Estimation of methane fugitive emissions from hydrogen

production process via coal gasification

S Shabana, H Mimi Haryania*, A A Yousefa

*Department of Chemical Engineering, Universiti Teknologi Malaysia, 81310

Johor Bahru, Johor, Malaysia,
a
Department of Chemical Engineering, Universiti Teknologi Malaysia, 81310
Johor Bahru, Johor, Malaysiails

Keywords: Fugitive Emissions; Hydrogen Production; Coal Gasification; Methane.

ABSTRACT
Coal gasification is one of the cheapest ways to manufacture hydrogen on a large scale. However, significant quantities of
methane and carbon dioxide can be generated depending on the gasification technology employed. This paper presents the
estimation of methane and carbon dioxide fugitive emissions from hydrogen production process via coal gasification route. It
was imperative to first establish a database for fugitive emission rates for the new process modules (gasifier and cyclone). This
was accomplished by studying typical piping and instrumentation diagrams of the gasifier and cyclone used in a coal based
process and analyzing the number of potential leak sources in these operations. The stream weight composition data was then
obtained through simulation. The stream emission rates were already tabulated, making it possible to calculate the fugitive
emission rates of each chemical component present in the production process. Carbon dioxide had the highest fugitive
emissions whereas hydrogen sulfide had the least. The highest release of fugitive emissions was from the absorber and the least
from the cyclone. Although methane is reported to have a global warming potential value 21 times greater than that of carbon
dioxide by the IPCC, the production of hydrogen via coal gasification yields more carbon dioxide fugitive emissions whose
contribution to global warming potential is much more significant than methane.

ABSTRAK
Dewasa ini, berikutan permintaan tenaga yang semakin meningkat, seluruh dunia mempertimbangkan hydrogen sebagai
pengganti bahan api fosil pada masa depan sebagai usaha untuk mencapai keseimbangan antara krisis tenaga dan isu alam
sekitar. Proses pegegasan arang batu adalah salah satu cara yang paling murah untuk menghasilkan hydrogen pada skala yang
besar. Walaubagaimanapun, kuantiti metana dan karbon dioksida yang besar boleh dihasilkan bergantung kepada teknologi
proses pengegasan yang digunakan. Kajian ini membentangkan nilai anggaran metana dan karbon dioksida yang dilepaskan
daripada proses penghasilan hydrogen melalui proses pengegasan arang batu. Ia amat penting untuk mewujudkan suatu
pengkalan data mengenai kadar pelepasan gas-gas metana dan karbon dioksida untuk proses modul baru (gasifier dan cyclone).
Objektif ini dapat dicapai dengan mengkaji saliran paip dan diagram instrumentasi gasifier dan cyclone yang digunakan dalam
proses berasaskan arang batu dan menganalisis jumlah sumber kebocoran yang berpotensi dalam operasi ini. Datakomposisi
jisim aliran kemudiannya diperoleh melalui simulasi. Kadar pelepasan aliran yang telah dijadualkan memudahkan pengiraan
kadar pelepasan setiap komponen kimia yang hadir dalam proses pengeluaran. Karbon dioksida mempunyai pelepasan pintasan
tertinggi berbanding hydrogen sulfida. Pembebasan tertinggi pelepasan pintasan adalah daripada absorber, manakala cyclone
mencatat pelepasan yang lebih rendah. Walaupun IPCC melaporkan bahawa metana berpotensi mempunyai nilai pemanasan
global 21 kali lebih besar daripada karbon dioksida, pengeluaran hydrogen melalui pengegasan arang batu menghasilkan kadar
pelepasan karbon dioksida yang lebih banyak, di mana sumbangannya terhadap pemanasan global adalah lebih besar
berbanding metana.

energy conversion efficiency with essentially zero emissions

INTRODUCTION
Hydrogen is being considered worldwide as a future
replacement for gasoline, diesel fuel, heating oil, natural gas,
and other fuels in both the transportation and industrial
sectors because it is environmentally friendly, it has a high
(Stiegel and Ramezan, 2006). Hydrogen has become a more
attractive clean fuel (Inayat et al., 2010) and its economy has
been promoted due to lager number of hydrogen applications
in petroleum and chemical sectors such as upgrading crude oil
and synthesizing of methanol and ammonia. Currently, about
98% of hydrogen is produced from fossil fuels (Kalinci et al.,

1
2009). This over dependence on fossil fuels can eventually
lead to their exhaustion since they are finite resources and this
has become a serious concern, hence the search for alternative
feedstock for hydrogen production has been intensified (Khan
et al., 2010). Hydrogen can be produced from a variety of
widely available primary energy sources, including coal,
natural gas, biomass, wastes, solar, wind, or nuclear power
(Kim, 2003).
Coal gasification is one of the cheapest ways to
manufacture hydrogen in large scale industry however it only
accounts for about 19% of the worldwide production of
hydrogen (Stiegel and Ramezan, 2006). Gasification is a key
technology for a more efficient power generation from coal
because (i) of the readily global availability of coal as a raw
material, (ii) it is a cheaper power generation option to natural
gas, (iii) it can be utilized to produce valuable products and
(iv) the ability of eliminating nearly all air pollutants and
potential greenhouse gas emissions. The process possesses
good environment performance compared to the other
combustion technologies (Suárez-Ruiz and Crelling, 2008). A
good gasification process should provide relatively high
hydrogen concentration with nearly zero carbon dioxide and
tar concentrations in the gasification products. Coal
gasification has been identified as a key enabling technology
for a range of efficient and sustainable systems for producing
low emissions electricity and other energy products from coal
(Corella et al., 2006, Yunhan, 2001, EIA, 2006).
During the gasification process, oxygen reacts with coal
to form heat, carbon dioxide and water whereas steam reacts
with carbon to form carbon monoxide and hydrogen (Vick,
1981). Depending on the gasification technology employed,
significant quantities of water, carbon dioxide and methane
may be present (Speight, 2014). The major concern however
is that the resulting emissions from the utilization of coal are
greater than those from any other method of producing
hydrogen. According to the study conducted by Jin, Lu, Liao,
Guo, & Zhang (2010) - when the concentration of coal is low,
the order of gaseous product fraction is H2 > CO2 > CH4 >
CO. They further indicated that when the concentration of
coal is high, the reaction (C + H2O → CO + H2) is inhibited
and reaction (CO + 3H2 → CH4 + H2O) is promoted due to
insufficient supply of water. This signifies that with
increasing concentration of coal, the hydrogen fraction
decreases while that of methane increases (Jin et al., 2010).
Therefore this motivated this study which was to estimate the
amount of methane fugitive emissions from hydrogen
production process via coal gasification route.
TECHNIQUES OF FUGITIVE EMISSIONS ESTIMATION
The average emission factor is the most suitable option
for quantifying fugitive emissions. It only requires limited
process information which can be obtained even from a very
early stage of conceptual design. This approach however
requires equipment and piping item count for P&ID stage as
well as average emission factors (Hassim et al., 2010). As
described in Hassim et al (2010), pre-calculated modules refer
2
to a set of fugitive emission rates data that has been pre-
calculated for standard module types in a chemical process.
The pre-calculated modules data was created by analyzing the
number of potential leak sources in these operations. This was
accomplished by studying typical piping and instrumentation
diagrams (P&IDs) of the process modules. For
comprehensiveness, the emission from each module stream is
calculated for all possible types of service - gas/vapor, light
liquid, and heavy liquid (EPA, 1988).
Detailed PFDs provide additional process data of mass
and energy balances. Process drawing is first divided into
standard modules. Based on process descriptions, chemicals
present in each module stream are then identified. The
stream’s service type is then classified based on the pure
chemical vapor pressures of components at 20 oC in the
mixture. In a particular stream, if the chemicals with vapor
pressure above 0.3 kpa (at 20 ⁰C) represents ≥ 20 wt% of the
total weight composition, the stream is in a light liquid
service - else, it is in a heavy liquid (Hassim et al., 2010). The
fugitive emissions from the module streams are determined
by referring to the database of pre-calculated fugitive
emission rates for process module stream summarized in
Table 2 as shown in Hassim et al (2010). The stream
emission rate is multiplied with the weight composition of the
respective components in that particular stream. Weight
compositions are used throughout the calculation since the
EPA emission factor data is weight-based. Similarly, the
emissions of the same chemical substances throughout the
process are summed up.
CASE STUDY – HYDROGENE PRODUCTION VIA COAL
GASIFICATION ROUTE
As illustrated in Figure 1, the gasification process begins
with coal entering the system mixed with water creating
slurry that has the consistency of heavy oil. The slurry is
injected into the gasifier along with oxygen where it is heated
to very high temperatures to produce syngas, which is
primarily hydrogen and carbon monoxide. The cyclone is
responsible for the separation of entrained particles from the
syngas for recycle to the gasifier. The hot syngas is then fed
into the radiant syngas cooler where the heat from the gas is
transferred to the high pressure steam system for integration
into the steam power production cycle of the plant. The
syngas moves to the low temperature gas cooling system
where more heat is extracted for useful work. The syngas
passes through an activated carbon bed that removes mercury
and once it leaves this area, there are almost undetectable
amounts of mercury. It then continues to the absorber where
hydrogen sulphide is separated from the syngas and later
converted into elemental sulphur that can be used in chemical
processing. Syngas goes to a highly efficient and cleaner
burning gas turbine combined cycle plant to create electricity.
Excess high pressure nitrogen from the air separation unit is
used in the gas turbine as a diluent in the combustion process
to reduce the formation of nitrogen oxides, a regulated
pollutant that is known to create smog (Stiegel and Ramezan,
2006, DOE, 2013). The synthesis gas must be cleaned of
these minor and trace components to pre-determined levels count for the gasifier and cyclone process modules are
consistent with further downstream processing. The PSA unit summarized in Table 1.
purifies the hydrogen to approximately 99.9%. Once the
synthesis gas is sufficiently cleaned, it is routed to the water- Process module (Fugitive emission rate, kg/h)
gas shift reactor where the CO in the gas is reacted with water
Stream Service Gasifier Cyclone
over a catalyst to produce additional H2 and CO2. The H2
and CO2 are then separated with hydrogen being used in gas G/V 0.0756 0.03207
turbines, highly efficient fuel cells, or distributed for use as Inlet LL 0.0659 0.02819
fuel in the transportation sector, while the CO2 can be HL 0.0469 0.02059
sequestrated and is injected deep into geological formations
such as aquifers for permanent storage (gas-tail) (DOE, G/V 0.04122 0.00366
2013). Outlet LL 0.03734 0.00366
HL 0.02974 0.00366
DEVELOPMENT OF PRE-CALCULATED EMISSIONS G/V: Gas/Vapor, LL: Light Liquid, HL: Heavy
DATABASE FOR NEW PROCESS MODULES Liquid
As described in the previous sections, the hydrogen
production process for this particular case study involves Table 1: Database of pre-calculated fugitive emission rates for
several process units, that is, gasifier, cyclone, low new process module stream.
temperature and high temperature shifting reactors, absorber,
pressure swing adsorber and the tank tail. However, fugitive FUGITIVE EMISSION RATE FOR EACH PROCESS
emission rates for the gasifier and cyclone are not available in MODULE
the database. Therefore it was imperative to establish a
database for fugitive emission rates for the new process Table 2 summarizes fugitive emission rates for each
modules, that is, the gasifier and cyclone. The pre-calculated process module. However certain conditions were taken into
modules data was created by analyzing the number of consideration, (i) The inlet stream emission rate for the
potential leak sources in these operations. This was gasifier was considered to be of a heavy liquid service type
accomplished by studying typical piping and instrumentation because the slurry fed into the gasifier has properties similar
diagrams (P&IDs) of the gasifier and cyclone used in a coal to heavy oil, (ii) Most plants normally have 2 absorbers, one
based process, that is, hydrocarbon upgrading gasification as the functioning unit and the other as back-up. Initially, the
program (Darby, 2011). inlet and outlet emission rates were 0.024 kg/h and 0.109 kg/h
but since 2 absorbers were taken into consideration, the new
emission rates were 0.048 kg/h and 0.218 kg/h.

Process Inlet Outlet 1 Outlet 2

Unit (kg/h) (Kg/h) (kg/h)
Gasifier 0.0469 0.041225528

Cyclone 0.032074301 0.003660505

LTSR 0.0589705 0.1629996

HTSR 0.058999855 0.162999642

Absorber 0.047999895 0.217998852

PSA 0.057299698 0.0573 0.057302599
Storage
0.147536692 0
tank
Figure 1: Process flow diagram for the hydrogen production
process from coal gasification. Table 2: Fugitive emission rates for each process module.

This approach needs equipment and piping item count
for P&ID stage and calculations. The calculation made use of
the average emission factors provided by the U.S.
Environmental Protection Agency for traditional component
types (EPA, 1988). Consideration was however given to the
main inlet and outlet streams and details of the equipment
TOTAL EMISSIONS OF EACH CHEMICAL FROM EACH
PROCESS MODULE
As described in Hassim et al (2010), to be able to
determine the fugitive emissions of each individual chemical
component, the stream emission rates (Table 2) are multiplied
by the chemical’s weight compositions (data obtained

3
through simulation) results of which are summarized in Table
3. Several chemicals were identified throughout the Emission GWP
production process. However major consideration was given GHGs GHG (%) GWP1 GWP (%)
(g/kg of H2) Value2
to methane and carbon dioxide because of the role they play
CO2 0.0442 99.79 1 0.0442 95.88
in global warming, and carbon monoxide because of its
impact on public health. CH4 9.0759E-05 0.21 21 1.9E-03 4.12
1
Relative to CO2 (100 year IPCC)
GLOBAL WARMING POTENTIAL 2
GWP Value (g CO2- equivalent/kg of H2)
In order to calculate the GWP value, the individual
fugitive amounts were multiplied by the GWP values as Table 4: Global warming potential due to greenhouse gas
stipulated by the Intergovernmental Panel on Climate Change fugitive emissions.
(IPCC) (Danny Harvey, 1993), that is, 1 and 21 for Carbon
dioxide and methane respectively. As summarized in Table 4, CONCLUSION
the amount of carbon dioxide released during the production
The capacity of the plant after simulation was estimated
of hydrogen through coal gasification has a much higher
at 12120 kg of hydrogen per hour. This production process
GWP (95.88%) than the methane (4.12%) emitted during the
leads to the release of a fugitive amount of 1.153 kg/h with
same process. This might be likely due to the fact that coal is
the highest release coming from the Absorber (0.266 kg/h)
a high carbonaceous compound hence more carbon dioxide
and the least emissions from the cyclone (0.036 kg/h). Carbon
will be produced.
dioxide had the highest fugitive emission amount throughout
the whole production process (0.5358 kg/h) whereas
Fugitive emission rate for each chemical (kg/h) hydrogen sulfide had the least (0.0001 kg/h). Methane
Stream
CH4 CO CO2 NH3 H 2S fugitive emissions throughout the production cycle were
Gasifier estimated at 0.0011 kg/h whose contribution to global
0 0 0 0 0
Inlet: 1 warming potential is 4.12% while carbon dioxide fugitive
Outlet: 2 6.8E-05 0.0106 0.0064 8.4E-05 5.5E-06 emission rate is at 0.5358 kg/h with a global warming
Cyclone potential contribution of 95.88%.
5.3E-05 0.0083 0.0050 6.6E-05 4.3E-06 Although methane is reported to have a global warming
Inlet: 2
potential value 21 times greater than that of carbon dioxide by
Outlet: 4 6.2E-06 0.0010 0.0006 7.7E-06 5.0E-07 the IPCC, the production of hydrogen via coal gasification
LTSR yields more carbon dioxide fugitive emissions whose
0.00006 0.0175 0.0165 0.0001 0.00001
Inlet: 5 contribution to global warming potential is much more
Outlet 6 significant than methane.
0.00017 0.0290 0.0760 0.0002 3.0E-05
HTSR
Inlet: 6 0.00006 0.0105 0.0275 7.9E-05 1.1E-05 The study recommended that: 1. Due to the high amount
of carbon dioxide being released during the production
Outlet: 7
0.00017 0.0174 0.0942 0.0002 3.0E-05 process, there should be improved carbon capture and storage
Absorber technologies. 2. Direct measurement of fugitive emissions is
Inlet: 7 0.00005 0.0051 0.0277 6.5E-05 8.9E-06 recommended as a way to improve the efficiency and
Outlet: 8 effectiveness of leak repair and to quantify reductions in
0.0002 0.0232 0.1260 0.0003 0
PSA fugitive emissions as a result of improved leak detection and
Inlet: 8 0.00006 0.0061 0.0331 7.7E-05 0 repair. 3. If further studies were to be conducted, it would be
Outlet: 9 0 0 0 0 0 recommended that estimates of stack emissions from
hydrogen production process via coal gasification be
Outlet:10 measured and comparisons made with the results obtained in
0.00006 0.0063 0.0343 8.0E-05 0
Tank this study.
Inlet: 10 0.0016 0.0163 0.0885 0.0002 0
Total 0.0011 0.1513 0.5358 0.0014 0.0001 REFERENCES

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