and CO and H2 reaction (7), (Yaying, et al. 2001):
(5)

(6)

(7)
However, the results showed that adding promoters Cr, Ba, and La2O3 to nickel-alumina catalyst reduced fast and
heavy coke formation which was also confirmed by (Olsbye, et al. 2002). To achieve long runs, catalyst regeneration is
necessary at a certain time.

Natural Gas Conversion V

Shenglin Liu, ... Weishen Yang, in Studies in Surface Science and Catalysis, 1998

3.1 Comparison of carbon deposition between NiO/γ-Al2O3 and LiNiLaO/γ-Al2O3

The introduction of Li and La improves the ability of carbon-deposition resistance, besides the activity of the nickel
based catalyst[10]. The deposition of surface carbon over the NiO/Al2O3 catalyst during the POM reaction results in
the deactivation of NiO/Al2O3[7,8,12]. It is well known that the acidity of catalyst surface favors carbon-deposition
and the basity of catalyst surface prevents carbon-deposition[13]. Hence, the addition of Li and La oxides is
reasonable to prevent carbon-deposition over catalyst surface[14]. The TG results of the samples after the POM
reaction for 10 h (CH4/O2 = 2; GHSV = 27000 1/kg.h; 1123 K; 1 atm) indicated that the carbon-deposition resistant
ability of LiNiLaO/γ-Al2O3 was much better than that of NiO/γ-Al2O3. During the period of 10 h of POM reaction,
there was almost no carbon deposition over LiNiLaO/y-Al2O3 and the amount of carbon-deposition over
LiNiLaO/Al2O3 was only 0.24% of its net weight, but that over NiO/γ-Al2O3 was about 12% of its net weight. It was
shown that the introduction of Li and La oxides could suppress the carbon-deposition of the nickel based catalyst.
TPO tests were also performed to demonstrate the above results. According to the TPO results (see Fig. 1), the only
gaseous product was CO2 during the TPO tests of NiO/γ-Al2O3 and LiNiLaO/γ-Al2O3 catalysts after POM reaction for
10 h under the same reaction conditions, and no CO and H2O were detected. Two CO2 desorption peaks at 813 K
and 1013 K for NiO/γ- Al2O3 and two at 793 K and 933 K for LiNiLaO/γ-Al2O3 appeared in the profiles, which
indicates there were two different kinds of carbon produced during the POM reaction. The amount of carbon over

NiO/γ-Al2O3 was far more than that over LiNiLaO/γ-Al2O3 and it was more difficult to be depleted the carbon by
oxygen.

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 g g

Figure 1. TPO profiles of catalysts after POM reaction for 10 h (m/e = 44) a: NiO/γ-Al2O3 b: LiNiLaO/γ-Al2O3

Another interesting phenomenon was that no H2O was detected, and it was inferred that the carbon species
produced during the POM reaction was carbon but no other carbon species with hydrogen atom

Natural gas-fired combined cycle (NGCC) systems

A.D. Rao, in Combined Cycle Systems for Near-Zero Emission Power Generation, 2012

Decarbonized syngas generation

Sulphur-resistant reforming catalysts are under development which also resist carbon deposition while operating
under low steam to carbon (contained in the hydrocarbon fuel) ratio in the feed gas. The downstream shift catalysts
also resistant to sulphur poisoning are available but the design and selection of the CO2 separation process suitable
for such applications will have to take into account the presence of sulphur in the syngas (as H2S).
High-temperature membranes which are under development for separation of H2 (Roark et al., 2003) have the
potential for significant improvement in plant performance and possibly cost for separation of the CO2 from the
syngas without having to cool it down to near ambient temperatures. Reactors utilizing such high-temperature
membranes and containing reforming and shift catalysts to combine the function of the reformer, shift reactors and
CO2 separation have the potential to make further substantial improvements in plant thermal performance and cost.
High-temperature ion transport membranes, which are also under development for air separation (Dyer et al., 2000),
should provide some improvement in plant thermal performance and possibly cost for the partial oxidation option.
Another area for improvement in plant performance and cost lies in the synergistic integration of the reforming
process with the gas turbine. Chemical recuperation consisting of supplying at least a fraction of the endothermic
heat demand of a steam-methane reformer by the gas turbine exhaust has the potential to improve plant thermal
performance. Extraction of the air required by the autothermal reformer from the gas turbine compressor discharge

followed by humidification after it is cooled and further compressed (Rao, 2003) is another example of synergistic
integration between these two major components of the system.
The process of cooling the shifted syngas before CO2 separation and then preheating the decarbonized (humidified)
syngas prior to injection into the gas turbine combustor decreases the efficiency of the overall system. A CO2
removal process with an operating temperature that is close to the water gas shift reaction operating temperature
(while contrained only by the maximum allowable fuel gas temperature for the gas turbine) can eliminate the cooling
and heating of the syngas and thus improve the thermal efficiency as well as the economic performance of the power
plant. Furthermore, the moisture in syngas is preserved upstream of the gas turbine, thus eliminating the heat load
and cost associated with a humidification system. Sorbent-based processes for CO2 separation suitable for such
applications are under development, for example, magnesium hydroxide-based sorbent (Siriwardane and Stevens,
2009) operating in the range of 200–400 °C and requiring a regeneration temperature of around 375 °C. Heat in the
form of superheated steam generated in the gas turbine exhaust could potentially be utilized for this regeneration
process.
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