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R&D Opportunities

for Development of
Natural Gas Conversion
Technologies
for Co-Production of Hydrogen and
Value-Added Solid Carbon Products

November 2017

Argonne is a multi-program national laboratory


operated for the U.S. Department of Energy
Office of Science by UChicago Argonne, LLC,
under contract DE-AC02-06CH11357

ANL-17/11

PNNL is a multi-program national laboratory


Operated for the U.S. Department of Energy
Office of Science by Battelle, under contract
DE-AC05-76RL01830.

PNNL-26726
An Overview of Natural Gas Conversion
Technologies for Co-Production of
Hydrogen and Value-Added Solid Carbon
Products

This report was prepared in response, in part, to the U.S. Department of Energy Fuel Cell
Technologies Office’s fiscal year 2017 Congressional direction1 to support research on
carbon dioxide-free production of hydrogen using new chemical synthesis methods that
break apart natural gas to solid carbon and hydrogen.

R Dagle2
V Dagle2
M Bearden2
J Holladay2
T Krause3
S Ahmed3

November 2017

Operated for the U.S. Department of Energy Office of


Science by UChicago Argonne, LLC, under contract
DE-AC02-06CH11357

Operated for the U.S. Department of Energy Office of


Science by Battelle, under contract DE-AC05-76RL01830.

1
https://www.congress.gov/114/crpt/srpt236/CRPT-114srpt236.pdf, p. 65
2
Pacific Northwest National Laboratory
3
Argonne National Laboratory
Executive Summary

This report was prepared, in part, in response to the U.S. Department of Energy Fuel Cell Technologies
Office fiscal year 2017 Congressional direction to support research on carbon dioxide-free production of
hydrogen using new chemical processes that use natural gas to produce solid carbon and hydrogen. The
purpose of this report is to provide an overview of the status in the field and help guide activities,
including additional research and development (R&D) areas required for technical and commercial
viability.

The United States produces approximately 10 million metric tons of hydrogen annually and more than
95% of the hydrogen is produced by steam-methane reforming (SMR) of natural gas. SMR is attractive
because of its high hydrogen yield, but it also converts the carbon to carbon dioxide (CO2). Methane
pyrolysis, the non-oxidative thermal decomposition of methane to carbon and hydrogen, is an alternative
to SMR and produces CO2-free hydrogen. The produced carbon can be sold as a co-product, thus
providing an economic credit that reduces the delivered net cost of hydrogen. The combination of
producing hydrogen with potentially valuable carbon byproducts has market value because it allows
greater flexibility to match the market prices of hydrogen and carbon. That is, the higher value product
can subsidize the other in pricing decisions.

Thermal decomposition of natural gas is currently used in the carbon black industry to produce carbon
black for use in tires and electrical equipment, but natural gas as the feedstock has been largely replaced
by heavy oil fractions from crude oil processing. The high reaction temperature (>1000oC) required for
methane conversion contributes greatly to process inefficiencies, limits the choice of materials of
construction, adversely impacts catalyst life, and exacerbates heat losses. Catalytic thermal decomposition
has been extensively researched at the laboratory scale with the primary purpose of decreasing the
temperature required for conversion. However, steam pressure buildup and loss of catalytic active sites
due to carbon fouling are problematic. Non-thermal plasma processes for producing carbon and hydrogen
have been reported as alternatives, but they require a significant amount of electric power. Molten-metal
technology has been reported to have a major benefit from the relative ease of solid carbon separation
from the molten metal due to density differences; however, a high conversion temperature is still
required. Solar thermochemical processes leverage the use of inexpensive solar heat, but non-catalytic
processes require high temperature (e.g., 1600°C), and the high conversion temperature requires the use
of expensive construction materials. Catalytic processes drive down operating temperature requirements,
but solid carbon handling is still an issue.

Solid carbon separation and high energetic requirements (e.g., high temperature or electrical
requirements) are key challenges for methane pyrolysis. Additionally, while hydrogen production is
relatively easy with the high effective temperatures in pyrolysis processes, and cleanup/purification is
manageable with pressure-swing adsorption, the steps of hydrogen compression and delivery can
significantly increase cost. High-value byproducts, including different solid carbon products produced
through pyrolysis, can offset this cost. Examples of existing high-value carbon markets are listed below.
 Graphite is a high-value product used in lithium-ion batteries.
 Carbon fiber is a premium product used in carbon-reinforced composite materials.
 Nanotube carbons are high-value products used in polymers, plastics, and batteries.
 Needle coke is used in graphite electrodes for electric arc steel furnaces.

Suitable technologies optimized to produce both hydrogen and valuable carbon byproducts must be
developed, as no known commercial process produces both carbon and hydrogen as commercial products.

iii
Commercial processes for producing carbon black typically burn the hydrogen to generate process heat
with a portion of the heat used for the reaction process and remainder used at the plant or sold to nearby
facilities. Commercial processes also exist for producing fuel cell-quality hydrogen, but carbon is not
recovered. Instead, carbon is burned to regenerate the catalyst and to provide process heat.

Techno-economic analysis performed in this study suggests that the production and sale of solid carbon
byproducts can significantly reduce the hydrogen net cost. For example, based on ASPEN modeling of a
small-scale plasma system the cost of hydrogen was estimated at $7.0/kg for a natural gas price of
$5/MMBtu without carbon credit, and decreased to $2.5/kg when selling carbon black at $1.35/kg. For
comparison the cost of hydrogen produced by conventional SMR is < $2.0/kg at comparable natural gas
pricing. Nevertheless, this analysis demonstrates the potential for significant reduction in hydrogen cost
in emerging technologies with the sale of valuable carbon byproducts— yet the carbon selling price is a
critical factor and needs to be high in order for such technologies to compete today with the incumbent
SMR technology. Further development of natural gas pyrolysis methods that yield high-value forms of
carbon, such as carbon fiber or carbon nanotube is critical for successful commercial implementation.

Key attributes for methane decomposition are that the gaseous product stream contains a very high
concentration of hydrogen, the relatively low heat of reaction, and production of a solid carbon that can
be sequestered or sold as a commodity byproduct. Table ES.1 highlights different types of potential
valuable carbon products, their applications in industry, and market pricing, size, and relevance. Potential
carbon products are varied and include carbon black, carbon nanotubes, carbon nanofibers, carbon fibers,
graphene, and needle coke. Carbon product pricing can vary tremendously and depends on product
characteristics and purity. Carbon black is the oldest and most mature market for carbon. In Section 4.0,
we provide additional details for these carbon markets, including both current and potential new market
opportunities. It should be noted that solid carbon as a byproduct can reduce the cost of the methane
decomposition reaction only if sufficiently large markets for the carbon products are found. Some of the
carbon markets shown in Table ES.1, with the possible exception of carbon black and needle coke, would
be saturated before a fraction of the overall hydrogen market demand is met.

In this report, we highlight the relevant technologies reported in the literature—primarily thermochemical
and plasma conversion processes—and recent research progress and commercial activities. Longstanding
technical challenges include the high energetic requirements (e.g., high temperatures and/or electricity
requirements) necessary for methane activation and, for some catalytic processes, the separation of solid
carbon product from the spent catalyst. We assess current and new carbon product markets that could be
served given technological advances, and we discuss technical barriers and potential areas of research to
address these needs. We provide preliminary economic analysis for these processes and compare them to
conventional (e.g., SMR) processes for hydrogen production. The overarching conclusion of this study is
that the cost of pyrolytically produced CO2-free hydrogen can be potentially reduced to levels < $2/kg
target with the co-production and sale of sufficiently high-value carbon products. Technological advances
are required to understand the reaction conditions, design reactor systems that can achieve high yields of
the selected carbon products, segregate or separate the high-value carbon products, and optimize the
production process for both hydrogen and carbon.

Additionally, the report identifies key areas for further R&D in the CH4 pyrolysis technical space
including:

 Improved fundamental understanding of the conditions at which the different grades of carbon
will be formed during the decomposition process, since production of high-value carbon
byproduct is desirable to help to offset the cost of hydrogen production.

iv
 Innovation/ breakthroughs in technology to overcome the thermodynamic limitations that restrict
the high yields of H2 and carbon under high-pressure and low-temperature operating conditions
which would allow dramatic reductions in the cost of the products.

 Further catalyst development. Despite the availability of well-established catalysts for natural gas
reforming and pyrolysis, further catalyst material development is needed to better address
ongoing challenges associated with extensive catalyst recycling (i.e., carbon deposition/carbon
removal). Catalyst mechanical stability remains an issue because the process of carbon deposition
on catalysts surfaces can lead to catalyst detachment from the support.

 Innovation to resolve fundamental issues associated with solid carbon separation and process
challenges associated with solid carbon management.

Suitable technologies optimized for producing both H2 and valuable carbon byproduct must be developed.
Solid carbon as a byproduct could reduce costs only if sufficiently large markets for the carbon products
are found. One alternative to the production of solid carbon is the production of hydrocarbons such as
BTX that have large global market demand of ~100 million tons/yr. Challenges in this area include low
conversion levels and catalyst stability, which are key technological barriers to commercial
implementation.

Table ES.1. Market Analysis for Potential Carbon Products (K = thousand, M = million,
MT = metric ton)
Types of Expected Price for Size of the Market Corresponding Hydrogen
Type of Carbon Applications Carbon (current/ projected) Production(a)
Carbon black [1] Tires, printing inks, $0.4–2+ /kg depending U.S. market U.S. market
[2] [3] high-performance on product requirements  ~ 2M MT (2017)  0.67M MT
coatings and plastics
Global market Global market
 12M MT (2014)  4M MT (2014)
 16.4M MT (2022)  5.4M MT (2022)
Graphite [4] Lithium-ion batteries $10+/kg Global market Global market
 80K MT (2015)  27K MT (2015)
 250K MT (2020)  83K MT (2020)
Carbon fiber [5] Aerospace, $25–113/kg depending Global market Global market
[6] [7] automobiles, sports on product requirements  70K MT (2016)  23.3K MT (2016)
and leisure,  100K MT (2020)  33.3K MT (2020)
construction, wind
turbines, carbon-
reinforced composite
materials, and
textiles
Carbon nanotubes Polymers, plastics, $0.10–600.00 per gram Global market Global market
[8] [9] electronics, lithium- depending on application  5K MT (2014)  1.7K MT (2014)
ion batteries requirements  20K MT (2022)  6.7K MT (2022)
Needle coke [10] Graphite electrodes ~$1.5/kg Global market Global market
for electric arc steel  ~1.5M MT (2014)  ~0.50M MT (2014)
furnaces
(a) Based on stoichiometric ratio of carbon to hydrogen present in methane. Does not take into account process efficiency or use
of hydrogen to provide process heat or loss of hydrogen during hydrogen recovery.

v
Acknowledgments

The authors thank the U.S. Department of Energy Fuel Cell Technologies Office within the Office of
Energy Efficiency & Renewable Energy for funding the authoring of this report. We also thank the staff
from that office for technical assistance, including Maxim Lyubovsky, Eric Miller, Richard Farmer, and
Sunita Satyapal. Thanks also to Cary Counts and Susan Ennor from Pacific Northwest National
Laboratory for their technical editing support.

This report was peer reviewed by Professor John Hu from West Virginia University, Drs. Christopher
Matranga and Peter Balash from the U.S. Department of Energy’s National Energy Technology
Laboratory, Dr. Marc Von Keitz from the U.S. Department of Energy’s Advanced Research Projects
Agency-Energy, as well as Joe Cresko and Rudy Kashar from the U.S. Department of Energy’s Advanced
Manufacturing Office.

vii
Acronyms and Abbreviations

AC alternating current
ANL Argonne National Laboratory
ASTM American Society for Testing and Materials
BTU British thermal unit
BTX benzene, toluene, and xylene
CAC CO2 Avoidance Cost
CCS carbon capture and storage
CH4 methane
CNT carbon nanotube
CO carbon monoxide
CO2 carbon dioxide
DC direct current
DOE U.S. Department of Energy
FBR fluidized bed reactor
FCTO Fuel Cell Technology Office
GREET Greenhouse Gases, Regulated Emissions, and Energy Use in Transportation
(Model)
IEA International Energy Agency
LCOH levelized cost of hydrogen production
LHV lower heating value
mcf million cubic feet
mmBTU a million BTUs
MT metric tons
MWCNT multi-walled carbon nanotube
3
Nm /hr normal cubic meter per hour
PAN polyacrylontitrile
PBR packed-bed reactor
PEP Process Economics Program
PSA pressure-swing adsorption
R&D research and development
RF radio frequency
SLPM standard liter per minute
SMR steam-methane reforming
SWCNT single-walled carbon nanotube
tcf trillion cubic feet
WGS water-gas shift

ix
Contents

Executive Summary .......................................................................................................................... iii


Acknowledgments.............................................................................................................................vii
Acronyms and Abbreviations ............................................................................................................ix
1.0 Introduction ............................................................................................................................. 1.1
1.1 Steam-Methane Reforming ............................................................................................. 1.1
1.2 Steam-Methane Reforming with Carbon Capture ........................................................... 1.2
1.3 Methane Pyrolysis ........................................................................................................... 1.4
1.4 Report Objectives ............................................................................................................ 1.5
2.0 Engineering Review ................................................................................................................ 2.1
2.1 Reactants, Products, and Energy ..................................................................................... 2.1
2.2 Thermal (Non-Catalytic) Reactions ................................................................................ 2.1
2.3 Catalytic Reactions.......................................................................................................... 2.2
2.3.1 Catalytic Reactors Types ...................................................................................... 2.2
2.3.2 Catalysts ............................................................................................................... 2.5
2.3.3 Catalyst Regeneration .......................................................................................... 2.7
2.4 Plasma Reactions ............................................................................................................ 2.7
2.5 Separations Required....................................................................................................... 2.9
3.0 Process Technologies .............................................................................................................. 3.1
3.1 Thermal Catalytic Processes ........................................................................................... 3.2
3.2 Concentrated Solar Power ............................................................................................... 3.3
3.3 Plasma Processes ............................................................................................................. 3.3
3.4 Chemical Processes for Decomposing Methane ............................................................. 3.5
4.0 Market  Current and New Opportunities ............................................................................... 4.1
4.1 Current Markets .............................................................................................................. 4.1
4.1.1 Natural Gas........................................................................................................... 4.1
4.1.2 Hydrogen .............................................................................................................. 4.3
4.1.3 Carbon .................................................................................................................. 4.5
4.2 New Market Opportunities for Methane Conversion to Carbon and Hydrogen ............. 4.6
4.2.1 Graphite/Graphene ............................................................................................... 4.7
4.2.2 Carbon Fibers ....................................................................................................... 4.8
4.2.3 Carbon Nanotubes .............................................................................................. 4.10
4.2.4 Needle Coke ....................................................................................................... 4.11
4.2.5 Aromatics from Natural Gas .............................................................................. 4.12
4.3 Techno-Economic Assessment ..................................................................................... 4.13
5.0 Technology Barriers to Commercial Implementation and R&D Opportunities ...................... 5.1
6.0 Conclusions ............................................................................................................................. 6.1
7.0 References ............................................................................................................................... 7.1

xi
Figures

1.1 LCOHs for the Six Cases Taken from Figure 8 in Reference [14] .................................................... 1.2
2.1 Conceptual Representation of Conversion and Yields as a Function of Reactor Conditions.
“Carbon” represents particles of soot and graphite. ........................................................................... 2.2
2.2 Equilibrium Yields of Methane and Products as a Function of Temperature at P = 1 Atm
during Methane Pyrolysis .................................................................................................................. 2.3
2.3 Effect of Pressure and Temperature on the Equilibrium Yields of Methane and Products
during Methane Pyrolysis .................................................................................................................. 2.4
2.4 Simplified Rotary Bed Reactor Process Flow Diagram..................................................................... 2.5
2.5 Summary of Published Data on Catalysts, Temperature, and Carbon Products from Methane
Decomposition ................................................................................................................................... 2.5
3.1 Direct Current Spark Discharge Plasma Experiments Produced Hydrogen and Carbon [82] ........... 3.4
4.1 Location and Projected Reserves for Major U.S. Shale Gas Basins in the United States [92] .......... 4.2
4.2 Historical and Projected Price of Natural Gas from 1990 through 2040 [91] ................................... 4.2
4.3 Total U.S. Natural Gas Production and Consumption from 1990 through 2040 [91] ....................... 4.3
4.4 Historic and Projected Growth in the Production of Natural Gas from Shale Basins and Tight
Oil between 1995 and 2040 [91]........................................................................................................ 4.3
4.5 U.S. Carbon Black Market Volume by Application from 2012 Projected through 2022.
Volume is in kilotons [2]. (Reproduced with permission from Grand View Research.) ................... 4.6
4.6 Comparison of the Structure of (A) Graphite, (B) Graphene, and (C) a Single-Walled Carbon
Nanotube [108] .................................................................................................................................. 4.7
4.7 Global CNT Market Estimates and Forecast by Application from 2012 through 2022.
Volume is in tons [9]. (Reproduced with permission from Grand View Research.) ....................... 4.11
4.8 Break-Even Price of Carbon Products vs. the Cost of Methane as a Percentage of the
Revenue from the Sale of Hydrogen and Carbon Products, as Functions of the Price of
Methane. Price of H2 = $4/kg. ......................................................................................................... 4.13
4.9 Sensitivity of Carbon Black Selling Price on Net Hydrogen Cost for the Small-Scale Plasma
Case Study 4.14

Tables

1.1 Summary of Data for LCOH, CO2 Emissions, and CO2 Avoidance Cost [14].................................. 1.3
3.1 Summary of Methane Decomposition Processes ............................................................................... 3.1
3.2 Hydrogen from Thermal Plasma Decomposition of Methane [61] .................................................. 3.4
4.1 Relative Hydrogen Production on Basis of Stoichiometry and Co-Product Values for
Carbon, Benzene, and Ethylene Product Routes.............................................................................. 4.12
4.2. Hydrogen Cost, Requirements, and Byproduct Production Summary for the Techno-
Economic Cases Analyzed in this Study ......................................................................................... 4.15
5.1 Summary of Carbon Products and Natural Gas Conversion Technology Status, Major
Barriers to Commercial Implementation, and R&D Needs to Overcome Barriers............................ 5.1

xiii
1.0 Introduction
Use of abundant natural gas and its efficient conversion to fuels and chemicals has been an important area
of research. In addition to energy independence, development of new technologies that produce no
emissions and carbon dioxide (CO2)-free energy and fuels has also received significant interest in recent
decades [11]. Hydrogen (H2) in particular has received substantial attention in part because it can be
produced from diverse domestic resources, used in multiple applications across sectors, and its use in fuel
cell applications is completely pollution-free. Furthermore, because fuel cells convert H2 and oxygen
directly to electricity more efficiently than internal combustion engines, they can reduce systemic energy
losses. The ability to produce H2 cost effectively will be a major determining factor for future
implementation of this energy resource [12]. Natural gas is an abundant resource in the United States, and
coupled with its available and growing infrastructure, it offers a pathway to building H2 infrastructure.
Today, 95% of the H2 produced in the United States is made by natural gas reforming in large central
plants. This is an important technology pathway for near-term H2 production [13]. This report will first
cover the conventional process of SMR, followed by an assessment of natural gas to solid carbon and H2
processes.

1.1 Steam-Methane Reforming


SMR is a mature production process in which high-temperature steam (700°C–1000°C) is used to
produce H2 from a methane (CH4) source, such as natural gas. In SMR, CH4 reacts with steam under
3–25 bar pressure in the presence of a catalyst to produce H2, carbon monoxide (CO), and a relatively
small amount of CO2. Steam reforming is endothermic—that is, heat must be supplied to the process
for the reaction to proceed (Equation SMR (1.1)). Subsequently, in what is called the water-gas shift
(WGS) reaction, the CO and steam are reacted using a catalyst to produce CO2 and more H2 (Equation
WGS (1.2)). Combining the SMR and WGS reactions results in primary products H2 and CO2 (Equation
Net Reaction (1.3)) [13]. In a final process step called pressure-swing adsorption (PSA), CO2 and other
impurities are removed from the gas stream, leaving essentially pure H2. Steam reforming can also be
used to produce H2 from other fuels, such as ethanol, propane, or even gasoline.

CH4 + H2O = CO + 3H2 Ho = 206 kJ/mol SMR (1.1)

CO + H2O = CO2 + H2 Ho = -41 kJ/mol WGS (1.2)

Combining Equations SMR (1.1) and WGS (1.2), the net reaction is:

CH4 + 2H2O = CO2 + 4H2 Ho = 165 kJ/mol Net Reaction (1.3)

Currently, SMR is the technology with the greatest advantage in terms of the lowest cost and highest
energy efficiency and is the preferred choice of industry today. SMR is used industrially to produce ~95%
of the H2 consumed in the United States [11]. However, the process generates significant quantities of
CO2. The reaction stoichiometry (Equation Net Reaction (1.3)) suggests 5.5 kgCO2/kgH2 is produced, but
the quantity is much higher in practice. Being a strongly endothermic process, it requires additional
energy that results in the release of additional CO2. Depending on the energy sources used and efficiency
of the process, SMR generates 9–14 kgCO2/kgH2. Based on low-cost shale gas, the cost of H2 production
from SMR can be less than $2/kg. If CO2 capture is considered as part of a SMR technology option, this
presents additional cost.

1.1
1.2 Steam-Methane Reforming with Carbon Capture
To understand the cost of deploying a CO2 capture system in a H2 production plant, the International
Energy Agency (IEA) Greenhouse Gas R&D Program commissioned Amec Foster Wheeler to undertake
a study, which resulted in a report entitled, Techno-Economic Evaluation of Hydrogen Production with
CO2 Capture [14]. The primary purpose of the study was to evaluate the performance and cost of a
greenfield modern SMR plant producing 100,000 Nm3/h of H2 from natural gas as feedstock/fuel
operating in merchant plant mode. (Note that 100,000 Nm3/h of H2 corresponds to 216 tons per day
production; for comparison, the Air Products’ Port Arthur II plant has capacity of 265 tons per day).
The IEA study focused on the economic evaluation of five different options to capture CO2 from SMR,
and these include the following cases:
 Base Case: Modern SMR Plant with feedstock pre-treatment, pre-reforming, high-temperature WGS,
and PSA
 Case 1A: SMR with capture of CO2 from the shifted syngas using methyl diethanolamine
 Case 1B: SMR with burners firing H2-rich fuel and capture of CO2 from the shifted syngas using
methyl diethanolamine
 Case 2A: SMR with capture of CO2 from the PSA tail gas using methyl diethanolamine
 Case 2B: SMR with capture of CO2 from the PSA tail gas using cryogenic and membrane separation
 Case 3: SMR with capture of CO2 from the flue gas using monoethanolamine.

For this study, the price of natural gas was assumed to be 6€/GJ (LHV) (~ $7/MMBtu) and the price of
electricity 80€/MWh (~$0.09/kWh; 1€ = 1.1$ is assumed for cost conversion throughout the report).
The levelized cost of H2 production (LCOH) was calculated for these six cases, and results are shown in
Figure 1.1. Some export of electricity takes place in the base case (from excess steam fed to a steam
turbine), thus lowering the LCOH, but this accounts for only a small fraction of the overall H2 cost.
The cost of natural gas is the major fraction in the LCOH.

Figure 1.1. LCOHs for the Six Cases Taken from Figure 8 in Reference [14]

1.2
Costs of CO2 avoidance (CAC) were calculated by comparing the CO2 emissions per Nm3 H2 and the
LCOH of plants with capture and a reference plant without capture:

CO2 Avoidance Cost (CAC) = (LCOHCCS – LCOHRef )/ (CO2Emissions Ref – CO2Emissions CCS) (1.4)

where CAC is expressed in € per tonne (metric ton) of CO2 (or in $/tonne), LCOH is expressed in € per
Nm3/h H2 (or in $/kg), and CO2 emission is expressed in tonnes of CO2 per Nm3/h H2 (or in tonnes CO2
per kg H2). The notation CCS stands for carbon capture and storage.

Table 1.1 summarizes data for the LCOH, CO2 emissions, and CAC. It can be seen that it would require a
cost of €76.8/tonne of CO2 emissions to make the higher capture rate option (Case 3) more attractive than
the base case.

Table 1.1. Summary of Data for LCOH, CO2 Emissions, and CO2 Avoidance Cost [14]
CO2 CO2
Case Emissions Avoided LCOH Cost of Avoided CO2
3
kg_CO2/ % €c/Nm $/kg €/tonne $/tonne
kg H2
Base Case 9.0 11.4 1.39
Case 1A 4.1 54.2 13.5 1.65 47.1 51.8
Case 1B 3.2 63.9 14.6 1.78 62 68.2
Case 2A 4.3 52.2 14.2 1.74 66.3 72.9
Case 2B 4.2 53.4 14 1.71 59.5 65.5
Case 3 1.0 89.0 16.5 2.02 69.8 76.8

H2 production cost when coupling SMR with CO2 capture can be compared to renewable or pyrolytic H2
production processes which do not produce CO2. Equation (1.4), which defines the CAC for the cases
with CCS relative to the base case SMR, can be used to compare the cost of H2 produced from renewable
sources or through NG decomposition (with no CO2 emissions) to the cost of H2 from SMR. The CAC is
assumed to be $80/tonne (as for Case 3, where 90% of CO2 emissions is avoided), and CO2 emissions
from the average SMR plant are assumed to be 10 kg CO2/kg H2. Note that the base case in this study
uses 9 kg/kg, but this is apparently a more efficient plant model than most commercial SMR plants. By
comparison, SMR GREET Model suggests greenhouse gas emissions to be 11 kg/kg. Substituting these
values in Equation (1.4) results in the following price difference [14]:

H2 renew - H2 SMR = 0.8 $/kg (1.5)

A $1.4/kg hydrogen cost in the base case SMR suggests that the cost of pyrolytic H2 should be below
$2.2/kg to compete with the SMR-CCS strategy. Sales of carbon co-produced with pyrolytic H2 can help
offset the prosecution price and reach the CO2 free hydrogen price point that is competitive with the
SMR-CCS.

1.3
1.3 Methane Pyrolysis
The prevalence of fracking has revolutionized the U.S. natural gas industry, making it economically
competitive to recover large reserves of natural gas that were previously considered uneconomical to
recover and leading to an unprecedented increase in natural gas production coupled with a drop in the
price of natural gas to historical lows. As such, there is considerable interest in developing new process
technologies that use natural gas for producing fuels and chemicals, including H2. One potential
technology is the thermal decomposition of natural gas. Methane can be decomposed into carbon (C) and
H2 according to the following endothermic reaction:

CH4 → C(s) + 2H2 Ho = 74.8 kJ/mol (1.6)

The reaction stoichiometry suggests that the molar ratio of H2 and carbon to the feedstock CH4 as 2 and 1,
respectively. Actual processes will yield less because of the production of byproducts (e.g., olefins,
aromatics) and the need to oxidize part of the feedstock to generate the heat for the process. Muradov
estimates the H2/CH4 molar ratio from a process to be 1.7 [15]. Assuming the carbon-containing products
will be sequestered or sold as carbon black, the efficiency of producing H2 via decomposition using a
molar yield of 1.7 translates to (1.7 × LHV of H2/LHV of CH4) = 51%.

For the pyrolysis reaction above, each mol of CH4 can yield a mass-balanced maximum of 12 g of carbon
and 4 g of H2. This 3:1 mass ratio (2:1 molar ratio) is skewed in practice by the formation of byproducts
and the process energy required. The heat of formation of CH4 is 74.8 kJ, i.e., the energy required to
decompose a mol of CH4. If the energy for the decomposition is derived by combustion of CH4, then that
requires another 0.093 mol of CH4. Thus, the mass and energy balanced maximum yields for H2 and
carbon are reduced to 10.98 g of carbon and 3.66 g of H2 per mol of CH4. Stated in terms of energy, the
minimum energy that will be consumed for the production of the H2 and carbon via CH4 decomposition
are 240 kJ/gH2 (66.7 kWh/kgH2, 5.96 kWh/m3H2) and 73 kJ/gcarbon (20.3 kWh/kgcarbon), respectively. The
yield of practical systems will necessarily require more energy as a result of inefficiencies that include
incomplete CH4 conversion, loss of products (H2, C), formation of byproducts, heat transfer limitations,
energy recovery, heat loss, etc.

The pyrolysis process does not produce CO or CO2 as byproducts, and thus the need for WGS or CO2
removal is eliminated [11]. Without inclusion of the WGS and preferential oxidation of CO reactions,
processing for CH4 decomposition is greatly simplified relative to steam reforming [16]. Thus, the energy
requirement for CH4 catalytic cracking is nearly half of that required for steam reforming on a per mole
CH4 decomposed basis [16]. One study reports that per mol of H2 produced, the energy requirement is
37.4 kJ/mol for CH4 decomposition, compared to 63.3 kJ/mol for steam reforming [16]. However, about
half of the amount of H2 per mol CH4 is produced.

CH4 decomposition is an endothermic reaction, and because of the strong carbon-to-hydrogen (C-H)
bonds, non-catalytic thermal cracking of CH4 requires a temperature >1200oC to obtain a reasonable
yield. By using a catalyst, the temperature can be significantly reduced [11]. Thermodynamically,
breaking all four C-H bonds of CH4, such as with steam reforming CH4, into synthesis gas or CH4
decomposition into C and H, is much easier than breaking only one or two of the C-H bonds, under either
oxidative or non-oxidative conditions [12]. Direct conversion of CH4 with the assistance of oxidants is
thermodynamically more favorable than under non-oxidation conditions, and thus has received much
more attention [12]. However, there are potential benefits for non-oxidative conversion. At high
temperatures of between 1300 and 1600°C, CH4 and other hydrocarbons present in natural gas decompose
to yield H2 and solid carbon in an inert atmosphere. Compared to SMR, the reaction is less endothermic
and produces no CO2 emissions if the produced carbon is not burned in subsequent processes.
Furthermore, there is the potential for a considerable reduction in capital and operating costs compared to

1.4
SMR. This is because the gas stream exiting the reactor in the thermal decomposition process has a
considerably higher H2 concentration and does not contain CO2 or CO, compared to the composition of
the gas stream existing the steam reformer. Therefore, the gas stream should require considerably less
downstream processing to produce commercial-grade H2 compared to SMR. In addition, sale of the
carbon product (i.e., carbon black, carbon fibers, etc.) can be used to offset the cost of the H2.

Commercially, the thermal decomposition of natural gas has been employed in the carbon black industry
since the 1920s to produce selected grades of carbon for use in manufacturing tires and electrical
components [17]. The H2 could, in theory, be recovered and sold as merchant H2, but in practice, the
carbon black industry uses a portion of the H2 to provide the required process heat, and the remainder of
the H2 is used to generate process heat for the facility or nearby facilities adjacent to the fence line. The
ability to offset the cost of producing H2 by the sale of carbon is a promising scenario. To the best of our
knowledge, there is no commercial process based on producing both carbon and H2 for the carbon black
and H2 markets, respectively.

A number of excellent recent articles provide reviews of CH4 decomposition. These include discussion of
catalysts and reaction mechanisms and kinetics [11, 18, 19], technologies that use renewable energy
options for producing H2 by thermal decomposition [20], and engineering design considerations [19]. For
example, an in-depth review by Amin et al. [16] discusses the catalytic cracking of CH4 for H2 production
and reports on the thermodynamics, catalysts and supports used, catalyst deactivation and regeneration,
the growth of carbon product particles, and the cracking reaction mechanism with inclusion of kinetic
models. Additionally, the cost of H2 production is reported for a number of different pathways. Abbas and
Wan Daud [11] also review decomposition processes and discuss insights about heating sources, reactor
types, catalysts employed, catalyst regeneration, and the quality of the carbon produced. The effects of
temperature and flow rate on the product distribution, the energy sources, the reactors and their operating
condition, and catalysts are also reported.

1.4 Report Objectives


Given the opportunity to develop the thermal decomposition of natural gas that can take advantage of
low-cost natural gas for producing H2 and carbon for commercial sale, the purposes of this report are to:
1. Evaluate the thermodynamics and processing requirement and discuss the different thermal and non-
thermal (e.g., plasma) approaches to CH4 pyrolysis.
2. Identify and describe specific technologies—both commercial and those under research and
development (R&D)—for decomposition of natural gas to produce carbon and/or H2.
3. Identify specific carbon market opportunities and synergies for producing both carbon and H2 for
merchant sale.
4. Provide a techno-economic analysis that provides the cost of producing H2 and quantifies the energy
demand to provide the basis for comparing it to alternative technologies for producing H2, as well as
to identify where R&D is needed to lower cost and increase energy efficiency.
5. Identify barriers to market adaption and potential R&D opportunities for producing both valuable
solid carbon product and H2.

1.5
2.0 Engineering Review
In this section we report in broad terms the thermodynamic and processing requirements for each of the
classes of process technologies (e.g., thermal, catalytic, plasma). In Section 3.0 we report on specific
processes that have been reported in the literature—both commercial and those under R&D—that use
different approaches to tackle the issues described above.

2.1 Reactants, Products, and Energy


Several approaches to supplying heat for the highly endothermic CH4 pyrolysis reaction have been
proposed. These include direct heating of the reaction zone, externally heated catalyst particles used as
the heat carrier, similar to fluidized bed reactors (FBRs), and addition of a small amount of oxygen to
generate the necessary heat, which is an autothermal pyrolysis type process [21]. Fluidized bed and fixed
bed reactors are the most commonly used reactors for CH4 decomposition.

The endothermic heat of reaction and sensible heat requirements have also led to some processes in which
air or oxygen are co-injected to generate the heat and thus lead to other byproducts that require
separations downstream. Depending on the source of heat for the reaction, the process may be termed
autothermal—in which the heat of reaction is generated by oxidation of the CH4 or other hydrocarbons
present in the natural gas, or allothermal—in which the energy is supplied from an external source and
transferred via a heated surface or transmitted with waves, or electric power. These reactions may be
conducted with or without catalysts; the catalysts offer the benefits of faster kinetics at lower temperature
and may improve the selectivity of the product streams.

Because the main products of CH4 decomposition are solid carbon and H2 gas, the problem with FBRs is
carbon deposition on the catalyst particles [11]. As the reaction proceeds, carbon will deposit on the
catalyst surface, blocking the pores and the interparticle spaces. Because of this pore-blocking process,
the pressure drop through the bed will rise as the gas flow is impeded [11]. Thus, the deposited carbon
must be removed periodically. Muradov studied different types of reactors and concluded that FBRs were
the most promising type of reactor for large-scale operations because it provides a constant flow of solids
through the reaction zone, making it suitable for continuous addition and withdrawal of catalyst from the
reactor and catalyst regeneration [11, 22].

There are many reports about the use of an electric furnace as a heating source for the high energetics
needed to drive CH4 decomposition. Other reports focus on the use of plasma, concentrated solar energy,
and a molten-metal bath as alternative means of supplying the required energy. The ensuing sections
provide brief overview descriptions of various means of providing the reactor energetics and the various
reactor technologies as reported in the open and closed literature.

2.2 Thermal (Non-Catalytic) Reactions


Thermal cracking of CH4 removes and separates carbon in a single step [23]. A major drawback of this
technique is that non-catalytic cracking is very slow for practical applications below 1000C, while
catalytic cracking of CH4 can be conducted at temperatures as low as 500C [16]. The function of the
catalyst is to reduce the activation energy required for CH4 decomposition, thereby leading to lower
operating temperatures. In this section we focus our attention on thermal approaches.

Thermal decomposition of CH4 at temperatures above 1000°C will yield H2 gas and soot or coke (carbon-
rich species) with higher temperatures, favoring faster and higher conversion. The combination of higher

2.1
temperature and longer residence times favors the production of H2 and carbon [24-26]. The product
distribution favors more gaseous products with higher yields of olefins and aromatics at lower
temperatures in short contact time reactors. Low pressure favors higher conversion of CH4, but also tends
to produce more olefins. The olefins decompose to carbon and H2 with increasing residence time. The
morphology of the solid carbon is affected by the prevailing decomposition mechanism, which in turn is
determined by the combination of temperature, pressure, catalyst, and residence time. Figure 2.1 shows a
conceptual representation of the conversion of CH4 during the decomposition process as a function of the
operating conditions. The intermediates, olefins and aromatics, are initially formed and then decompose
further to “carbon” and H2. The soot part of “carbon” is essentially a C-H molecule where the C/H ratio is
near 1 at low temperatures and increases with residence time at high temperatures [27]. The soot particles
are considered to be aggregates formed from smaller spherical primary particles.

Low CH4 High Yields


Conversion Olefins and Aromatics “Carbon” + H2

Temperature
Residence Time
Pressure

Figure 2.1. Conceptual Representation of Conversion and Yields as a Function of Reactor Conditions.
“Carbon” represents particles of soot and graphite.

Holmen et al. [26, 28] studied the conversion of CH4 in high-temperature processes and reported on the
yields of products that include carbon, H2, and olefins, with mechanisms and reaction kinetics.

Equilibrium product distributions of CH4, H2, and carbon (typically graphite) can be derived from
calculations using correlations for the equilibrium constants or Gibbs free energy minimization [16].
Snoeck [29] provides experimental results and correlations for catalytic cracking on nickel (Ni).

Figure 2.2 shows the equilibrium yields from the decomposition of CH4 in the temperature range of 25 to
1000°C at a pressure of 1 atm [30]. The dominant products are CH4, carbon, and H2. A small amount (less
than 2 × 10-5 mol/mol-CH4) of ethane is formed and peaks at 500°C. Small amounts of ethylene and
acetylene are also predicted at temperatures above 500°C and 1300°C, respectively. The effect of pressure
can be seen in Figure 2.3, where the higher pressure shifts the conversion of CH4 and yields of carbon and
H2 toward a higher temperature.

2.3 Catalytic Reactions

2.3.1 Catalytic Reactors Types

The choice of reactor type is an important consideration in the design of an economically viable process.
Packed-bed reactors (PBRs) and FBRs are the most commonly used reactors for CH4 decomposition. The
review by Abbas and Wan Daud [11] discusses different reactor technologies evaluated and reported upon
in the literature. The in-depth review by Amin et al. [16] also specifically describes the reaction kinetics
and models available for predicting reaction rates. Here we discuss the highlights for the various reactor
approaches reported in the literature, as well as the means for separation of the carbon product from the
process.

2.2
FBRs offer advantages that include the ability to continuously add catalyst particles and withdraw the
carbonaceous solid products, avoidance of reactor clogging due to carbon deposits, uniform temperature
distribution, and good mass and heat transfer. Challenges include the need to capture the fine particles and
large gas flows required to maintain fluidization and the particle size reduction by attrition.

Figure 2.2. Equilibrium Yields of Methane and Products as a Function of Temperature at P = 1 Atm
during Methane Pyrolysis

2.3
Figure 2.3. Effect of Pressure and Temperature on the Equilibrium Yields of Methane and Products
during Methane Pyrolysis

PBRs are simple in design; they require only the CH4 reactant to flow through the reactor. The reactor
may or may not contain catalysts, but the design demands a temperature profile conducive to fast
conversion and effective removal of the carbon products.

A rotary bed reactor is designed like a rotary kiln. The CH4 flows through an inclined tube that moves the
catalyst layer forward as the bed rotates. The carbon forms on the catalysts and the carbon and catalysts
are withdrawn at the bottom of the tube. Energy to drive the reaction can be provided by heating sources
either outside or inside the tube wall. Figure 2.4 shows a schematic of a rotary bed. This design allows a
continuous withdrawal of the solid products and possible regeneration of the catalyst [31, 32].

2.4
Figure 2.4. Simplified Rotary Bed Reactor Process Flow Diagram

Plasma reactors, described in more detail below, use gas and electrical energy to create a strong
electromagnetic field to generate a gaseous mixture of electrons and highly charged positive ions. A
plasma torch increases the temperature of the CH4 to very high temperatures (~2000°C), causing its
decomposition [26, 33-36].

2.3.2 Catalysts

Muradov [37] summarizes published data available on the conversion of CH4 to carbon products as
shown in Figure 2.5. Ni- and iron (Fe)-based catalysts operate in the 500 to 700oC and 700 to 950oC
ranges, respectively, and produce carbon filaments (including carbon nanotubes [CNTs]). Carbon-based
catalysts operated in the 850 to 950oC range produce both carbon filaments and turbostratic carbon.
Graphitic and turbostratic carbon are formed in the 700 to 1000oC range using a variety of catalysts.
Amorphous carbon is produced non-catalytically at operating temperatures >1150oC [15]. Amorphous
carbon includes carbon black and thermal black. Here we highlight the key attributes reported for both
metallic and carbon types of catalysts and the nature of carbon produced from each.

Figure 2.5. Summary of Published Data on Catalysts, Temperature, and Carbon Products from Methane
Decomposition. Catalysts: 1Ni-based, 2Fe-based, 3carbon-based, 4Co, Ni, Pd, Pt, Cr,
Ru, Mo, and W catalysts, 5non-catalytic decomposition. Carbon products: CFcarbon
filaments, TCturbostratic carbon, GCgraphitic carbon, AmCamorphous carbon [15].
(Reproduced with permission from Elsevier.)

Deactivation of the catalyst by coke formation is seen as the most important problem with CH4 pyrolysis.
The capacity of the catalyst to accumulate a significant amount of carbon filaments limits its time on
stream or the residence time required. Two main types of catalysts—metallic and carbonaceous—have
been the focus of most investigations [38]. In their comprehensive review, Abbas and Wan Daud [11] go
into more detail on the various catalysts reported and discuss catalyst deactivation and regeneration.

2.5
2.3.2.1 Metal Catalysts

Numerous metal-based catalysts have been studied for CH4 decomposition. Their practical application
requires development to increase their specific activities and lifetimes. It has been reported that the rate of
CH4 decomposition activity of the metals follows the order: Co, Ru, Ni, Rh > Pt, Re, Ir > Pd, Cu, W, Fe,
Mo [11]. However, much attention has been given to Ni- and Fe- based catalysts [11].

The effectiveness of a catalyst should be based on its activity, and given the large amount of carbon
produced during conversion, its operating lifetime. A key finding regarding catalyst deactivation pertains
to the mechanism by which carbon dissolution occurs on the metal surface and diffuses through the
particle. The carbon then precipitates at the metal-support interface, detaching the metal particle from the
support and forming a carbon filament with an exposed metal particle at its tip. This mode of carbon
accumulation allows the catalyst to maintain its activity for an extended period of time without
deactivation. It has been shown that thousands of carbon atoms can be deposited on the catalyst by
surface nickel atoms. However, eventually the catalyst is deactivated as access to active site becomes
limited [11]. Regardless of the catalyst activity and lifetime, two overarching problems with the use of a
metal catalyst are regeneration and practical separation of the produced carbon.

The operating conditions and kinetic results for metal catalysts, as reported from reference [11], are as
follows:
 Reaction Order: 1 [29]
 Activation Energy (kJ/mol): 29.5 to 46 [39]
 Temperature (°C): 500 to 1000
 Space Velocity (per hr): 50 to 50,000
 Sustainability Factor (ratio of the reaction rate after 1 hour time on stream divided by the initial
reaction rate): 0.14 to 1.

Reaction Mechanisms. Various reaction mechanisms have been developed by different groups and can
be summarized as follows [16]:
 Non-dissociative adsorption of CH4
– CH4 + I (Vacant site) = CH4 (ad)
– CH4 (ad) = CH3 (ad) + H (ad)
– CH3 (ad) = CH2 (ad) + H (ad)
– CH2 (ad) = CH (ad) + H (ad)
– CH (ad) = C (ad) + H (ad)
– C (ad) = C (dissolved)
– 2H (ad) = H2 + 2I.
 Dissociative adsorption of CH4
– CH4 + I (Vacant site) = CH3 (ad) + H (ad)
– CH3 (ad) = CH2 (ad) + H (ad)
– CH2 (ad) = CH (ad) + H (ad)
– CH (ad) = C (ad) + H (ad)
– C (ad) = C (dissolved)
– 2H (ad) = H2 + 2I.

Holmen et al. [26] reviews and summarizes the conversion of CH4 to carbon, H2, olefins, and aromatics,
and presents values for the reaction rate parameters. Considerable mechanistic and kinetic information is
available from the work on CH4 coupling reactions [40].

2.6
2.3.2.2 Carbon Catalysts

Industrial catalysts typically consist of metals supported on appropriate catalyst supports. Alumina, silica,
and carbon are the most widely used industrial supports [11]. One strategy for CH4 decomposition is to
use carbon as not only a support, but as the catalyst itself [11, 41]. The separation of carbon product from
the carbon catalyst itself is thus not necessary. Also, the process can be autocatalytic with the carbon
produced serving as the catalyst for further reaction [11, 15]. Additional benefits reported for using
carbon include its relatively low cost, high-temperature resistance, and tolerance to sulfur and other
contaminants found in the feedstock [11].

Several types of carbon materials have been evaluated for catalyzing CH4 decomposition: activated
carbon, carbon black, glassy carbon, acetylene black, graphite, diamond powder, CNTs, and fullerenes
[42]. Among these materials, most studies have focused on activated carbon because of its activity, good
stability, and availability. The catalytic activity of carbon forms for CH4 decomposition has been reported
to vary according to the ordered nature of carbon as follows: amorphous > turbostratic > graphite [11].
With all carbon types, deactivation occurs through deposition of carbon on the catalyst surface that blocks
active sites and reduces the catalyst surface area. The deposit has lower surface area and activity
compared to the original carbon catalyst [11]. Physical attributes of the carbon, such as surface area, pore
volume, and particle size, are important characteristics that affect deactivation. In addition, at higher
temperatures (e.g., >850C), carbon catalysts tend to deactivate at a slower rate. The reason is that at
higher temperatures, the rate of diffusion and deposition increases inside the pores where the majority of
the surface area is located [11].

Operating conditions and results have been summarized for carbon catalysts as follows [11]:
 Reaction order: 0.4 (activated carbon); 2 (carbon black) [43, 44]
 Activation energy (kJ/mol): 138 (activated carbon); 236 (carbon black) [37, 43]
 Temperature (°C): 750 to 1500
 Space Velocity (per hr): 360 to 36,000.

2.3.3 Catalyst Regeneration

The regeneration of deactivated catalysts is usually done by burning off the carbon with air or steam, both
of which lead to CO2 production in amounts nearly comparable to the quantity of CO2 produced in the
SMR process [11]. Regeneration by oxidation generates high temperatures on the catalyst surface, which
leads to sintering and loss of active area. Regenerating with CO2 has also been reported, but doing so
produces CO [38]. Thus, carbon oxides are produced regardless which process is used. Other researchers
have also evaluated catalyst regeneration via physical removal of carbon deposits on the catalyst surface
by attrition [11]. However, these results have been mixed in that only the carbon deposited on the external
surface of the catalyst particle can be removed, and this carbon represents only a fraction of the total
carbon produced by decomposition [11]. Therefore, not all solid carbon product is separated, and this
carbon will need to be removed from the catalyst surface by the methods described previously, which
results in the production of carbon oxides.

2.4 Plasma Reactions


Plasma processes can be classified as either thermal plasmas (hot plasma, usually greater than ~700ºC) or
non-equilibrium plasmas (cold plasma, less than ~700ºC). Thermal plasmas include direct current (DC)
arch torch, alternating current (AC), radio frequency (RF) inductively coupled torch, and high-frequency
capacitive torch. Non-equilibrium plasma (cold plasma) includes microwave, corona discharge plasma,

2.7
dielectric barrier discharge plasma, atmospheric pressure glow discharge plasma, and gliding arc
discharge. Generally, thermal plasmas achieve higher CH4 conversions than non-thermal plasmas.
Operating under plasma conditions requires the use of electric power, temperatures in the range of 700 to
5500ºC (for thermal plasma) [45-48], pressures close to atmospheric [45, 48-50], and the use of a plasma
gas (e.g., nitrogen, argon, helium, H2, CO) [48]. Plasma-assisted CH4 conversion can be carried out with
or without catalysts. Two types of catalysts that have been evaluated for CH4 dissociation with plasma
include metal-based catalysts (e.g., Ni, Co, La, Fe/Si, Pd, and Pt) [45, 51-54] and carbon-based catalysts
[55]. Catalysts have not been reported to enhance CH4 conversion significantly [53, 54], although in one
study conducted with a microwave plasma-catalytic system, CH4 conversion was reported to be improved
by about one order of magnitude with the use of Pd and Pt catalysts [52]. Cold plasmas are
inhomogeneous in discharge space, which results in a limited reaction region and restricted conversion
[56]. However, in one case, Longmier et al. [57] developed an RF non-thermal plasma reaction chamber
that was efficient for fully decomposing CH4 into H2 and carbon graphite. Thermal plasma processes
enable high CH4 conversion (>80%) with H2 as a major product [48, 49, 58, 59]. Other products may
include carbon, acetylene, benzene, and ethane [58].

Plasma technologies for converting CH4 into H2 and carbon present several advantages. High yields of H2
and carbon (100% carbon yield) can be obtained. The size of plasma reactors is an order of magnitude
smaller in comparison to traditional reactors [57, 60]. A large range of feedstocks can be used in the
plasma process, thereby making the process flexible. Also, the use of non-thermal plasmas, for example,
have been reported to work at temperatures in the 850 to 900oC range, which is approximately 500oC
lower than temperatures used for non-catalytic CH4 decomposition [55]. Thus, there are many benefits to
using plasma to provide the high energetics required for the process.

Overall, the following advantages of microwave energy over conventional thermochemical processes
have been summarized by Abbas and Wan Daud [11]:
 Noncontact heating.
 Energy transfer without heat transfer.
 Rapid heating.
 Quick startup and shutdown.
 Volumetric heating, which can be more uniform throughout the material body.
 Higher level of safety and automation.
 Microwave energy can be transported from the source through a waveguide (a hollow, nonmagnetic
metal tube) to the applicator (where the electromagnetic energy interacts with the material), which
can be designed to optimize absorbed energy.
 At higher temperatures, different grades of product carbon can be made [49].

Disadvantages of plasma processes relate to the energy requirements and the fact that energy is provided
by externally supplied electricity. A study by Longmier et al. [57] indicates that the energy required per
kilogram of H2 produced is 37 times higher than that required for steam reforming of CH4, but the energy
comparison does not include the energy required to sequester the emitted CO2 during SMR. Nonetheless,
the high energy requirements for plasma processing have been a distinct drawback of this approach.
Another potential issue with plasma processes is low solid carbon product yield. In the decomposition
process, a relatively high fraction of methyl radical enables the formation of stable hydrocarbons and
polymeric species, and a significant amount of energy is needed to crack CH4 all the way to solid carbon
[61]. However, as discussed above, some plasma processes provide sufficient energy to achieve complete
decomposition.

2.8
2.5 Separations Required
A major challenge for the continuous catalytic CH4 pyrolysis process is separation of the solid carbon
product and regeneration of the spent catalyst (if used), which are critical in the overall economics of the
process [16]. Some have also described the aggregation of carbon deposits in the reactor as a main
obstacle; one report describes it as the main technological “show stopper” [18]. In a PBR, carbon buildup
will eventually cause pressure increases and ultimately block process flow through the reactor. To
maintain catalytic activity and to avoid plugging of the reactor, the deposited carbon reactant must be
periodically removed. In a review, Muradov [62] evaluated various reactor types (e.g., PBR, FBR, free-
volume reactor, spouted-bed reactor, and tubular reactor) and concluded that the FBR is the most
promising reactor for large-scale application because it provides a constant flow of solids through the
reaction zone, making it suitable for continuous addition and withdrawal of catalyst particles from the
reactor. Fluidization of catalyst particles also increases heat and mass transfer rates [11].

Different methods have also been used to separate the carbon byproduct from the H2 stream. For example,
bag filters have been used to remove carbon elutriates [11]. Bag filters also have been employed in
plasma processes. Economic analysis for CH4 pyrolysis technology employing this separation method
needs to be evaluated. Also, the use of a molten-metal reactor makes it possible to skim carbon from the
top of the metal surface because of its density difference. While this may offer one solution to the issue of
solid carbon separation, relatively high temperatures are still required (as with non-catalytic thermal
pyrolysis). Geisler et al. [63] report liquid metal temperatures in the range of 930 to 1175oC are required.
This technology, being pursued by Arenius Systems, is discussed in the next section.

The conversion of CH4 to carbon and H2 would ideally not include any other chemical species in the
reactor stream. However, natural gas contains impurities (moisture, air, sulfur species, etc.) and requires
separations in the process. If the pyrolysis process is conducted at elevated pressures, then PSA is an
effective solution for extracting the product H2. For low pressure pyrolysis, alternative gas separation
techniques must be adopted.

2.9
3.0 Process Technologies
In Section 2.0, we report in broad terms the thermodynamic and processing requirements for each of the
classes of process technologies (e.g., thermal, catalytic, plasma). Here we report on specific technologies
that have been reported in the literature— at various stages of commercialization —that use different
approaches to tackle the issues described above. Methane decomposition processes considered in this
study are summarized in Table 3.1. More detail is provided for each process, as classified within thermal,
plasma, microwave, and hybrid technology classes.

Table 3.1. Summary of Methane Decomposition Processes


Wulff [64]  Thermal cracking
 Intermittent: Natural gas combustion followed by cracking
 Packed media: carborundum
 1200–1650°C
 Desired product: olefins
 Research & development phase
HYPRO [65]  Solid recirculating catalyst
 Methane thermal cracking
 Carbon deposited on catalyst burned to regenerate the catalyst
 Pilot scale
Fluidized Bed [66,  Activated carbon catalyst
67]  Electrical heating or by alternately switching between combustion and catalytic cracking
 Research & development phase
EGT Enterprises  Methane pyrolysis reactor
[68]
 2000°C
 Energy demand 14 kJ/gC and 43 kJ/gH2
 Research & development phase
Institut Francais  Combustion followed by CH4 pyrolysis on ceramic honeycomb
du Petrole [69]  1200°C
 Pilot-scale demonstration
 Desired product: olefins
 Research & development phase
Steinberg and  Methane decomposition in molten metal (tin, 232°C or copper, 1083°C)
Arenius Systems  Methane bubbled through bath, carbon floats to the surface, gas is mainly H2
[70, 71]  H2 purified by PSA
 Pilot scale
BASF [72-74]  Methane pyrolysis, 1200–1400°C, produces carbon and H2
 H2 reacted with CO2 from external process to produce syngas
 Fluidized bed with support materials and carbonaceous granules
 Research & development phase
Monolith  Plasma reactor
Materials [75, 76]  Produces carbon black and H2
 H2 combustion to produce steam (replacing coal-fired boiler)
 Commercial (early stage)

3.1
Kvaerner [34, 77]  Plasma torch decomposes CH4 to form carbon
 H2 is the plasma gas
 1000–2000°C
 Research & development phase
GasPlas [78]  Co-axial vortex flow reactor
 Microwave induced plasma
 Research & development phase
Remarks on  Use of inert gases such as argon.
Plasma Processes  Electrical power is a premium, available from the grid at efficiencies of less than 40%.

3.1 Thermal Catalytic Processes


One of the earlier technologies for the thermal cracking of CH4 to produce useful products is the Wulff
process [64], which uses high-temperature steam to crack natural gas to acetylene, producing significant
byproducts of H2 and carbon. It is an intermittent process that begins with natural gas combustion to heat
the chamber and the packed media made of carborundum crystals. In subsequent steps, the combustion air
is stopped, and the CH4 cracks in contact with the heated surfaces of the chamber and the particles, which
can be at temperatures as high as 1650°C (3000°F). This process continues until the temperature cools
down to 1200°C. The products are primarily H2, acetylene, ethylene, carbon oxides in the gas stream, and
solid carbon deposited on the media. The valued gas products need to be subsequently separated from the
small amounts of nitrogen, oxygen, and unreacted CH4.

Another pioneering process for producing H2 by thermal decomposition of CH4 is the HYPRO [65]
process, which was demonstrated by UOP in McCook, Illinois. A solid recirculating catalyst was used.
The process employed a Ni-based catalyst to lower the decomposition temperature and two FBRs with a
solids-circulation system. The carbon deposited on the catalyst was burned to regenerate the catalyst and
provide process heat. This process was not CO2-free.

Muradov [79] compared the thermodynamically predicted yield of H2 as a function of temperature to


experimental yields observed using several different catalysts. Iron oxide was shown to achieve
equilibrium-predicted H2 yields at 900°C. Carbon in the form of graphite crystallites was observed on the
catalyst based on X-ray diffraction. A later patent and progress report [66, 67] proposed the use of
activated carbon or carbon as the catalyst in an FBR. The fluidized bed could be heated using either
electrical heaters or by using a dual bed reactor system where one of the reactors is decomposing CH4,
while the other is being regenerated and heated by combustion [80].

EGT Enterprises developed a pyrolysis reactor using a series of heating zones with an electric resistance
heating screen capable of operating up to 2000°C [68]. One configuration showed the process operating at
a feed rate of 4600 ft3/hr at a temperature of 1370°C and producing 9180 ft3/hr of product gas containing
97% H2 with the balance being mainly unreacted CH4. The 97% H2 in the product corresponds to 94%
CH4 conversion. The energy demand for the process was 260 kW, which is 128% more than the required
heat of reaction (i.e., the process has an efficiency of 44%) equivalent to 14 kJ/g of carbon and 43 kJ/g of
H2.

Weill et al. [69] used a ceramic honeycomb pyrolysis reactor in which combustion gas was used to heat
the CH4 to be pyrolyzed at 1200°C. When demonstrated at the pilot scale, the process showed yields of
ethylene, acetylene, benzene, coke, and tars.

3.2
BASF, Linde Group, and ThyssenKrupp [72] have developed a pyrolysis-based process for producing
syngas and solid carbon. The H2 produced by this pyrolysis process is reacted with CO2 (captured
elsewhere) to produce syngas via the reverse WGS reaction. The pyrolysis reaction occurs in a FBR
containing support materials and carbonaceous granules and operating at 1200 to 1400°C.

Steinberg [70] proposed a molten metal-based CH4 decomposition process that bubbles CH4 through a
molten-tin (melting point of 232°C) or copper (1083°C) bath. Because of its lower density, the carbon
floats to the surface of the bath, which facilitates its recovery. The gas stream contains primarily H2 with
lesser amounts of unreacted CH4 and other byproducts. Arenius Systems is developing such a process at a
pilot scale to provide H2 for fuel cells with carbon black as a byproduct [71].

3.2 Concentrated Solar Power


Concentrated solar power is a renewable source of high-temperature process heat, and direct solar
irradiation of the reactants provides for a very efficient heat transfer directly to the reaction site [81]. A
recent review article by Steinfeld discusses several solar natural gas conversion approaches and provides
a comparative analysis for the different approaches in terms of exergy efficiency, which was reported to
be about 30% for solar cracking of CH4 [82]. Hirsch and Steinfeld also report the design of a solar
chemical reactor that uses a cavity-receiver that directly irradiated a vortex flow of natural gas premixed
with carbon particles, which serves as both a radiant absorber and as a catalyst [83]. After exiting the
reactor, the products are cooled and the solid products are collected in filters. A continuous mode of
operation was demonstrated at the 5 kW scale with 67% CH4 conversion at 1600K and 1 bar. The carbon
formed was filamentary in nature [83].

In a different study by Steinfeld, a sun-tracking heliostat and stationary parabolic concentrators were used
to supply to a small-scale FBR [81]. The direct irradiation of a Ni/Al2O3 catalyst provided effective heat
transfer to the reaction site. Methane underwent pyrolysis at 850K with the conversion decreasing with
time on stream as the carbon product accumulated, which caused the catalyst to deactivate. Yields of
200 g carbon/g catalyst were reported.

Generally, catalytic-based solar thermochemical applications have issues similar to other catalytic-based
thermochemical conversion processes, such as recovery of the carbon from the catalyst and regenerating
the catalyst. One disadvantage with using solar power specifically is difficulty in maintaining stable heat
flux. However, there is great potential benefit in utilizing solar for supplying the energy for highly
endothermic reactions.

3.3 Plasma Processes


Fulcheri et al. [49] extensively studied CH4 conversion to H2 and carbon. They developed a plasma
reactor with three electrodes, creating a compound arc by applying an AC current to the electrodes [45,
47-49]. The major advantage of this process is the total conversion of the hydrocarbon into carbon (100%
carbon yield) and pure H2. This process allows the production of different carbon materials with defined
nanostructures (e.g., carbon black, fullerenes, and nanotubes) by controlling the operating conditions [45,
48]. In addition, the feedstock may contain or consist of CH4, acetylene, propylene, C4 hydrocarbons,
light or heavy oil, waste oil, and pyrolysis fuel oil [48]. The feedstock can also comprise solid carbon
material (e.g., carbon black, acetylene) for production of CNTs [45].

Recently, Monolith Materials partnered with Fulcheri and Schwob’s group and Aker Solutions to build a
pilot plant, located in Redwood City, California. The plant uses a plasma-based process for converting
natural gas into H2 and carbon black [75]. Monolith is building a production-scale plant in Hallam,

3.3
Nebraska, expected to be online in 2018, that will sell the H2 to an adjacent power plant to produce CO2-
free electricity [76].

Kim et al. [35] studied the thermal decomposition of CH4 by using a DC-RF hybrid thermal plasma to
demonstrate the production of H2, a small amount of olefins, and 20 to 50 nm carbon particles. Their
design simulation estimates a total power requirement of 40 kW to produce 10 Nm3/hr (0.89 kg/hr) of H2
and 2.5 kg/hr of carbon black, assuming 60% thermal efficiency of the DC-RF torch (see Table 3.2).
Their simulated process uses 83.5 SLPM of CH4 with a LHV of 49.8 kW. Considering only the 40 kW of
plasma power for the process, the specific energy demands are 161 kJ/gH2 and 57.6 kJ/gCarbon, or
cumulatively 42 kJ/gCarbon+H2 products. Comparing this to an SMR process operating with 70% efficiency
(LHV of H2 as a percentage of LHV of the CH4 feed), the specific energy demand is 172 kJ/gH2, which
compares favorably with the plasma process. However, if we include the LHV of the CH4 in the energy
input to the plasma process, then the specific energy demands for that process increase by a factor of 2+
to 362 kJ/gH2, 129 kJ/gCarbon, and 95 kJ/gCarbon+H2.

Table 3.2. Hydrogen from Thermal Plasma Decomposition of Methane (100% conversion assumed) [61]
Argon/CH4 Ratio Ar Flow CH4 Flow Plasma Power Total Input Power H2 Output
2 167 SLPM 83.5 SLPM 24 kW 40 kW 10 Nm3/hr

Moshrefi et al. [84] reported on CH4 conversion using a DC spark discharge plasma experiment designed
to produce olefins, where the gaseous products included acetylene, ethylene, and ethane accompanied by
the formation of solid carbon. With a conversion percentage of 45% and assuming all H2 in the converted
CH4 is available, the process efficiency based on the LHV of H2 only is 16% (Figure 3.1). Extrapolating
to 100% conversion, the efficiency would increase to 35%. From a H2-only perspective, the process
energy efficiency is low; however, if the carbon can be sold as a commodity, the process may be
economically attractive. The plasma was generated using argon gas, which is likely to pose an economical
challenge to scale up.

Figure 3.1. Direct Current Spark Discharge Plasma Experiments Produced Hydrogen and Carbon [84]

Kvaerner [34, 77] developed the Carbon Black and Hydrogen Process using a plasma torch for CH4
pyrolysis to produce H2 and carbon black. H2 is used as the plasma gas. A commercial plant was built and
operated in Canada between 1999 and 2004. The reactor temperatures vary between 700°C at the primary
gas inlet and reach a high of up to 2000°C. A secondary stream of CH4 is then decomposed by contacting
the hot gases.

GasPlas uses a microwave, non-thermal plasma to produce H2 and carbon [78]. Its noted features include
an ambient pressure process, use of a highly non-equilibrium plasma, scalability, and ability to control the
carbon formation and collection. One set of experimental results showed that a stream of CH4 (3 L/min)
mixed with Ni (17 L/min) when subjected to 1900 W of microwave power converted 53.9% of the CH4
[85].

3.4
3.4 Chemical Processes for Decomposing Methane
ETCH, LLC is developing a low-temperature, quasi-catalytic process for producing carbon and H2 from
natural gas based on a process invented by Professor Jonah Erlebacher at Johns Hopkins University under
a U.S. Department of Energy (DOE) Advanced Research Projects Agency-Energy (ARPA-E) grant [86].
The process is based on the reaction of hydrocarbons, such as CH4, with anhydrous nickel chloride to
form nickel metal, carbon, and HCl at a temperature of ~800°C. Lowering the temperature results in a
back reaction between the nickel metal and HCl to regenerate nickel chloride and release H2 gas. The
carbon is separated from the nickel chloride by sublimation. The reaction is tolerant to impurities found in
natural gas, such as sulfur, water, and other hydrocarbons. The process requires no water and uses
substantially less energy than SMR making it attractive for deployment in regions where process water is
not readily available. Initial estimates indicate that the process could produce 4.7 kg of carbon for every
kilogram of H2, with a projected H2 production cost competitive with SMR [87].

3.5
4.0 Market  Current and New Opportunities
The United States produces about 10 million metric tons of H2 annually, and SMR accounts for more
than 95% of this production. New markets for H2 such as fuel cell-powered vehicles are projected to
significantly increase the demand for H2 in the coming decades. A key challenge for fuel cell cars is the
ability to produce H2 at a cost that is competitive with the cost of producing gasoline on an equivalent
energy basis. The ability to monetize the carbon produced during the thermal decomposition of natural
gas offers the potential to reduce production costs of H2 compared to those of SMR. In a 1987 study,
Steinberg et al. [88] compared the production cost of H2 by several pathways, including CH4 cracking,
and estimated a cost of $5.10 per kilogram after taking credit for carbon black, exceeding SMR. To the
best of our knowledge, there are still no viable commercial processes based on producing both carbon and
H2 for the carbon black and H2 markets, respectively. This highlights the need for continued cost
reductions through research and development, and through creative market strategies.

Carbon is marketed in a number of different forms including carbon black, CNTs, carbon nanofibers,
carbon fibers, graphene, and needle coke. Carbon black is the oldest and most mature market for carbon.
Table ES.1 summarizes the market potential for the different types of carbons. More details for each of
the markets are included in this section.

4.1 Current Markets

4.1.1 Natural Gas

The development of hydraulic fracking and horizontal drilling has enabled the ability to recover natural
gas from shale and tight formations at cost-competitive prices resulting in significant growth in the
natural gas supply while leading to lower prices. For example, U.S. natural gas production rose from
23.7 trillion cubic feet (tcf) in 2005 to 32.6 tcf in 2016; consumption rose from 21.7 tcf in 2005 to 27.5 tcf
in 2016; and prices dropped from $8.12 per million cubic feet (mcf) to $2.35 /mcf. U.S. natural gas
reserves have increased from 213.3 tcf in 2005 to 307.7 tcf in 2015 [89]. Figure 4.1 shows the location
and reserve potential for the major shale gas basins in the United States.

According to the Energy Information Administration Annual Energy Outlook (AEO) 2017 [90],
natural gas prices are projected to increase its Reference Case, rising modestly through 2030 to $5.00
to $6.00/mmBTU4 as the use of natural gas for electric power generation increases. Prices projected to
remain relatively flat after 2030 as technology improvements keep pace with the rising demand
(Figure 4.2). Under its High Oil and Gas Resource and Technology scenario, prices are projected to
remain relatively low at $3.00 to $4.00/mmBTU due to lower production costs and higher resource
availability. Under its Low Oil and Gas Resource and Technology case, prices are projected to approach
$10.00/mmBTU, driving down domestic production and consumption. U.S. natural gas production is
projected to grow at an annual growth rate of around 4% between 2016 and 2020 spurred by large,
capital-intensive projects such as new liquefaction export terminals and petrochemical plants built in
response to the low natural gas prices (Figure 4.3). Beyond 2020, natural gas consumption is expected to
grow at a rate of about 1% annually as export growth moderates and domestic use becomes more
efficient, causing prices to rise more slowly. Natural gas from shale gas and tight oil is projected to
account for nearly two-thirds of U.S. production by 2040 (Figure 4.4).

4
The unit mmBTU is a thousand-thousand, or million BTUs.

4.1
Figure 4.1. Location and Projected Reserves for Major U.S. Shale Gas Basins in the United States [91]

Figure 4.2. Historical and Projected Price of Natural Gas from 1990 through 2040 [90]

4.2
Figure 4.3. Total U.S. Natural Gas Production and Consumption from 1990 through 2040 [90]

Figure 4.4. Historic and Projected Growth in the Production of Natural Gas from Shale Basins and Tight
Oil between 1995 and 2040 [90]

4.1.2 Hydrogen

The United States produces about 10 million metric tons of H2 annually and SMR accounts for 95% of
the H2 produced. The major consumers of H2 are petroleum refining (47%) and fertilizer production
(45%). Methanol production consumes about 4% of the H2 produced and the electronics, metals, and
food industries combined consume the remaining 3% [92].The U.S. demand for H2 by industry was
13.8 million metric tons in 2015 and the demand in oil refining accounted for 10.5 million metric tons,
which is equivalent to 76% of the total demand [93]. The industrial demand is met by either on-purpose
production or the recovery of byproduct H2. On-purpose H2 is produced by both the consuming industry,
referred to as captive production, and by merchant gas companies. In 2015, approximately 10 million
tons of H2 was produced; 6.4 million tons were produced by captive production, and 3.6 million tons
were produced by merchant gas companies. Approximately 5.8 million metric tons of byproduct H2 was
recovered by the oil refining industry and from multiple other processes. Of this amount, approximately

4.3
3.8 million metric tons of H2 were recovered for self-use or for sale to merchant gas companies and the
remaining 2.0 million metric tons were combusted for process heat. Merchant gas companies recovered
0.29 million metric tons of H2 (including ethylene, chlor-alkali, styrene, acetylene, and propylene) from a
number of industries, and another 0.10 million metric tons were recovered from other unidentified
sources. In terms of production cost, the price of H2 is tied to the price of natural gas given that SMR
accounts for more than 90% of the H2 produced in the United States. As a “rule of thumb,” the cost of H2
produced by SMR is approximately three times the cost of natural gas per unit of energy produced [94].
Given the current cost of natural gas of about $3.00/mmBTU, the production cost of H2 equates to
$9.00/mmBTU or approximately $1.00/kg based on the LHV of H2.

Demand for H2 in the United States and globally is dominated by the oil refining, ammonia, and methanol
industries [95]. In the United States, captive H2 production accounts for nearly all the H2 used in ammonia
and methanol production. Growth in these markets appears promising with the price of natural gas in the
United States likely to be competitive with world prices over the next decade. In oil refining, slightly
more than half of the H2 demand is met by recovering byproduct H2 from catalytic reforming units with
the remaining H2 demand met by captive production and merchant supply. While captive production has
increased substantially over the past 25 years, merchant supply has increased from nearly nothing to 15%
over the same period. Growth in demand in the methanol industry is due to a fourfold increase in
methanol production since 1990. In oil refining, the growth in demand is due to stricter limits on the
sulfur content in gasoline and diesel fuel resulting in an increase H2 demand for hydrodesulfurization and
the increasing need for H2 for hydroprocessing heavier crudes to favor distillates over residuals. Growth
in the merchant supply market has been driven by the increasing demand of oil refineries with more than
90% of U.S. merchant H2 production being delivered to oil refineries [96]. Long-term growth in the
demand for H2 for oil refining is uncertain given the projected flat or decreasing demand for petroleum
products in the transportation sector in the coming decades due to increasing penetration of electric
vehicles into the light-duty vehicle market coupled with projections that U.S. petroleum consumption
peaked in 2006 and that annual miles driven is expected to peak in 2018 [90].

Globally, the demand and supply of H2 was estimated to be 87 million metric tons in 2015 with captive
production accounting for more than 60 million metric tons. Ammonia production accounted for about
30 million metric tons or nearly 50% of the captive H2 production with methanol production and oil
refining each accounting for approximately 25% of the total production. Merchant supply of H2 accounted
for less than 10% of the total demand; however, it is the fast growing market, growing at an annual rate of
15.3% since 1990 [97].The global market for H2 is projected to grow from an estimated $115.25B in 2017
to $154.74B by 2022, at a compound annual growth rate of 6.07% [98]. The growing demand for H2 is
due to: 1) an increasing demand in oil refining to further reduce the sulfur content of gasoline and diesel
and an increasing demand for a lighter mix of products (i.e., a higher percentage of distillates and a lower
percentage of residual products); and 2) an increasing demand for methanol for use as a transportation
fuel and as a feedstock for producing olefins [95]. Fuel cell-powered vehicles represent a potential
disruptive technology that could have a significant impact on the world demand for H2. With about one
billion light-duty vehicles on the road globally, the potential demand for H2, assuming all vehicles are fuel
cell-powered, is estimated to be around 150 million metric tons (based on 10,000 miles driven annually
and a fuel economy of 67 miles per kilogram).

4.4
4.1.3 Carbon

Carbon black is essentially pure carbon, typically 97% or greater by weight, in the form of colloidal
particles formed by the thermal decomposition of gaseous or liquid hydrocarbons under controlled
conditions[47]. Because the thermal decomposition of CH4 is endothermic, some processes add some
oxygen to the feed resulting in the partial oxidation of CH4 to accelerate the reaction. Carbon black is
distinct from soot or black carbon, which typically contains less than 60% carbon and as much as 50%
ash by weight. Carbon black is used as filler and a strengthening/reinforcing agent in the manufacture of
tires and other rubber and plastic products. It is used in printing inks to enhance formulations and in high-
performance coatings to provide pigmentation, conductivity, and protection from ultraviolet light. Certain
grades of carbon black are approved by the U.S. Food and Drug Administration for use in items such as
coffee mugs, food trays, and cutlery [99]. Approximately 90% of the carbon black produced is used in
rubber applications, primarily tires, 9% as a pigment, and the remaining 1% in a number of diverse
applications [47].

Carbon black can be produced by a number of processes including the furnace black or oil-furnace
process, the thermal black process, and the acetylene black process. In the furnace black process, heavy
aromatic oils are atomized and injected into a natural gas-heated furnace under controlled conditions
[100]. The oils are partially combusted or undergo thermal decomposed at temperatures ranging from
1600 to 1800°C to form microscopic carbon particles. The exhaust gas containing the carbon particles is
cooled using water quenches and heat exchangers. The carbon is separated from the cooled gas stream
using water sprays and a fabric filter. The recovered carbon is densified and processed into pellets of
various grades and sizes. Yields range from 35 to 65% depending on the composition of the grade of
carbon black produced. The residual gas contains a variety of compounds, including H2 and CO, and is
used without further purification to produce heat, steam, or electric power.

In the thermal black process, natural gas is thermally cracked to produce carbon black [100]. Two
furnaces are used in the process and natural gas undergoes thermal cracking in the first furnace. Similar to
the furnace black process, the exhaust from the first furnace is cooled and the carbon is filtered out. The
exhaust gas, which contained upwards of 90% H2 and a balance of CH4 and other light hydrocarbons, is
burned to heat the second furnace. When the temperature of the first furnace becomes too low to promote
cracking, the order of the furnaces is reversed. Typically about 15 to 20% of the exhaust gas is used to
heat the furnace, and the remaining gas is used without further processing to produce heat, steam, or
electric power.

In the acetylene black process, acetylene is used instead of natural gas [101]. Whereas the thermal black
process is endothermic, the acetylene process is highly exothermic. Because of the higher purity of the
feedstock and exothermic nature of the process compared to the thermal black process, the acetylene
process produces a very pure carbon black that has a greater degree of crystallinity than that produced by
the other methods.

Each process produces different grades of carbon black that have unique physical properties (e.g., particle
size, agglomerate size, surface area, structure/void volume, color, etc.). Rubber-grade carbon black is
classified as either ASTM or Specialty Grade, and each classification contains a large number of grades
based on physical properties such as particle size and structure [102, 103]. Today more than 95% of the
carbon black produced in the United States is produced using the furnace black process, because it can
produce nearly all of the different grades by carefully controlling the process conditions [104].

4.5
The price of carbon black depends on the product specifications (i.e., the grade and volume purchased).
Prices can range from $400 to over $1000 per ton for ASTM-grade carbon black for use in tires to over
$2000 per ton for specialty grade carbon black based on a survey of commercial price lists [1]. Given that
the vast majority of carbon black produced worldwide is produced from oil, the price of crude oil has an
overriding influence on the carbon black market [105].

The United States currently produces about 2 million metric tons of carbon black annually with a
projected 4.2% annual growth rate through 2022 (Figure 4.5) [2]. Producers headquartered in the
United States include Cabot Corporation (Boston, MA), Continental Carbon Company (Houston, TX),
and Sid Richardson Carbon & Energy Co (Fort Worth, TX). The two other major industrial manufacturers
are Birla Carbon, headquartered in India, and Orion Engineered Carbon, headquartered in Luxembourg
[104]. Given favorable market factors, new companies such as Monolith are entering the market [99].
Monolith’s plant located in Redwood City, California, is the first carbon black manufacturing facility
built and licensed in the United States in the last 30 years.

Figure 4.5. U.S. Carbon Black Market Volume by Application from 2012 Projected through 2022.
Volume is in kilotons [2]. (Reproduced with permission from Grand View Research.)

The global demand for carbon black was nearly 12 million metric tons in 2014. Global demand is
projected to increase to 16.4 million metric tons by 2022, representing a market value of $28B dollars,
with most of the growth in demand occurring in China and India [3]. Global demand is being spurred by
the increasing demand for automobiles in the Asian market that will drive tire sales. Analysts predict that
U.S. tire manufacturers will face a shortfall in the availability of carbon black manufactured in the United
States beginning in 2020 due to the projected global growth in the demand for tires worldwide. Specialty
carbon black for use in plastics and lightweight automotive components is expected to be the fastest
growing market segment [106].

4.2 New Market Opportunities for Methane Conversion to Carbon


and Hydrogen
Other forms of carbon besides carbon black may be considered as products. Examples for carbon include
graphite/graphene, carbon fiber precursors, CNTs, and needle coke. We also discuss hydrocarbons in the
form of aromatics that can be produced from CH4 pyrolysis. Each of these forms of carbon is discussed
below.

4.6
4.2.1 Graphite/Graphene

Graphite/graphene materials are all nearly 100% carbon and differ primarily in topology (Figure 4.6).
Graphite is the naturally occurring material. It has a layered, planar structure. The individual layered
sheets are called graphene. In each layer, the carbon atoms are arranged in a honeycomb lattice with a
separation of 0.142 nm, and the distance between planes is 0.335 nm [9]. Atoms in the plane are bonded
covalently, with only three of the four potential bonding sites being satisfied. The fourth electron is free to
migrate in the plane, making graphite electrically conductive. However, it does not conduct in a direction
at right angles to the plane. Bonding between layers is via weak van der Waals bonds, which allows layers
of graphite to be easily separated or to slide past each other. A rolled up layer is a CNT.

(A)

(B) (C)

Figure 4.6. Comparison of the Structure of (A) Graphite, (B) Graphene, and (C) a Single-Walled Carbon
Nanotube [107]

Demand for natural graphite is 1 to 1.2 million tons per year and consists of several different forms
of graphite—flake, amorphous, and lump. Historical applications primarily use amorphous and lump
graphite, while most newly emerging technologies and applications use flake graphite. Of the up to
1.2 million tons of graphite that are processed each year, just 40% is the flake form. Historically, China
was responsible for the large decline in graphite prices in the 1990s as product was dumped on the market
to earn foreign exchange. Much like rare earths, this essentially killed the industry in the West, making
the United States highly dependent on supply from China. It is unlikely China can do the same thing
again. The majority of Chinese graphite mines are small, many are seasonal, and labor and environmental
standards are poor. Easily mined surface oxide deposits are being depleted and mining is now moving
into deeper and higher cost deposits [108].

Graphite is used in electronic applications such as for Li-ion batteries where the market in 2015 was
80,000 tons/yr [4]. Additionally, the U.S. Geological Survey states that large-scale fuel cell applications
being developed today could consume as much graphite as all other uses combined. But even if only half
of the U.S. Geological Survey demand is realized, graphite use is going to explode just because of fuel
cells, let alone other known demand drivers and new applications [109]. Thus, the natural graphite market
is currently small, but it possibly will be very important for new fuel cell applications and/or batteries.

4.7
Graphene is a special form of graphite that is 100% carbon and only one layer or at most a few layers
thick. It potentially has all of the application space that graphite has but currently has little production.
The global market for graphene reached $9 million by 2012, with most sales in the semiconductor,
electronics, battery energy, and composites industries [110]. The market is projected to grow from
80,000 metric tons produced in 2015 to 250,000 metric tons by 2020 [4]. Generation as a co-product with
H2 could be a potential benefit, but the current market would soon be saturated unless demand increases.

There is little reason to believe a priori that carbon produced from a pyrolysis process would be well
ordered. However, one study has reported formation of well-ordered pyrolytic graphite structures as well
as fibrous carbon on transition metals. The pyrolytic carbon was reported to be of equal quality to
recrystallized graphite normally produced at much higher temperatures. Results appeared to be repeatable
[111]. However, the value of the carbon will depend heavily on the treatment of the feed gas. Carbon
black furnace processes operate by injecting a heated aromatic liquid hydrocarbon into the combustion
zone of furnace fired by natural gas, where the hydrocarbon is decomposed to form carbon black at
temperatures on the order of 1320 to 1540°C. Depending on the feed composition and the grade of black
produced, process carbon black yields have ranged from 35 to 65% [100].

4.2.2 Carbon Fibers

Carbon fibers are polycrystalline, two-dimensional planar hexagonal networks of carbon containing
between 92 to 100% carbon by weight formed by heating carbon-containing precursors at temperatures
ranging from 1000 to 1500°C [112]. If the fibers are heated above 2000°C, the hexagonal carbon network
undergoes conversion to graphene with yields in excess of 99%. These fibers are referred to as “graphite
fibers.”

Carbon fibers have a number of favorable mechanical and chemical properties, such as high tensile
strength and stiffness, low density, dimensional stability, low coefficient of thermal expansion, fatigue
resistance, and chemical inertness and biological compatibility [112]. Carbon fibers are finding increasing
use in a variety of applications such as aerospace, automobiles, sports and leisure, the chemical industry,
wind turbines, carbon-reinforced composite materials, and textiles [6, 7, 112-114]. The physical
properties (primarily tensile strength and modulus, as well as others) determine the proper utilization of
produced carbon fibers [115].

Carbon fibers are manufactured from precursor fibers using a combination of heat and stretching
treatments. The most common precursors are polyacrylonitrile (PAN) and pitch, which is a complex blend
of polyaromatic and heterocylcic compounds. Other linear and cyclic precursors include phenolic
polymers, polyacenephthalene, polyamide, polyphenylene, poly-p-phenylene, benzobisthiazole,
polybenzoxazole, polybenzimidazole, polyvinyl alcohol, and polyvinylidene chloride, and polystyrene.
[116]. Currently PAN is used to produce 95% of the carbon fibers worldwide, and pitch is used for the
remaining 5%. Precursors, namely PAN, account for approximately 51% of the manufacturing cost of
carbon fibers, and their high price is one of the barriers to their widespread use [115]. Additionally, the
current methods for manufacturing carbon fibers are slow and energy-intensive. Thus, both alternative
methods of manufacturing and use of cheaper precursors are under exploration.

Alternative precursors to PAN under investigation include biomass precursors such as lignin, glycerol,
and lignocellulosic sugars [115]. There has been a particular interest in using lignin as a precursor
because of its availability, low cost relative to other precursors, and enhanced structural properties.
However, it has been reported that no biomass-based carbon fiber has been developed with the necessary
structural properties to be used in the major carbon fiber applications (e.g., aerospace, wind, and
automotive. For more information the report authored by Milbrandt and Samuel Broth provides both

4.8
technical and market information about each bio-based carbon fiber precursor [115]. Also, the report
authored by Baker et al. provides a comprehensive review of carbon fiber manufacture specifically from
lignin, which includes a cost comparison of potentially low-cost carbon fibers [117].

The process for producing carbon fibers depends on the precursor and the desired physical properties. For
PAN, the process starts by polymerizing the PAN-based precursor, which is then spun into fibers. The
fibers are then treated using an air-based oxidation process at temperatures between 200 and 400°C to
stabilize the fiber. The stabilized fibers are heat treated in the absence of oxygen at temperatures ranging
from 800 to 1600°C to remove non-carbon impurities such as H2, oxygen, and nitrogen and to induce
carbonization. Next, a surface treatment is used to improve the mechanical properties of the carbon fiber.
Finally, the fiber is washed, dried, and sized [112, 116]. For pitch, the process starts by melting pitch so
that it can be extruded and drawn into fibers. Similar to the PAN-based process, the fibers are air-treated
to stabilize the fiber; they then undergo a higher temperature heat treatment to induce carbonization [116].
Pitch has the advantage of lower cost and producing a higher char yield than PAN, but the processing
costs are higher to achieve carbon fibers of similar performance to PAN [116].

An alternative to the PAN- and pitch-based processes is the “vapor-grown” production process. The
process involves exposing light-hydrocarbon gases [112, 118], such as CH4 [119], acetylene, or ethylene
or coal-gas [120], to a solid catalyst, such as Co, Fe, or Ni, to form carbon filaments with diameters as
small as 0.1 µm as precursors for carbon fiber growth. The filaments consist of graphitizable carbon that
is transformed into larger diameter graphite fibers by heat treatment at temperatures above 250°C.
Exposing these carbon filaments to subsequent chemical vapor deposition using the same carbonaceous
gases causes the filaments to grow in diameter ranging from 60 to 200 nm and approximately 100 µm in
length, yielding vapor-grown carbon fibers or gas-phase-grown carbon fibers [112]. Compared to the
complex PAN-based process, the manufacturing process for vapor-grown carbon fibers is simpler, faster,
and cheaper and could provide an innovative approach for fabricating high-performance fibers at lower
costs.

The global market demand for carbon fibers in 2016 was 70,000 metric tons [6]. The market is projected
to grow at an annual growth rate of 10 to 13% through 2020 with the market demand expected to exceed
100,000 metric tons in 2020 [7]. The global market value was approximately $2.15B in 2015 [7], which is
projected to grow to $4.2B by 2022. Combined, the aerospace industry including defense, the automotive
industry, and wind turbine manufacturing in the energy sector accounted for between 35,000 to 45,000
metric tons, and continuing growth in these industries is expected to support the high projected annual
growth rate. Although worldwide demand for carbon fibers has increased significantly over the past
decade, the high production costs have limited wider spread use of carbon fibers [112]. Owing to the
complex and multistage manufacturing processes required to produce carbon fibers, only a limited
number of companies are engaged in the mass production of carbon fibers. These companies include
Toray (including its purchase of Zoltek), Toho Tenax, Mitsubishi Chemical, Formosa Plastics, SGL,
Hexcel, DOW, and Kemrock [112, 121].

Analysts believe there is an excellent potential market opportunity for the use of carbon fibers in the
construction industry [6, 113, 114]. An increasing demand for fiber-reinforced plastic bathtubs, doors,
windows, and panels is being spurred on by the continual growth in the U.S. housing market [114].
Another application is concrete reinforced with carbon fibers (i.e., “carbon concrete”), which is
increasingly being used to repair bridges and other aging structures [113]. Using carbon concrete to repair
bridges that are in unsatisfactory condition is considered a major market opportunity. For example, more
than 150,000 of the 600,000 bridges in the United States are considered unsuitable for the current or
projected traffic demands, primarily because of corrosion of the steel reinforcement [122]. Germany is
projected to invest up to €16B to €17B to repair or replace bridges by 2030 [113]. Although the cost of
carbon-reinforced concrete is higher than steel-reinforced concrete, the higher cost is counterbalanced by

4.9
its high specific properties such as lower weight relative to a steel-reinforced concrete deck (which
reduces the load demand on the supporting structure), better corrosion resistance, better seismic
protection, and lower erection and maintenance costs [122]. Worldwide demand for carbon concrete in
2013 was 2300 metric tons, representing revenues totaling $590M. An annual growth rate of 6 to 9% is
projected through 2020, and revenues are projected to exceed $1B by 2022. Lowering the cost of carbon
concrete is considered key to more rapidly increasing its use in the construction industry. Finding
additional applications for carbon fiber and associated composites are also desired.

The Institute for Advanced Composites Manufacturing Innovation (IACMI) is working to advance the
composite industry, developing new manufacturing techniques and identifying potential new markets.
One project is aimed at optimizing vinyl ester resins and fiber sizings for the fabrication of carbon fiber
composites. Advancements will increase scrap and material costs and applications within the automotive
industry has been identified [123].

4.2.3 Carbon Nanotubes

CNTs, including single-walled carbon nanotubes (SWCNTs) and multi-walled nanotubes (MWCNTs),
are used in polymers, electronics, plastics, and energy storage. The major application for CNTs is in
composite fibers in polymers to improve thermal, electrical, and mechanical properties. This application
accounted for over 60% of the market share in 2014. The high molecular complexity of graphene in
MWCNTs increases their tensile strength. MWCNTs are increasingly being used in engineered polymers
including polyetherimide, polycarbonate, and polyetheretherketone. The growing demand for polymers
for use in the automotive and construction industries, particularly in China, India, Brazil, and the Middle
East, is expected to spur market growth [9]. CNTs also are increasingly being used in the production of
lithium-ion batteries for which their use can increase battery efficiency by a factor of 10. The application
growth in lithium-ion batteries for use in grid and renewable energy storage is expected to increase the
demand for CNTs for these applications.

The global CNT market demand for CNTs was slightly over ~5000 tons in 2014 and is projected to grow
to over 20,000 tons by 2022 (Figure 4.7) [9]. This is orders of magnitude lower than for other carbon
products such as carbon black (12 million tons per year). Estimates of market value range from $3.4B
(2022) [9] to $5.6B in (2020) [124]. MWCNTs are the largest production segment given that their
manufacturing cost is significantly lower than that of SWCNTs. Selling prices range from $50/lb
(MWCNT at Hyperion Catalysis) to $600 per gram (SWCNT in defense and niche markets) [8].

The Asia Pacific region is the fastest growing market due to increasing domestic demand coupled with
lower manufacturing costs compared to the United States and Europe. Among the major manufacturers of
CNTs are Arkema S.A. (France), Arry International Group LTD. (China), Carbon Solutions Inc. (United
States), Cheap Tubes Inc. (United States), CNano Technology LTD. (United States), CNT Company Ltd.
(Korea), Continental Carbon Company (United States), Hanwha Chemical Co. Ltd. (Korea), Hyperion
Catalysis international Inc. (United States), KLEAN CARBON Inc. (Canada), Kumho Petrochemical
Company LTD. (South Korea), Nano-C Inc. (United States), Nanocyl S.A. (Belgium), NanoIntegris Inc.
(United States), NanoLab, Inc. (United States), Nanoshel LLC (United States), Nanothinx S.A. (Greece),
Showa Denko K.K. (Japan), SouthWest NanoTechnologies Inc. (United States), Thomas Swan and Co.
Ltd. (United Kingdom), and Toray Industries, Inc. (Japan).

4.10
Figure 4.7. Global CNT Market Estimates and Forecast by Application from 2012 through 2022.
Volume is in tons [9]. (Reproduced with permission from Grand View Research.)

4.2.4 Needle Coke

Needle coke is a premium grade, high-value petroleum coke used in the manufacturing of graphite
electrodes for electric arc furnaces in the steel industry. The main differences between needle coke
and ordinary coke are their structural characteristics, coefficients of thermal expansion, electrical
conductivity, and oxidizability [125]. Needle coke has a high level of graphite resulting from its
microcrystalline structure. A high level of anisotropy, large crystalline size, and large crystal areas must
be achieved to obtain good quality needle coke [10]. The term “needle” is used to describe the acicular
morphology of the coke; it tends to form oriented needle-like structures that are visible to the naked eye.
The coefficient of thermal expansion is one of the most important characteristics of petroleum coke in
evaluating the feasibility of using a particular coke in the production of graphitized items that have a high
resistance to shock [125]. Put simply, carbon with a low coefficient of thermal expansion can dissipate
thermal energy without cracking [10].

Needle coke is typically produced by delayed coking of the heavies remaining after catalytic cracking in a
refinery. Delayed coking is a process for producing coke by transforming a complex mixture of aromatics
to solid carbon [10]. It provides thermal energy to form the mesophase of the precursor during
carbonization. To achieve excellent quality needle coke, two major steps are needed: first, coalescence of
the mesophase to its formation and second, rearrangement of the mesophase in the solidification stage.
Different starting materials will have different chemical make-ups, thus requiring different operating
conditions. These conditions, particularly temperature and pressure, need to be optimized to achieve
quality needle coke. Calcined needle coke is typically higher in carbon and lower in ash constituents, such
as sulfur and metals, than standard calcined petroleum coke. A calcined form of needle coke is the raw
material to produce graphite electrodes used in electric arc steel furnaces. The global market demand for
needle coke is currently approximately 1.5M tons/yr. It has been reported that demand has increased in
recent years and that this trend will continue.

4.11
4.2.5 Aromatics from Natural Gas
Solid carbon as a byproduct can reduce the cost of the CH4 decomposition reaction only if sufficiently
large markets for the carbon products are found. Muradov et al. [20] pointed out that if 100 million tons
of H2 were produced from CH4 decomposition, approximately 300 million tons of byproduct carbon
would be produced. However, annual worldwide consumption of all solid carbon products amounts to
only 15 to 20 million tons, and it is unlikely that there will be any dramatic increase in carbon use in the
near future (additional markets would need to be developed) [20].

An alternative to producing solid carbon product is the conversion of CH4 into hydrocarbons such as
ethylene and/or aromatics such as benzene, in addition to H2. Ethylene and aromatics are commodity
chemicals whose market sizes are greater than existing markets for elemental carbon. Ethylene is widely
used in the chemical industry and had a worldwide production of over 150 million tons in 2016. It is used
primarily to produce polyethylene, a widely used polymer. Ethylene is currently produced by the
petrochemical industry by steam cracking heavier molecular weight hydrocarbons into smaller ones,
which introduces unsaturation. This requires heating to high temperatures of 750 to 950oC. This process is
considered to be one of the most energy-intensive processes used by the chemical industry [126].
Aromatics such as benzene can also be produced via the aromatization reaction; ethylene is considered to
be an intermediate product [127, 128]. Single-ring aromatics, including mixtures of benzene, toluene, and
xylene (known as “BTX”), are generally produced primarily from two sources: refinery catalytic
reforming and pyrolysis gasoline cracking from olefin production. BTX has a large global market demand
of ~100 MT/year. Conventional feedstocks for BTX are currently being reduced because lighter
feedstocks derived from U.S. natural gas availability are reducing the pyrolysis gasoline supply and
gasoline production is declining [129]. A further supply reduction should occur as alternative fuel
vehicles displace internal combustion engine (ICE) vehicles. Thus, there is some incentive to find
alternative feedstocks for BTX in order to fulfill the potential demand. Additionally, the historical price
differential between natural gas and petroleum is an economic incentive to examine aromatics from
natural gas. Stoichiometrically, a majority of the H2 in natural gas would be a byproduct of aromatics
production, as illustrated in Table 4.1.

Table 4.1. Relative Hydrogen Production on Basis of Stoichiometry and Co-Product Values for Carbon,
Benzene, and Ethylene Product Routes
Hydrogen Molar Production Value, Co-Product
Reaction Co-Product
Relative to C Co-Product Case (%) (2014)[130]
CH4  C + 2H2 100.0 Carbon Black 58 ¢/lb
CH4  1/6 C6H6 + 9/6 H2 75.0 Benzene 290 ¢/gal
CH4  ½ C2H4 + H2 50.0 Ethylene 52.7 ¢/lb

We note that direct conversion of natural gas into hydrocarbon fuels and chemicals—not producing
intermediate syngas—has been a long researched field. However, no direct CH4 conversion processes
have progressed to the commercial stage because technical challenges persist [131, 132]. For example, the
yield to useful product and severe catalyst deactivation via formation of carbonaceous deposits (coking)
and metal sintering are problematic [132, 133]. For non-oxidative catalytic CH4 coupling to produce
olefins or BTX directly, the use of high reaction temperatures (~ 1100°C) [127] or catalytic membranes to
reduce the reaction temperatures (<900°C) by separating the H2 from the carbon products [134] to achieve
economically viable yields has met with limited success and faces a number of major technical challenges
including catalyst stability, long-term durability of the ceramic membranes, and cost-effective methods
for recovering the H2. Furthermore, oxidative approaches often over-oxidize products (e.g., CO2
formation) and often require costly separations [131]. Nonetheless, if these longstanding challenges could
be overcome pyrolysis of CH4 into hydrocarbons and hydrogen holds promise.

4.12
4.3 Techno-Economic Assessment
Commercial production of H2 and a carbon product from the decomposition of natural gas will ultimately
depend on the process economics. Capital investment and operating costs will vary with the technology
choice and scale of operations, but it is possible to set some target prices based on information known at
this time. The DOE Fuel Cell Technology Office (DOE-FCTO) has set the cost of H2 dispensed and
delivered at $4/gge (~$4/kg). The economic analysis presented below assumes the following simplifying
assumptions:
 The selling price of H2 is $4/kg
 The cost of CH4 (as the raw material) represents a certain percentage, x, of the total sales revenue.
The value of x will increase as the production process technology matures. That is, higher yield to
desired products will lead to improvements in energy efficiency and lower capital investments. Larger
plants will also improve the economics due to economies of scale. The product yields of H2 and
carbon are the same and proportional to their ratio in the CH4 (i.e., 2 moles of H2 per g-atom of
carbon, or 4 g of H2 per 12 g of carbon).

These assumptions allow one to set the lowest possible price for the carbon product at which the process
can be economically viable. Figure 4.8 shows the relationship between the break-even price of the carbon
product and the cost of CH4 in the plant as a percentage of the revenue from selling the H2 and carbon
products for three different prices of natural gas. For example, with x = 50% and a natural gas price of
$2.95 per million BTU (MBtu), the carbon product price needs to be greater than $6.53/kg.

Figure 4.8. Break-Even Price of Carbon Products vs. the Cost of Methane as a Percentage of the
Revenue from the Sale of Hydrogen and Carbon Products, as Functions of the Price of
Methane. Price of H2 = $4/kg.

It was found with this analysis that at less than a $1/kg, carbon black is not a viable final product.
However, higher value products such as graphite, graphene, nanocarbons, and/or needle coke would
enable the decomposition process to be economically viable.

4.13
With this high level pricing analysis in place, a separate set of process economics were evaluated in more
detail for low-temperature plasma conversion of CH4 using ASPEN modeling. The low-temperature
plasma conversion was modeled at the small scale of 1900 kg H2/day. Conversion at 700°C with a 100°C
approach to equilibrium was used to determine the reaction products. An ASPEN Plus® simulation was
used to determine the material and energy balance and operating costs. The ASPEN Process Economic
Analyzer® was used to assess capital cost. The capital cost and unit ratio information was then transferred
to an H2A spreadsheet for this process for economic evaluation.

The bottom-line energy requirements, CAPEX, byproduct production, and resulting H2 cost summary is
presented in 2007 U.S. dollars in Table 4.2. As expected it was found that the production and sale of
carbon black in the plasma process reduces the net cost of H2. However, it should be noted that the price
assigned to the carbon black byproduct greatly affects the resulting H2 cost, as illustrated in the sensitivity
analysis shown in Figure 4.9 for the small-scale plasma case. In Table 4.2, we assume a carbon black
selling price of $1.35/kg, resulting in an H2 cost reduction from $7/kg down to $2.5/kg due to the
byproduct credit. For comparison, the current cost of H2 from steam methane reforming of natural gas is
less than $2/kg over a wide range of natural gas prices and for different production volumes [135].
Nonetheless, these process economic results demonstrate how the cost of H2 can be substantially driven
down in emerging technologies such as plasma NG pyrolysis by the sale of valuable carbon byproduct-
and the carbon selling price is a critical factor. Ongoing research and development is needed to further
reduce the costs of such emerging technologies.

Figure 4.9. Sensitivity of Carbon Black Selling Price on Net Hydrogen Cost for the Small-Scale Plasma
Case Study

4.14
Table 4.2. Hydrogen Cost, Requirements, and Byproduct Production Summary for the Techno-
Economic Cases Analyzed in this Study. (Assumptions: hydrogen cost before compression
and delivery; electricity price = $0.056/kWh; natural gas price = $5/MMBTU; carbon black
selling price = $1.35/kg.)
H2 Carbon
Production Electric Power Natural Gas Black
Scale Requirement Requirement CAPEX Byproduct H2 Cost
Technology (kg/day) (kWh/kgH2) (MMBtu/kgH2) (MM$) (kg/kgH2) ($/kg)

Plasma 1,914 16.1 0.26 11.4 3.1 7.0


(Small Scale
without Byproduct
Credit)

Plasma 1,914 16.1 0.26 11.4 3.1 2.5


(Small Scale with
Byproduct Credit)

4.15
5.0 Technology Barriers to Commercial Implementation and
R&D Opportunities
In Table 5.1, we summarize potential carbon products and provide an assessment of the status of natural
gas conversion technology, major barriers to commercial implementation, and R&D needed to overcome
these barriers. We focus here on solid carbon versus hydrocarbon (e.g., aromatic) products.

Table 5.1. Summary of Carbon Products and Natural Gas Conversion Technology Status, Major
Barriers to Commercial Implementation, and R&D Needs to Overcome Barriers
Type of Technology Major Barriers in Technology R&D Needed to Overcome
Carbon Status Applications and Scaling Up Barriers
Carbon Commercialized  Ability to produce multiple grades of  Reaction studies to define
black, carbon black using natural gas as a operating parameters and reactor
thermal feedstock to provide greater flexibility designs for producing different
to meet to market demand grades of carbon black
 Lack of downstream processes to  Separations and recovery
recover and produce industrial-grade process technology development
high-purity H2 to produce industrial-grade high-
 Impact of producing industrial-grade purity H2 at a cost-competitive
high-purity H2 on the overall process price
efficiency and production costs of  Demonstrate an integrated
carbon black process for producing carbon
 Production cost of H2 needs to be black and recovering industrial-
competitive with H2 produced by SMR grade high-purity H2 that
maximizes overall product
yields of carbon black and H2
and produces both products at
market-competitive prices
 Techno-economic analysis to
determine the cost of recovering
H2 and its impact on producing
H2 and carbon black at market-
competitive prices at various
production capacities

5.1
Type of Technology Major Barriers in Technology R&D Needed to Overcome
Carbon Status Applications and Scaling Up Barriers
Carbon Pilot-scale tests  Ability to produce multiple grades of  Reaction studies to define
black, demonstrated, carbon black using natural gas as a operating parameters and reactor
plasma first commercial feedstock to provide greater flexibility designs for producing different
plant expected to to meet to market demand grades of carbon black
be operational in  Lack of downstream processes to  Separations and recovery
2018 recover and produce industrial-grade process technology development
high-purity H2 to produce industrial-grade high-
 Impact of producing industrial-grade purity H2 at a cost-competitive
high-purity H2 on the overall process price
efficiency and production costs of  Demonstrate an integrated
carbon black process to produce carbon black
 Production cost of H2 needs to be and recover industrial-grade
competitive with H2 produced by SMR high-purity H2 that maximizes
overall product yields of carbon
black and H2 and produces both
products at market-competitive
prices
 Techno-economic analysis to
determine the cost of recovering
H2 and its impact on producing
H2 and carbon black at market-
competitive prices at various
production capacities
Carbon fiber Commercialized  Lower production capacity of the  Process development to increase
vapor-grown carbon nanofiber process production capacity to allow
compared to PAN- and pitch-based vapor-grown carbon fibers
processes process to compete with PAN-
 Downstream processing to recover and and pitch-based processes
produce industrial-grade high-purity  Separations and recovery
H2 process development to recover
 Impact of producing industrial-grade industrial-grade high-purity H2
high-purity H2 on the overall process  Demonstrate an integrated
efficiency and production costs of process to produce carbon fibers
carbon fibers and recover industrial-grade
 Production cost of H2 needs to be high-purity H2 that maximizes
competitive with H2 produced by SMR overall product yields of carbon
fibers and H2 and produces both
products at market-competitive
prices
 Techno-economic analysis to
determine the cost of recovering
H2 and its impact on producing
H2 and carbon fibers at market-
competitive prices

5.2
Type of Technology Major Barriers in Technology R&D Needed to Overcome
Carbon Status Applications and Scaling Up Barriers
Carbon Commercialized  Low production capacity of vapor-  Process development to increase
nanotubes grown carbon nanotubes process production capacity of carbon
 Downstream processing to recover and nanotubes
produce industrial-grade high-purity  Separations and recovery
H2 process development to recover
 Impact of producing industrial-grade industrial-grade high-purity H2
high-purity H2 on the overall process  Demonstrate an integrated
efficiency and production costs of process to produce carbon
carbon nanotubes nanotubes and recover
 Production cost of H2 needs to be industrial-grade high-purity H2
competitive with H2 produced by SMR that maximizes overall product
yields of carbon nanotubes and
H2 and produces both products
at market-competitive prices
 Techno-economic analysis to
determine the cost of recovering
H2 and its impact on producing
H2 and carbon nanotubes at
market-competitive prices
Needle Coke Commercialized  Ability to produce highly crystalline  Process development aimed at
needle coke from natural gas is not producing needle coke needed
well understood  Understand quality of crystalline
 Downstream processing to recover and carbon formation and evaluate
produce industrial-grade high-purity suitability as a needle coke
H2 precursor
 Production cost of H2 needs to be  Separations and recovery
competitive with H2 produced by SMR process development to recover
industrial-grade high-purity H2
 Techno-economic analysis to
determine cost of recovering H2
and its impact on producing H2
and needle coke at market-
competitive prices

5.3
6.0 Conclusions
The major findings and conclusions from this study are outlined below:
 Processes for decomposing natural gas to generate carbon and H2 are attractive because of the current
low cost of natural gas and the available infrastructure for delivery of natural gas to the conversion
plant, which allows for flexibility in plant location. Production costs and demand for carbon and H2
will be key factors in determining the optimal production capacity and location of these plants.
 Non-catalytic thermal decomposition of natural gas is currently used in the carbon black industry to
produce carbon black for use in tires and electrical equipment, but natural gas as the feedstock has
been largely replaced by heavy oil fractions from crude oil processing. H2 is burned to provide
process heat. Because these processes operate at high temperatures, off-gas treatment that
significantly increases the capital cost is required to reduce nitrogen oxides and other emissions.
Additionally, the high reaction temperatures required for CH4 conversion contributes greatly to
process inefficiencies. The high reaction temperatures also limit the choice of materials of
construction, adversely impact catalyst life, and exacerbate heat losses.
– Despite historically low natural gas prices, it is not clear whether existing oil-furnace process
facilities can be retrofitted to burn natural gas (as is done in the power industry).
– Emissions control, particularly of nitrogen oxides, is a major issue with many of the major
U.S. carbon black producers that have been fined by the U.S. Environmental Protection Agency
in recent years and have had to install expensive gas cleanup systems. This could be a major
technical issue for a small-scale distributed facility.
– The purity of the H2 is not known because it is burned to provide process heat. Cleanup will be
necessary to produce fuel-cell-quality H2.
 Catalytic thermal decomposition has been extensively researched at the laboratory scale, primarily to
reduce the temperature required for conversion. A wide range of metal and carbon-based catalysts
have been reported in the literature. Nickle, cobalt, and iron are the most studied metal catalysts, and
they produce both amorphous and structured carbons. Amorphous carbons such as activated carbon
and carbon black are more active than structured carbons such as graphite and diamond. Data from
the literature do not delineate the effect of catalysts and process conditions on the quality/morphology
of the carbon product. Reactors have been demonstrated or proposed with intermittent fixed beds or
fluidized beds.
– At least one potentially commercial process, UOP’s HYPRO™ process, was developed in the late
1960s, but it was not cost-competitive with SMR. Carbon was burned during the catalyst
regeneration stage to generate process heat.
– The National Aeronautics and Space Administration, the U.S. Department of Defense, and the
DOE have funded a number of pilot-scale demonstrations for producing fuel-cell-quality H2 in
which the carbon is burned to regenerate the catalyst.
– Although several highly-active catalyst material formulations have been employed, further
catalyst material development is needed, since any process will require extensive recycling of the
catalyst (i.e., carbon deposition/carbon removal). Catalyst mechanical stability will be an issue
because the process of carbon deposition on catalysts surface leads to detaching the catalyst from
the support as the carbon is deposited. Separation of the catalyst and the carbon byproduct
remains a challenge.

6.1
– Cost-competitive and process-effective technologies for recovering the carbon (separating the
carbon from the catalyst) will require further R&D. It is not clear whether carbon can be
recovered without having to burn a portion of it to fully regenerate the catalyst. Retention of a
portion of the catalyst, particularly Ni-based catalysts, in the carbon product could be a regulatory
problem.
– It is not clear what effect catalysts have on the grade of carbon produced and how much this can
be controlled by the catalyst. Optimizing the catalyst/process to produce the desired grade of
carbon represents an R&D opportunity. Preventing the gas-deposition of carbon during a catalytic
process could be a major issue depending on the grade of carbon being produced and product
specifications.
– Optimizing the process to produce both the desired grade of carbon and fuel cell-grade H2,
particularly if a carbon with very tight product specification is being produced, could be a major
challenge. It may require less than ~100% single-pass CH4 conversion, which increases the
complexity with added separations and recycle burdens. Current processes for producing carbon
are not overly concerned with the H2 purity because the hydrogen is combusted to provide heat. It
will be a major challenge for processes targeting high-value carbons, such as nanofibers, to
achieve high-quality product carbon and H2 products.
 Plasma processes for producing carbon and H2 require electric power (expensive and produced with
low efficiencies) and plasma gas.
– Non-thermal equilibrium plasmas are not considered energetic enough to produce carbon and H2
at the production scales required.
– Studies have suggested that DC plasma processes could be economically competitive for
producing H2 with alternative processes. DC plasma processes operate at extremely high
temperatures and producing large reaction volumes with DC plasma is an issue.
– The AC three-phase plasma process is being commercialized by Monolith Materials in Hallam,
Nebraska. The technology has been demonstrated at various pilot scales in Europe.
 Molten-metal technology has been reported and a major benefit is its relative ease of solid carbon
separation from the molten metal. Density differences make separation of carbon from molten metal
easier. However, high temperature for conversion still is required.
 Solar thermochemical processes rely on solar augmentation for heating. However, non-catalytic
processes require high temperature (e.g., 1600°C) and this makes the use of costly materials of
construction. Catalytic processes would drive down operating temperature requirements, but solid
carbon handling remains an issue. Finally, the cost of a “solar” plant is an issue.
 Our techno-economic analysis suggests that the net cost of H2 can be drastically reduced to below the
$2/kg - the Office of Energy Efficiency & Renewable Energy H2 cost target (before compression and
delivery) when the carbon is sold as byproduct. However, the economics are largely driven by the
value and quality of the carbon byproduct.
 No known commercial process produces both carbon and H2 (fuel cell quality) as commercial
products. There are commercial processes for producing carbon that burn some of the H2 to provide
process heat for the reaction and burn the rest to provide process heat to the facility or nearby
facilities. There are also commercial processes for producing fuel-cell-quality H2, but carbon is not
recovered. Carbon is burned to regenerate the catalyst and to provide process heat.

6.2
Areas of opportunity for R&D in the CH4 pyrolysis technical space include the following:
 The natural gas infrastructure allows for setting up a distributed H2-refueling network and distributed
fuel cell power networks. Producing H2 is also achievable using SMR or water electrolysis using
wind (or other renewable) energy. These processes also produce pressurized H2. The natural gas
decomposition process will have to compete with the above alternatives to produce a higher value
product—derivable from the carbon combined with any environmental credit for not producing CO2.
 High-pressure, low-temperature decomposition would reduce the cost of the product. Innovation/
breakthroughs in technology will be required to overcome the thermodynamic limitations that restrict
the high yields of H2 and carbon at these conditions.
 Solid carbon separation, classification by value, and handling are key challenges. H2 production is
relatively easy because all of these processes use high temperatures. Even cleanup/purification is
manageable with PSA. The next steps of compression and delivery drive up the cost of H2. Therefore,
a high-value byproduct is needed to offset this cost.
 High-value carbon markets do exist. For example, graphite is a high-value product used in lithium-ion
batteries. Nanotube carbons also are high-value products (20 kilotons/yr by 2022). However, suitable
technologies optimized for producing both H2 and valuable carbon byproduct must be developed.
Furthermore, solid carbon as a byproduct could reduce costs only if sufficiently large markets for the
carbon products are found. One alternative to the production of solid carbon is the production of
hydrocarbons such as BTX that have a large global market demand of ~100 million tons/yr.
Challenges include low conversion levels and catalyst stability, which are key technological barriers
to commercial implementation.
 The overarching challenges for producing these high-value carbon products are 1) identification of
the conditions at which the different grades of carbon will be formed during the decomposition
process, 2) separation of the different grades of carbon, and 3) competition from alternative feedstock
sources. For example, petcoke from refineries is cheap and can be processed to produce graphite.

6.3
7.0 References
[1] Alibaba.com, "Market price for carbon black," https://www.alibaba.com/showroom/market-price-for-
carbon-black.html, Accessed August 14, 2017.

[2] Grand View Research, "Carbon black market analysis by application (tires, high performance
coatings, plastics) and segment forecasts to 2022," http://www.grandviewresearch.com/industry-
analysis/carbon-black-market, Accessed August 14, 2017.

[3] Grand View Research, "Carbon black market size to reach USD 28.05 billion by 2022,"
http://www.grandviewresearch.com/press-release/global-carbon-black-market, Accessed August 14,
2017.

[4] Benchmark Mineral Intelligence, "Graphite demand from lithium ion batteries to more than treble in
4 years" http://benchmarkminerals.com/graphite-demand-from-lithium-ion-batteries-to-more-than-treble-
in-4-years/, Accessed on August 14, 2017.

[5] S. Das, J. Warren, D. West, S.M. Schexnayder, Global carbon fiber composites supply chain
competitiveness analysis, Technical Report ORNL/SR-2016/100 | NREL/TP-6A50-66071 Oak Ridge
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7.9
 
R&D Opportunities
For Development of
Natural Gas Conversion
Technologies
For Co-Production of Hydrogen and
Value-Added Solid Carbon Products

ANL-17/11; PNNL-26726 • November 2017

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