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Removal of Sulfur Contaminants in Natural Gas Streams
Removal of Sulfur Contaminants in Natural Gas Streams
A Thesis
Presented to the
Master of Science
Fall 2019
© Jerry F. Conerly III
2019
APPROVED:
Chapter 3: Objectives........................................................................................................ 17
iv
5.2.2 Graphite blend experiments. ............................................................. 49
5.2.3 Clay blend experiments. .................................................................... 53
5.2.4 Sulfatreat experiments....................................................................... 56
5.2.5 Anthracite blend experiments. .......................................................... 57
5.2.6 Experimental catalysts comparison to literature. ............................. 61
5.3 Economics ......................................................................................................... 75
Bibliography ...................................................................................................................... 82
Appendix A ........................................................................................................................ 86
Abstract ............................................................................................................................. 87
v
List of Tables
Table 10: Material Cost per 1000 ft 3 Treated Gas at each Variation ................................... 77
vi
List of Figures
Figure 7: Micromeritics ASAP 2020 Surface Area and Porosimetry Analyzer .................... 29
vii
Figure 24: Graphite Methyl Mercaptan Breakthrough vs Time ........................................... 52
Figure 36: Methyl Mercaptan Breakthrough at 100 psi 100℃ 50 mL/min .......................... 63
Figure 37: Ethyl Mercaptan Breakthrough at 100 psi 100℃ 50 mL/min ............................. 64
Figure 39: Methyl Mercaptan Breakthrough at 100 psi 100℃ 36 mL/min .......................... 65
Figure 40: Ethyl Mercaptan Breakthrough at 100 psi 100℃ 36 mL/min ............................. 65
Figure 42: Methyl Mercaptan Breakthrough at 100 psi Amb 50 mL/min ............................ 66
Figure 43: Ethyl Mercaptan Breakthrough at 100 psi Amb 50 mL/min ............................... 67
Figure 45: Methyl Mercaptan Breakthrough at 100 psi Amb 36 mL/min ............................ 68
Figure 46: Ethyl Mercaptan Breakthrough at 100 psi Amb 36 mL/min ............................... 68
Figure 48: Methyl Mercaptan Breakthrough at 200 psi Amb 36 mL/min ............................ 69
viii
Figure 49: Ethyl Mercaptan Breakthrough at 200 psi Amb 36 mL/min ............................... 70
Figure 51: Methyl Mercaptan Breakthrough at 200 psi 100℃ 36 mL/min .......................... 71
Figure 52: Ethyl Mercaptan Breakthrough at 200 psi 100℃ 36 mL/min ............................. 71
ix
Chapter 1: Introduction
effluents. One particularly undesirable compound is hydrogen sulfide (H2 S), and it causes
complications primarily in the energy sector whose products such as natural gas, liquefied
petroleum gas, tail gas, fuel cells and the transportation gases like diesel, gasoline and jet
fuel, either naturally contain, consume, or form the compound in the production process. It is
considered a major problem in industry due to health hazards, catalyst poisoning, and strict
Natural gas production contains H2 S, which is an acid gas. Natural gas containing
more than 5.7 mg/m3 H2 S is labeled sour gas. The Scientific Advisory Board on Toxic Air
Pollutants has set acceptable levels of ambient H2 S to be in the range of 20-100 ppb (Vikrant
et al., 2018). OSHA has set the H2 S allowable exposure limit to be 10 ppm time-averaged
over 8 hours (Tian, Wang, Yu, Li, & Guo, 2017). It is detrimental to pipeline health due to
corrosion such as hydrogen blistering, hydrogen embrittlement, pitting, and stress cracking
(Fontana, 1986).
convert various sulfur compounds into H2 S and sulfur-free organics using catalytic treatment
with hydrogen. Most catalysts in use are alumina-based that has been impregnated with
cobalt and molybdenum. The HDS reactor is typically operated at elevated temperature
ranges from 573 K to 673 K and elevated pressures ranging from 30 atm to 130 atm. The
converted H2 S is then removed from the gas stream via amine scrubbing and the Claus
1
Process. HDS is considered expensive due to the energy demand and costs of high purity
Amine scrubbing has been used for H2 S removal along with CO2 for many years.
Alkanolamines, being basic in nature, are suitable for acid gas absorption, such as H2 S, due
to the hydroxyl and amino functional groups. The amino group provides the needed alkalinity
to the aqueous solution that is essential for acid gas absorption. Chemically, the lone pair on
the amino group allows the alkanolamine to function as a base, thus increasing the pH and
allowing H2 S/CO2 to dissolve in the solution. There are four typical alkanolamines that are
used for acid gas treatment, each used under different conditions. These alkanolamines are
H2 S that is removed through HDS and amine stripping is processed and cleaned up
through the Claus Process. This is the main industrial process for large quantity removal of
kJ
(ΔH = −519 mol) (1)
The first reaction step, the thermal step, combusts one-third H2 S to form SO2 and
water with combustion temperatures between 980℃ to 1540℃ and pressures usually below
10 psia. The second step is a catalytic reaction that takes place over activated alumina- or
titania-based catalysts. The SO2 produced from reaction (1) is reacted with the remaining H2 S
with the final products obtained being elemental sulfur and water. This process is responsible
for the majority of H2 S removal, leaving a much smaller quantity of H2 S that still has to be
2
removed in tail gas treatment units. The Claus process can be operated in either a straight-
with H2 S concentrations greater than 40%. If the concentration of H2 S is not high enough,
carsul formation, a carbon-sulfur polymer, will take place instead of commercial grade
combustion. This typically occurs with C3 and larger hydrocarbons (Optimized Gas Treating,
2018).
used. With split-flow configuration, streams containing 20%-40% H2 S can be treated. In this
configuration 2/3 of the gas stream is fed to the catalytic reactor while the other 1/3 is fed to
the burner. Regardless of configuration used, the stream leaving the Claus reactor, while
being purer, still needs further treatment. SCOT (Shell Claus off-gas treating) is a common
tail gas treatment improvement to the Claus process. H2 is added to the catalytic reactor to
reduces gases such as COS, SO2 , and CS2 to H2 S which is then recycled to the Claus unit.
There have also been improvements to the Claus process such as the Superclaus process
which can offer a sulfur recovery up to 99.5%. However, this is highly selective to H2 S alone
Due to other sulfur impurities found in natural gas streams, there has been a shift to
find better methods compared to HDS, amine scrubbing, and the Claus Process to remove
sulfur contaminants that can decompose H2 S and other small-chain yet problematic organic
compounds such as thiols. In this study, an iron-based catalyst was characterized, tested to
determine sulfur removal, and compared to a local industry standard. This industry standard
3
Chapter 2: Literature Review
2.1.1 Properties and analysis. Hydrogen sulfide is a colorless gas that is extremely
toxic and flammable. It naturally occurs in crude petroleum, natural gas, volcanic gases and
hot springs with the odor of rotten eggs that is common for sulfur compounds. When in
According to OSHA, the odor threshold for H2 S is from 0.01 to 1.5 ppm with rapidly
worsening health effects at higher concentrations. When exposed, these symptoms include
nausea, headache, insomnia, cough, fatigue, dizziness, eye irritation, loss of smell,
breaths of air containing 700 to 1,000 ppm H2 S and near instantaneous death at
concentrations higher than 1,000 ppm (Occupational Safety and Health Administration,
2006).
analyzed by gas chromatography (GC) through the use of a flame photometric detector, a
achieved with adsorbents, the Claus process, and/or absorption into aqueous solutions.
2.1.2.1 Adsorption.
2.1.2.1.1 Zeolites/clays. Zeolites have been utilized for H2 S removal. Even though the
cost of these adsorbents is relatively low, their adsorption capacities are considered poor
compared to activated carbons and metal oxides (J. Wang, Guo, Parnas, & Liang, 2015). Due
to its low cost, zeolites have been used as a support while having been modified with metals
4
and metal oxides via impregnation and ion exchange. A study conducted by “(Micoli,
Bagnasco, & Turco, 2014)” showed that adding Cu or Zn improves 13X zeolite’s H2 S
adsorption. Almost all modifications yielded at least twice the breakthrough time of the
unmodified zeolite. The ion exchange modification showed a much longer breakthrough time
when compared to unmodified 13X zeolite and the metal impregnated 13X zeolite. It was
theorized that the adsorption increase found in the ion exchange sample is due to the initial
cations being replaced in large quantities by Cu2+ or Zn2+ ions while the impregnated samples
contain Cu and Zn in their respective oxide forms instead of direct replacement. The metal
content between the types of modifications confirm this. For Cu, the ion exchanged zeolite
has roughly 2.5 times the Cu content when compared to the impregnated zeolite. For Zn, the
ion exchanged zeolite has 11 times the Zn content when compared to the impregnated
zeolite. In the case of the ion exchange modification, it was assumed that H2 S was
Where Na can be substituted with other cations such as Cu2+ and Zn2+ to give similar
reactions. The H2 S adsorption onto the impregnated zeolites is due both to the cations in the
sorbents’ cavities and the reactions between CuO or ZnO and H2 S (Micoli et al., 2014).
Na-A zeolites produced from kaolin, a type of clay, were modified by impregnating
varying amounts of zinc oxide: 10, 20 and 30 wt %, in an attempt to increase the hydrogen
sulfide capacity (Abdullah, Mat, Somderam, Abd Aziz, & Mohamed, 2018). Experimental
results showed that H2 S adsorption capacity was increased in all three cases. The baseline
Na-A zeolite H2 S capacity was 0.58 mg S/ g adsorbent. The 10 wt % ZnO addition showed
5
S/ g adsorbent. The 20 wt % ZnO loading showed the highest H2 S capacity of 15.75 mg S/ g
adsorbent and thus considered the optimal loading (Abdullah et al., 2018). It is theorized that
the reasons for the 20 wt % ZnO loading is higher than the 30 wt % ZnO loading are that
there could be pore blockage, damage/collapse of pore structure, and an aggregation of ZnO
particles on the surface due to exceeding the critical dispersion capacity of the zeolite,
possibly creating a less reactive aggregate of active sites. Other studies conducted by Li et al.
showed similar results when modifying SBA-16, MCM-48 and KIT-6 with ZnO and ran at
room temperature. An increased H2 S adsorption capacity was observed when ZnO was added
to all three of these 3-D mesoporous structures (Li, Sun, Shu, & Zhang, 2016).
Another study investigated modifying the clay subtype kaolin with iron chlorides,
copper chlorides and iron oxide to determine the effects had on H2 S adsorption. The kaolin
was modified by ion exchange through dropwise dispersion. In the H2 S breakthrough tests,
the iron oxide showed the most effective removal of 90% at 95 minutes followed closely by
iron with 85% at 100 minutes. The copper modification yielded approximately 75% removal
at 100 minutes while unmodified kaolin had 66% removal at this time. The three different
depositions onto kaolin increased its BET surface area, effectively enhancing H2 S adsorption
capacity. This is reflected by the increased experimental breakthrough time when compared
2.1.2.1.2 Activated carbon. Activated carbons have been utilized as sorbents for
sulfur removal but typically have a low sulfur adsorption capacity while unmodified.
Modifications such as surface oxidation, metal impregnation, and ion exchange have been
investigated by several researchers (Figueiredo, Pereira, Freitas, & Órfão, 1999; Ning et al.,
2018). Results in these studies have shown that modifications added more adsorption sites
6
and acid groups on the activated carbon surface. In a study by Cui, Turn and Reese, coconut
shell activated carbon was used as the base material for modifications through metal
impregnation and oxidation (Cui, Turn, & Reese, 2009). The impregnation modifications
were metal from Zn, Cu, Fe, K and Na sources with approximately 0.4 mmol of metal loaded
per gram of virgin AC. Virgin AC had the lowest H2 S capacity out of all the sorbents
investigated, while Cu and Zn sorbents never experienced breakthrough during the conducted
test. All modifications resulted in an increase H2S sorption capacity. The most effective
modification for H2 S removal was the Cu impregnation followed by the Zn. The alkaline
metals, K and Na, showed slightly better results when compared to Fe and oxidation
Hydrogen sulfide removal has also been examined using non-thermal plasma
modification on Fe-walnut shell AC, particularly NH3 -plasma, in hopes that it could
adsorption or oxidation capacity. Ning, Liu et al. utilized dielectric barrier discharge to
through transforming the discharge gas. It was shown that H2 S removal was improved when
the treatment input voltage and time were in the ranges of 5.6-6.8 kV and 5-10 min,
respectively. However, H2 S removal was shown to decrease when treatments extended past
carbonate onto coal-based AC on H2 S oxidation (Xiao, Wang, Wu, & Yuan, 2008). Xiao et
al. proved that both the unmodified and modified AC have catalytic activity for H2 S
oxidation. It was observed that water had a beneficial effect on the oxidation process by
7
changing the relative humidity in the experiments. The highest sulfur capacity of this
impregnated AC was 420 mg S/g. This experiment was conducted with a relative humidity of
80% at 30℃. Due to the Na2 CO3 impregnation the pH was made more basic. This gave
hydrosulfide ion concentration a more preferred environment due to the acidity of H2 S, thus
improving the H2 S oxidation allowing full utilization of the AC pores. The unmodified AC
deactivated rapidly. It was postulated that this rapid deactivation was caused by the formation
of sulfuric acid produced as a byproduct of H2S oxidation. According to Xiao, this suppresses
H2 S dissociation. The impregnation of Na2 CO3 onto the unmodified and impregnated ACs
provided a basic environment instead of an acidic one, avoiding deactivation until the pores
Figure 1: H2 S removal capacities of literature adsorbents (Elyassi et al., 2014; Fang, Zhao,
8
2.1.2.2 Reactions.
2.1.2.2.1 Metal oxides reactions. Due to its high selectivity for H2 S the iron oxide
process has been a prevalent means of removing H2 S since implemented in England during
the nineteenth century (Crynes, 1977). The iron oxide catalyst removes H2 S by forming iron
The process is typically operated with 2 towers in parallel. A tower is operated until
the bed is saturated with sulfur and the sweetened gas stream begins to show H2 S. Once this
point is reached, the tower is removed from service and regenerated by circulating gas with a
small portion of air contained throughout the bed. While the primary tower bed is undergoing
regeneration, the sweetening process is changed over to the parallel tower. The regeneration
of the catalyst is achieved by exposing the spent catalyst to an oxygen stream and can be
repeated several times before disposal. The regeneration reaction is shown in reaction (6).
could cause the iron oxide structure to dehydrate. This leads to highly reduced reaction rates
and possible decomposition of Fe2 S3 to FeS2 and Fe8 S9 . These are vastly more difficult to
regenerate. The water produced in reaction (3) does provide some of the needed moisture to
allow the catalyst to work optimally. The elemental sulfur formed from the oxidation of
ferric sulfide will eventually cover the majority of the catalyst’s surface after numerous
9
regeneration cycles. This will lead to a loss of activity of the oxide’s surface and can cause
excessive pressure drop and bed channeling. The regeneration reaction is highly exothermic
(Kouichi Miura et al., 1992). Due to this, the spent catalyst can be pyrophoric when exposed
to air or low oxygen content streams so care should be exercised when change-out occurs.
reactions for the ferric oxide-H2 S interactions set by Wiȩckowska (Davydov, Chuang, &
Sanger, 1998). Due to the thermodynamically unstable Fe2 S3 product formation, it was
proposed that Fe2 S3 reacted further to form pyrite (FeS2 ) and greigite (Fe3 S4 ). Wiȩckowska
proposed that iron oxides only perform desulfurization when they are in their hydrated form
Fe(OH)3 is proposed to be part of the catalyst after the initial regeneration of the
spent catalyst. The regeneration of the ferric sulfide and pyrite are shown as follows:
3
2FeS + 3H2 O + O2 → 2Fe(OH)3 + 3S (10)
2
3
Fe2 S3 + 3H2 O + O → 2Fe(OH)3 + 3S (11)
2 2
3
Fe2 S3 + O2 → Fe2 O3 + 3S (12)
2
The overall desulfurization and regeneration reactions are shown in the equation:
In this reactions (9) and (10), it is shown that water is needed to regenerate the spent
catalyst back to ferric hydroxide or hydrated ferric oxide. Due to the highly exothermic
10
process, like in the initial mechanism, it is noted that the oxygen or air used in the
Zinc and calcium oxides have also been studied and used to remove H2 S through the
following reactions:
was studied by Kim and Park (K. Kim & Park, 2010). Inlet concentrations of 100, 500 and
800 ppmv were added to a gas mixture consisting of 22% CH4 , 18.7% H2 , 8.8% CO2 , and
5.5% CO which was balanced with steam. Breakthrough threshold was chosen to be at 2
ppmv H2 S detected in the effluent stream. It was observed that sulfur removal at each
different inlet concentration was independent of space velocity, which was varied from 6000,
8000, and 12000 hr −1 . The breakthrough times linearly decreased as the inlet concentration
was increased. It was found that while the H2 S loading capacities were approximately
constant at each space velocity, the H2 S capture capacity increased when inlet concentration
was changed. At 100 ppmv, the capacity calculated was 10.9-12.5 g S/ 100 g sorbent; 500
ppmv, 24.8-26.4 g S/ 100 g sorbent; and 800 ppmv; 28.3-30.4 g S/ 100 g sorbent. It was
theorized that the non-steam components alter the ZnO sulfidation mechanism and its
equilibration to explain the increased H2 S capacity when the sorbent is exposed to higher
2.1.2.2.2 Biological methods. Oxidation has been used for odor control in gas
streams in numerous industries and in wastewater treatment for hydrogen sulfide and other
11
odorants. In this instance, hydrogen sulfide is converted to sulfuric acid in the presence of
Beggiato have been studied and utilized for this purpose along with removing other inorganic
and organic sulfur compounds (Arellano-García, Le Borgne, & Revah, 2018; Awe, Zhao,
Nzihou, Minh, & Lyczko, 2017; Zhu, Li, Wu, & Dumont, 2017). Hydrogen sulfate, and
sulfuric acid once protonated, can be produced from hydrogen sulfide through the sulfite-
1
HS − + O2 → S 0 + H2 O (18)
2
1
S 0 + H2 O + O → SO4 2− + 2H + (19)
2 2
1 1
S2 O3 2− + H2 O + O2 → SO4 2− + H + (20)
2 2
The overall products will be converted into sulfuric acid. Due to this sulfuric acid
formation and associated pH reduction, microbial activity, mass transfer rate into the biofilm
and removal efficiency can be negatively affected (Ben Jaber et al., 2016; Jaber et al., 2014).
observed. However, this efficiency decreased to 78% when H2 S loading was increased to 360
ppm, lowering the pH to 0.5 (Ben Jaber et al., 2016). This is attributed to sulfate buildup and
lower H2 S mass transfer at more acidic conditions (Ben Jaber, Couvert, Amrane, Le Cloirec,
12
& Dumont, 2017). Upping the watering flow rate and using basic packing media can counter
2.2 Mercaptans/Thiol
room temperature that has a highly malodorous smell akin to that of rotten cabbage and
rotten eggs and is flammable. It occurs naturally in the human body, particularly in the brain
and blood, and is present in natural gas in certain US regions, coal tar and some crude oils. It
is produced, desired and undesired, in multiple industries such as plastics, animal feeds, pulp
and paper, jet fuel, pesticides and natural gas. At high concentrations methyl mercaptan is
toxic and affects the central nervous systems. It is absorbed rapidly through inhalation and
Ethanethiol (ethyl mercaptan) is a clear liquid at room temperature with a low boiling
point of 95-97 ℉ that is naturally found in natural gas and petroleum wells. Due to this low
boiling point, it is typically in the gas phase at bulkhead when removed from the petroleum
odorless gaseous products to help warn of gas leakage. Ethyl mercaptan’s scent, similar to
skunks and cooked cabbage, can be detected by scent at extremely low threshold
2007). It is also used as an adhesive stabilizer in some industries. In addition to being highly
flammable, it is also toxic. Vapor inhalation can cause muscular weakness, convulsions and
respiratory paralysis. Pulmonary irritation may occur at high concentrations. The liquid
irritates the eyes and skin while ingestion can cause nausea and irritation of the mouth and
13
stomach (U.S. National Library of Medicine, 2005). Both mercaptans can also be
Methyl and ethyl mercaptan are usually monitored via infrared sensors for in-situ
or a mass spectrometer.
2.2.2 Activated carbons. Like H2 S, activated carbons have been utilized to remove
the low chain mercaptans as well but still show some of the same problems; mainly low
removal. A study conducted by Zhao et. al showed that metal addition modification greatly
enhanced the catalytic activity when compared to the unmodified coconut shell based
activated carbon. They found that the Cu-AC and Ni-AC modified catalysts had the best
catalytic activity when removing methyl mercaptan followed by Al-AC, then Fe-AC and
finally Zn-AC (Zhao et al., 2015). In the study conducted by Cui et al., Fe-impregnated AC
showed to have the most effective removal of methyl and ethyl mercaptans when compared
to Zn, Cu, K and Na impregnated AC and oxidized AC. In the case of methyl mercaptan, Fe
and Cu showed approximately the same removal efficiency followed closely by Zn and then
oxidation. The alkaline impregnations showed a slight increase in methyl mercaptan capacity
when compared to virgin AC. Fe showed the highest affinity for ethyl mercaptan capacity
followed by Zn and Cu and then oxidation. Again, the alkaline impregnations showed a slight
increase in ethyl mercaptan uptake capacity when compared to virgin AC (Cui et al. 2008).
to H2 S, metal oxides have also been studied in the removal of low chain mercaptans such as
14
oxides were synthesized and tested in the desulfurization of municipal gas using methyl
mercaptan as the model contaminant. The feed gas was methane containing 291 μmol/mol
hydrothermal and aerogel. The aerogel MgO showed the highest adsorption capacity when
compared to the PMT and hydrothermal MgO at both temperatures studied, 278K and 288K.
The sorption capacities of the hydrothermal and aerogel MgO were approximately 6 times
and 180 times, respectively greater than the PMT MgO at 278K. This was magnified at 288K
where the hydrothermal MgO showed 15 times removal and the aerogel MgO showed 476
times the removal of PMT MgO. The aerogel MgO was also slightly more favorable when
compared to AC in terms of adsorption capacity and mass transfer rate even though AC has a
higher surface area (Y.-H. Kim, Tuan, Park, & Lee, 2014).
2.2.4 Biofiltration. Biofiltration has been utilized for sulfur contaminant removal,
primarily H2 S, but it has also been tested for other compounds such as ethyl mercaptan. One
such study conducted by Ben Jaber et al. delved into the effectiveness of this technique for
ethyl mercaptan removal alongside H2 S and dimethyl disulfide contaminants present in the
stream (Jaber et al., 2014). Three different columns inoculated with activated waste sludge
upon pine bark and composted wood mulch were used. Each column was watered with a
different solution at a fixed rate of 0.344 L/day. The effects of nutrient concentration were
the main factor observed in this study. The first column operated without a nutrient supply
while different nutrient solutions were supplied to the second and third columns. The second
solution consisted 0.12 g/L K 2 HPO4 , 0.08 g/L (NH4 )2 SO4 , and 0.39 g/L Na2 CO3 , while the
third consisted of deionized water, 0.48 g/L (NH4 )2 SO4 , and 1.97 g/L Na2 CO3 . Ethyl
mercaptan removal was highly affected by the different nutrient solutions. In Column 1, only
15
30% was removed in the pine bark portion of the bed and only 72% on the total bed height of
the column without nutrients present. However, there was 90-97% ethyl mercaptan removal
when nutrients were present in the watering solution. An overall improvement was shown for
ethyl mercaptan removal with the high nutrient supply due to the neutral/alkaline pH of the
system. Without the nutrient supply and the simultaneous removal of H2 S, the biofilter bed is
highly acidic, leading to ethyl mercaptan microbial inhibition (Jaber et al., 2014).
16
Chapter 3: Objectives
The overall objectives of this study are to understand the characterization, and
catalytic and removal behavior of an iron-based catalyst for H2 S, methyl mercaptan, and
ethyl mercaptan removal and compare these results to a commercial standard. The other
major objective is to blend the catalyst with different filler materials in order to save on costs
while still exceeding the commercial standard’s sulfur removal. The catalyst was provided by
Coastal Chemical LLC. Methyl and ethyl mercaptan removal were studied because these
emissions and corrosion issues. Many characterization methods for solid and gas matrices
were applied in this study ranging from Brunauer-Emmett-Teller (BET) surface analysis,
Fourier Transform Infrared Spectroscopy (FTIR), X-ray fluorescence (XRF), X-ray powder
spectroscopy (GC-MS), and Proton Induced X-ray Emission (PIXE) Spectroscopy. The
7. Test sulfur removal using a 1:9 catalyst/filler ratio and compare removal to the
Chemical LLC.
17
Chapter 4: Materials and Methods
4.1 Chemicals
Both catalysts (Coastal and Sulfatreat) and the three supplied filler materials
(anthracite, clay and graphite) used in the experiments were provided by Coastal Chemical
Co., LLC (Broussard, LA). The model gas used in the flow reactor system was obtained from
CSI Gas, LLC (Humble, TX) while the hydrogen sulfide (H2 S), methyl mercaptan (CH3 SH),
and ethyl mercaptan (C2 H6 S) standards used for the analytical works were obtained from
The Coastal catalyst was sent through a series of sieve trays to obtain a desirable
particle size, between 425 μm and 850 μm (US Mesh 40). In early testing, some of the
Coastal catalyst samples were heat-treated at 300℃ to remove water and any trace
hydrocarbons potentially present on the surface of the raw catalyst to study the effect of these
compounds had on sulfur removal. It was determined that the heat treatment had a negative
effect on the removal of the three target sulfur compounds. The Sulfatreat catalyst, initially in
pellet form, was crushed with a pestle and mortar to obtain a similar particle size to the
Coastal catalyst and also to fit in the reactor bed. The filler materials were each mixed with
1:9 weight proportion of Coastal catalyst to filler material. The mixtures were then run
through a grinder to attain smaller and more uniform pieces. These ground mixtures were
then separately sieved to collect the 425 μm to 850 μm particle sizes. Glass wool, 1g of
catalyst/mixtures, followed by more glass wool were inserted in a steel tube serving as the
18
Figure 2: Pilot Reactor System
All pilot scale experiments were carried out using a continuous flow packed column
reactor. The initial systems are depicted in Figures 2 and 4 showing the gas flow piping,
heating, valves, pumps, flow meters, and sampling ports. This system was later modified
with a T-joint at the base of the reactor to add a slip stream for flow to be sent to the Agilent
490 Micro GC for analysis. All of the gas flow lines used were 1/8 th stainless steel tubing.
19
Figure 3: Bench Scale Reactor System
All bench scale experiments were carried out using a continuous flow packed column
reactor shown in Figure 3. The reactor effluent was sent to the Agilent 6890N GC System
After the pilot-scale reactor bed depicted in Figures 2 and 4 was loaded with catalyst,
it was connected into the system. It was pressurized at either 100 psig or 200 psig with a
nitrogen gas flow rate of either 36 mL/min or 50 mL/min controlled with a needle valve
before Flow Meter 2. Once the operating pressure for that particular run was reached, Valves
1 and 18 were closed to block in the system. With these valves closed, the system was leak
checked using Snoop and was then left for an hour to determine if there were any small leaks
that the Snoop did not find by measuring the pressure drop on the pressure gauge. Once the
20
system was determined to be leak free, the reactor was wrapped with a heating coil for
temperature requirements above ambient temperature. The rheostats for the pre-heater and
the reactor were then turned on and adjusted. The pre-heater rheostat was maintained at
approximately 50 V, heating the stream up to 150 °C. This vaporized any moisture in the
tubing before the reactor. The reactor rheostat was increased to the appropriate voltage to aim
for 100 °C and 200 °C, respectively. The correct voltages for the rheostats were determined
Once the reactor was brought up to and stabilized at the desired temperature, the
system block valve before Flow Meter 18 was opened and the nitrogen was allowed to vent.
21
The feed valve, Valve 2, was then opened to send the feed gas into the reactor system. This is
noted as time zero. The flow rate was adjusted to the desired flow, and the temperature was
allowed to equilibrate.
In the bench-scale experiments, the reactor was loaded with 1 gram of material.
Depending on the parameters, a heater coil was wrapped around the reactor and a
thermocouple. These were then wrapped with insulation, and the temperature was raised and
held at 100°C via a rheostat. While the reactor system was brought up to temperature, a
nitrogen flow was introduced to the system and blocked in. This allowed for leak testing
along all connections from the gas tank all the way to the downstream mass flow controller.
Once the temperature has stabilized and all connections checked and corrected for leaks, the
nitrogen was purged from the reactor. Then, the online GC-MS sequence was prepared. Like
the pilot system, the model gas flow was then introduced into the system at either 36 mL/min
or 50 mL/min depending upon manual settings on the mass flow controller. The GC-MS
sequence was immediately started once the flow was stabilized at the correct pressure.
While the pilot-scale reactor was used, sampling began an hour after startup by
withdrawing 0.5 mL of gas. Initially, the effluent gas was tested every 4 hrs. After 12 hrs, the
sampling time was changed to every 2 hrs. After an additional 6 hrs, sampling was conducted
hourly until breakthrough. Breakthrough was defined differently between H2 S and the
mercaptans due to concentration differences and compound sensitivity with the MS detector.
original concentration while the mercaptans were defined when concentrations reached 40%
22
contaminants in bulk methane, gas samples were taken from the gas port after Flow Meter 1
shown in Figure 4. A gas-tight syringe was used to take samples. The syringe was plunged
into the septum of the gas port and flushed numerous times prior to sample collection to
During the bench scale experiments conducted in the reactor system shown in Figure
3, the reactor effluent stream was directly introduced into the GC-MS. This online method
utilized a valve as the connection for the effluent stream to pass into the GC-MS column.
This valve served as the “injection” of the effluent sample. When closed, the effluent gas was
diverted and passed to the exhaust line that was fed into a vent for safety.
An experimental run was deemed complete once breakthrough was achieved. When
this occurred, the shutdown procedure was initiated. The inlet gas and rheostat for controlling
the reactor temperature were turned off. Once the pressure due to the test gas was reduced in
the line, the nitrogen valve was opened to purge the system of remaining test gas. The system
was allowed to purge for approximately 2 hours. Once the reactor came down to room
temperature and the nitrogen was finished purging, the nitrogen source valve was closed.
When the system pressure dropped to atmospheric pressure, the packed bed reactor was
removed from the system. The catalyst was removed as quickly as possible from the reactor
segment and into a closed scintillation vial for further analysis. The reactor was then washed
4.7.1 GC Analysis of gas samples. Two different GC units were utilized to analyze
the concentrations of the test gas downstream of the pilot scale reactor. Initially, samples
23
were injected into an Agilent Technologies 6890N Network Gas Chromatograph with a 30 ft,
0.320 mm inner diameter GS-GASPRO column equipped with an Agilent Technologies 5975
Inert Mass Selective detector and a thermal conductivity detector. The MS filament
temperature was set at 170℃ and scanned from 30 m/z to 80 m/z. The data and chemicals
were quantified and identified through the use of the Enhanced MSD Productivity
ChemStation’s library and data analysis programs. Later, an Agilent Technologies 490 Micro
GC was installed downstream of the reactor to better integrate and automate the effluent
analysis. Two different columns were used in this Micro GC. A PoraPLOT U column was
used in the first channel while a CP-Sil 13 CB for TBM column was used in the second
channel. The PoraPLOT U column was used for H2 S detection while the CP-Sil 13 was used
for the mercaptan detection due to the columns’ selectivity for the analytes and separation
Two of the original eight parameter variations, 200 psi, 100℃, and 50 mL/min and
200 psi, ambient, and 50 mL/min, were not included in this document. Both of these
experiments were conducted in either the pilot reactor system that did not utilize the
automated sampling for Agilent Technologies 6890N GC/5975 Inert MS. One variation was
manually sampled using a different time schedule and GC-MS method for detection. The
other variation used an inline Agilent 490 Micro GC for detection. This GC was provided by
Coastal and had been already used for other experiments in removing higher chain and
heavier sulfur compounds. Due to how this GC worked, the gasifier maxed out a temperature
that was insufficient for gasifying these heavier compounds which lead to inaccurate data to
24
Figure 5: Agilent Technologies 6890N Network GC equipped with Agilent Technologies
Originally, gas samples were extracted from the gas sampling port downstream of the
pilot scale reactor via a 1.0 mL gas syringe. The syringe was introduced into the sample port
and flushed numerous times to ensure a representative sample. After the sample was drawn
but before removal from the port, the valve of the syringe was closed to prevent any air from
entering the system and to prevent any of the sample to escape. The sample was then injected
directly to the reactor effluent stream, downstream of the mass flow controller. A
pneumatically controlled gas sample valve was connected to a split/split-less injector. Until a
25
sample injection was made, the valve controlling access to the GC column was closed. When
an injection was to be made, the valve was opened for a specified amount of time. Once
injected, the sample was analyzed using the method in Table 2. Once the designated time had
130℃ 25℃/min
4.7.1.1 Calibration curve. Calibration of the products was first carried out by
injecting different volume amounts of gas standards: 500 ppm H2 S, 50 ppm CH3 SH, and 50
ppm C2 H6 S in bulk CH4 , into the Agilent Technologies 6890N Network Gas Chromatograph
and recording the peak area counts at these volumes. A calibration curve was prepared from
known volumes injected and the area counts. Once the experimental setup changed to include
automated sampling, the calibration of the products was conducted by repeatedly flowing the
gas standards through an empty reactor bed every 26-30 min to obtain the average area count
for the gas standards’ unmodified concentrations. Calibration curves relate the average area
counts with the concentrations of the gas standards. The curve is used to later convert area
chromatograph of the model gas, and what is being replicated through the online calibration,
is shown in Figure 6.
26
Figure 6: Chromatograph of Model Gas
4.7.1.2 Reaction studies. The results from the GC analysis were analyzed using the
calibration data to provide the actual concentrations of H2 S, methyl mercaptan and ethyl
mercaptan entering and exiting the reactor system. These concentrations were used to
C
generate breakthrough graphs of Cf vs time for different reaction parameters evaluated for the
i
catalysts/fillers.
Due to the unknown speciation of the Coastal catalyst and that sorbents are used as
filler for the Coastal catalyst, sulfur removal was calculated using the following equation:
(Ci − Cf ) ∗ 𝑡 ∗ Q
q= (21)
M
Where q is the amount removed (g/g), Ci and Cf (ppm) are the individual initial and
volumetric flow rate of the model gas (mL/min), t is the time of the reaction (hr), and M is the
mass of the catalyst loaded (g). This equation was used to track the amount of sulfur removal
while varying the temperature, pressure, flow rate, and catalyst in the reactor.
4.7.2.1 Surface area and porosimetry measurement. The surface area, pore volume,
particle size and pore size were delivered upon completion through equations developed by
Brunauer, Emmett and Teller to explain the physical adsorption of gas molecules on the
27
catalyts’ solid surface. The BET theory is an extension of the Langmuir theory except that it
focuses on multilayer adsorption with some assumptions. The general BET equation is:
1 𝑐−1 𝑝 1
= ( )+ (22)
𝑣 [(𝑝0 ⁄𝑝) − 1] 𝑣𝑚 𝑐 𝑝0 𝑣𝑚 𝑐
𝐸1 − 𝐸𝐿
𝑐 = exp ( ) (23)
𝑅𝑇
With p and 𝑝0 , the adsorbates’ equilibrium and saturation pressures at the temperature of
adsorption, v is the adsorbed gas quantity and 𝑣𝑚 is the monolayer adsorbed gas quantity. In
the BET constant expression, 𝐸1 is the heat of adsorption for the first layer, 𝐸𝐿 is the heat of
adsorption for the second and higher layers and is equal to the heat of liquefaction or heat of
vaporization.
𝑝
This process can also be plotted as a straight line with 𝑝 on the x-axis and the left
0
side of equation 22 on the y-axis. The slope (A) and y-intercept (I) can be used to calculate
1
𝑣𝑚 = (24)
𝐴+𝐼
𝐴
𝑐 =1+ (25)
𝐼
These values are then used to calculate the total surface area (𝑆total ) and specific
𝑣𝑚 𝑁𝑠
𝑆total = (26)
𝑉
𝑆total
𝑆BET = (27)
𝑎
28
Where N is Avogadro’s number, s is the adsorption cross section of the adsorbing species, V
is the molar volume of adsorbate gas, and a is the mass of the adsorbent.
To run an analysis on the Micromeritics ASAP 2020 surface area and porosimetry
analyzer (Figure 7), a small sample of approximately 0.1 to 0.25 g was first placed in a tared
sample vial. The sample vial was then degassed at 350℃ for at 600 min with an empty
sample vial in the other port to ensure gas flow continued in the system. After degassing, the
sample was allowed to cool. While the sample cooled, the dewar was filled with liquid
nitrogen. The cooled, degassed sample vial was weighed to get the degassed sample weight
and screwed into the analysis port. The dewar was then placed on the elevator, and the
method was started. The elevator raised up until the dewar was in place over the vial in the
analysis port, and then the cover was placed over the analysis port and dewar unit. The gas
29
flow and liquid nitrogen levels were monitored throughout the entire analysis, about a 7 hr
process. The samples were run through method completion. The sample was then removed
the surface functional groups was made before anything was known about the chemistry of
the two catalysts and the blends. This was carried out using two different spectrometers. The
two machines used were a Jasco Ft/IR-4700 and an Agilent Technologies Cary 640 FTIR and
30
Figure 9: Agilent Technologies Cary 640 FTIR
spectra of iron oxide and calcium oxide. Both iron and calcium were confirmed to be the two
major components of the catalyst in XRF analysis, and the spectra agree with this finding.
The spectra band at approximately 520 is consistent with Fe2 O3 while the peaks at 874 and
31
Figure 10: IR spectra of Raw Coastal Catalyst
32
The catalyst was submitted to thermal treatment to find out water content and
possible contamination of compounds such as hydrocarbons. Once the catalyst weight was
recorded and placed inside the TGA’s heating chamber, the TGA was heated from ambient
temperature to 1000℃ at a heating rate of 20℃/min. The TGA continuously recorded mass
and the concurrent temperature during this heating rate. This data was used to plot a TGA
formation/removal.
PIXE analysis was used to determine the elemental composition of the catalyst as it is
a non-destructive technique and highly accurate for homogeneous particles. The catalyst was
bombarded with an ion beam from an ion accelerator. The beam’s energy displaced an inner
shell electron which caused a valence electron to drop an energy shell level by emitting
energy. This energy emitted was observable in the X-ray spectrum. Elements have signature
33
energy emissions and transitions which are measured by an energy dispersive detector. One
limitation of PIXE analysis is that elements below sodium do not show up as the elements’
34
Chapter 5: Results and Discussion
(Å)
When the catalysts presented in Table 3 are compared to other catalysts and sorbents
in the literature, such as the popular activated carbons, they are on the lower end of measured
BET surface characteristics. Most of the activated carbons have a minimum surface area of
approximately 700 m2 /g with many peaking over 1000 m2 /g (Guo et al., 2007; Xiao et al.,
2008). Activated carbons (AC) using Fe, Mn, Co, Ce, V, and Cu modifications via
impregnation still showed high BET surface areas in the 800-900 m2 /g range (Fang et al.,
2013). In the literature, mesoporous silica supported adsorbents were synthesized and
modified, greatly changing their surface chemistry. All of the unmodified adsorbents in this
study had roughly doubled BET surface areas when compared to their modified versions.
35
Once modified through impregnation via the incipient wetness method, these adsorbents had
comparable surface areas to the Coastal catalyst (Hussain, Abbas, Fino, & Russo, 2012)
compounds deposited on the catalyst surface, and the temperature region of potential catalyst
degradation. The result in Figure 13 show that approximately 8-10 weight % of the catalyst
weight is lost at 150℃ and exhibits a steady weight loss between 350℃ to 550℃. The first
two peaks of the derivative weight line show the more precise amount lost per ℃. It is
theorized that the first peak on the derivative weight line is water loss off of the catalyst
while the smaller second peak is an adsorbed volatile organic compounds. There is a small
peak between 200℃ to 250℃ that could possibly be attributed to adsorbed contaminants
being released while there is another 2-2.5 weight % loss between 650℃-700℃. It is
5.1.3 FTIR Characterization of spent catalyst. FTIR results of the spent catalyst
shown in Figure 15 showed some differences when compared to the raw catalyst’s spectra.
The water peak around 3400-3500 cm−1 disappeared as expected, since the water evaporates
36
at the conditions of the experiment. The CaO peaks also disappeared or was significantly
reduced in intensity. This is most likely due to sulfur product buildup, particularly iron pyrite
and greigite, on the catalyst surface. However, the expected peak for iron pyrite was not
observed because it is detected below 500 cm−1 , which is the minimum limit for the
instrument used in this study. The other speculated iron product based on the literature,
greigite, cannot be identified at this time due to the unavailability of a pre-existing spectra.
One of the peaks representative of CaO in the raw catalyst was also found in the spent
catalyst; however, the intensity of this peak (1424-1458 cm−1 ) was significantly weaker
when comparing transmittance level. The other indication of CaO presence, the peak at 874
was not found in the spent catalyst. The 30-40% transmittance strength difference between
the two spectra (lower for spent catalyst) suggests sulfur product buildup on the catalyst
surface. There is also possibly some regeneration of the catalyst between removal from the
system and the FTIR scanning due to air exposure which provides oxygen required for the
regeneration reactions.
3
2FeS + 3H2 O + O2 → 2Fe(OH)3 + 3S (10)
2
3
Fe2 S3 + 3H2 O + O → 2Fe(OH)3 + 3S (11)
2 2
3
Fe2 S3 + O2 → Fe2 O3 + 3S (12)
2
These reasons can explain why there is some CaO found in the catalyst post-reaction and
why the % transmittance is so low. Another possible explanation is that CaO was not
37
Figure 14: FTIR Spectra of Raw Coastal Catalyst
38
5.1.4 PIXE analysis.
MicroPixe analysis was conducted utilizing a 2 MeV proton beam from a 1.7 MV
Pelletron accelerator with an Amptek Silicon drift detector for X-ray detection and a silicon
surface barrier detector to measure the backscattering spectrum. PIXE mapping of the raw
Coastal catalyst in Figure 16 agrees with the FTIR results that iron oxides and calcium oxide
are the major components of the catalyst. The catalyst granules analyzed showed an Fe-rich
phase with Ca inclusions and trace concentrations of Cr, Mn, Mo, Ti, Zn, and S. Some of
these trace concentrations along with the Fe and Ca mappings are shown in Figure 17. It is
seen in Figure 18 that there are two forms of iron. It is likely that they are hematite and
magnetite, or Fe2 O3 and Fe3 O4 . Overlaying the different element mappings of the spent
catalyst shows the sulfur accumulated from the reactions deposited in the Fe-regions and
very little in the Ca pockets. In Figure 19, it is observed that sulfur is present in the spent
catalyst shown by a characteristic peak around 2.5 keV that is associated with the sulfur
39
element. This peak is not found in the virgin catalyst. The sulfur response is lower than
anticipated considering the run times for the Coastal catalyst experiments. This is likely due
to catalyst regeneration between reactor breakdown and the PIXE analysis and possibly no
40
Figure 18: PIXE Analysis of Unreacted Coastal Catalyst
100℃
50 mL/min
100℃
36 mL/min
Ambient
36 mL/min
100℃
36 mL/min
Ambient
50 mL/min
Ambient
36 mL/min
42
Table 5: Methyl Mercaptan breakthrough Times
Mercaptan
100℃
50 mL/min
100℃
36 mL/min
Ambient
36 mL/min
100℃
36 mL/min
Ambient
50 mL/min
Ambient
36 mL/min
43
Table 6: Ethyl Mercaptan Breakthrough Times
Mercaptan
100℃
50 mL/min
100℃
36 mL/min
Ambient breakthrough
36 mL/min
100℃
36 mL/min
50 mL/min
Ambient breakthrough
36 mL/min
44
H2 S, methyl mercaptan, and ethyl mercaptan removal were investigated as a function
of time, pressure, temperature, flow rate, and catalyst. Experiments provided the data to
optimize operating conditions for maximum removal efficiency per compound. Removal
efficiencies vs time graphs of the three compounds are shown in Figures 20-52. Removal
results can be observed as a function of time and operating conditions (temperature, pressure,
5.2.1 Coastal experiments. All runs that utilized the pure Coastal catalyst are shown
in Figures 20-22. In Figure 20, the experiment resulting in the longest breakthrough time
with an effective run time of 276.5 hr removing H2 S was conducted at 200 psi, 100℃, and 36
mL/min followed by the experiment at 200 psi, ambient, and 36 mL/min. This superior
performance (longer breakthrough time) is due to the higher pressure, temperature, and lower
flow rate (longer residence time) which are more desirable reaction conditions when
compared to the other variations. The higher temperature lends more energy that is needed to
meet the activation energy for the reaction to occur. The relationship between the rate
dependent, 𝐸𝑎 is the activation energy for the reaction (J/mol), R is the universal gas constant
(J/mol*K), and T is absolute temperature (K). Through the ~75 ℃ operating differential, an
approximate 30 hr difference between breakthrough was observed from the 200 psi, 100℃
and 36 mL/min run compared to the 200 psi, ambient, 36 mL/min run, the next variation with
the highest removal. This significant difference in performance indicates that a chemical
45
pressure as there is a 40 hr run time difference between the 200 psi, 100℃, and 36 mL/min
and 100 psi, 100℃, and 36 mL/min runs. The other major impact is the flow rate. Between
the most effective run and its high flow rate variation, there was approximately an 80 hr run
difference. This parameter exhibited the greatest change between removals when compared
to temperature and pressure changes. The residence time for the two flow rates are 2 seconds
V
𝜏= (29)
Q
Where 𝜏 is the residence time, V is the reactor volume, and Q is the flow rate. With the runs
within Figure 20, the temperature changes seemed to have the greatest affect alongside flow
rate changes. This is verified by the 80 hr difference in run time. With the energy from the
raised temperature, the activation energies for the three reactions were clearly met. The
pressure changes showed that the pressure increase positively impacted removal. The shortest
run, approximately half of the longest run, was at 100 psi, ambient, and 50 mL/min. The
ambient temperature does not provide the necessary energy to reach the reaction activation
threshold needed to break the compound bonds. The lower pressure correlates with lower
concentrations in and on the catalyst surface during gas phase heterogeneous catalysis. The
H2 S reaction is further affected by the higher flow rate which results in a lower residence
time for reactions with the catalyst. All Coastal runs showed improved H2 S removal
46
Figure 20: Coastal H2 S Breakthrough vs Time
The most effective run for methyl mercaptan removal by approximately 70 hours was
at 200 psi, ambient, and 36 mL/min with an effective removal time of 240 hours. The next
were 200 psi, 100℃, and 36 mL/min and 100 psi, 100℃, and 36 mL/min. The least effective
run in terms of breakthrough time was at 100 psi, ambient, and 50 mL/min with a run time of
100 hours. Unlike H2 S, methyl mercaptan does not show temperature dependencies for
removal. Pressure shows the greatest effect on removal. It is likely that physisorption rather
removal. The higher pressure reduces the gas volume and increases its density. This increases
the chance of a contaminant atom to be adsorbed onto the surface of the catalyst. Adsorption
is an exothermic process. When a molecule is adsorbed onto the surface, the molecule’s
heat. The lower temperature combats this heat increase by lowering gas volatility and
47
increasing the entropy change, maximizing the driving force for adsorption. The most
effective run time drops from 240 hours to 140 hours when the pressure is changed from 200
psi to 100 psi while at ambient temperature and 36 mL/min. Flow rate still plays a role in
removal. The lower flow rate gives a higher residence time, increasing the contact time for
adsorption.
In terms of ethyl mercaptan removal, the most effective parameter variation was also
at 200 psi, ambient, and 36 mL/min with an effective operating time of 245 hours. The next
highest efficiency parameter is 200 psi, 100℃, and 36 mL/min with approximately 180
hours. The most ineffective parameter set is 100 psi, ambient, and 50 mL/min with 100 hours
of run time. Like methyl mercaptan, there is not a positive impact of adsorption at high
temperature compared to the pressure effects on removal. When the pressure is changed from
200 psi to 100 psi while at ambient temperature and 36 mL/min, the runtime drops by 100
hours. This alongside with the reduced temperature effects suggest that adsorption rather than
48
Figure 21: Coastal Methyl Mercaptan Breakthrough vs Time
5.2.2 Graphite blend experiments. The graphite/Coastal blend showed that the most
effective removal parameters in the case of H2 S were the 200 psi, 100℃, and 36 mL/min and
100 psi, 100℃, and 36 mL/min. These two runs showed almost identical 100% efficient run
times at 8 hours. This shows that there is not a significant dependency on pressure while at
49
elevated temperatures. At this temperature and flow rate, the reaction appears to follow a 0 th
order reaction as pressure changes do not have an effect. A 0th order reaction is characterized
as follows:
Where k is the rate constant. However, this cannot be confirmed off of these two runs alone.
The following variations: 100 psi, 100℃, and 50 mL/min and 100 psi, ambient, and 50
mL/min showed the worst performance with similar breakthrough times of 2.5 hours. It is
inferred that at the lower pressure, temperature does not have a significant effect on removal.
For optimal removal, the higher temperature is needed to provide the activation energy
requirement for reaction using the graphite filler. The higher flowrate decreased the gas
residence time, allowing for less time along the catalyst bed. It is noted that at this higher
flow and low pressure that while the temperatures were varied, the results were
approximately the same. The surface chemistry of graphite coupled with the lower pressure
and higher flow are likely responsible for this performance. The surface area and pore
volume of graphite are poor compared to the other fillers and the Coastal catalyst. Graphite’s
small surface area has a negligible impact on the number of available active sites for
reaction/adsorption. The lower pressure further inhibits removal as stated earlier while the
50
Figure 23: Graphite H2 S Breakthrough vs Time
In the case of methyl mercaptan and ethyl mercaptan, the most effective parameter
variation in terms of breakthrough time is 200 psi, 100℃, and 36 mL/min. This is due to the
higher temperature providing the necessary heat for surpassing the activation barrier, higher
pressure for catalyst penetration through the pores by reducing gas volume and increasing
density, and the increased residence time thanks to the lower flow rate. This is the same as
the H2 S removal; however, the effective breakthrough time is approximately 6 and 6.5 hours,
respectively, compared to the 8 hours for H2 S. With methyl mercaptan, the next two most
effective runs were at 200 psi, ambient and 36 mL/min and 100 psi, 100℃ and 36 mL/min.
Due to the differences between the pressure and temperature in these two runs, one is more
likely an adsorption (200 psi, ambient and 36 mL/min) that is highly dependent on the
limited surface area of graphite while the other is a reaction (100 psi, 100℃ and 36 mL/min)
based on the Coastal catalyst dispersed in the graphite that both have similar removal
effectiveness for methyl mercaptan once mass transfer and surface chemisty is accounted for.
51
The high pressure would aid in adsorption. This happened due to methyl mercaptan and ethyl
mercaptan being larger molecules than H2 S. As such, the catalyst surface and pores are
52
5.2.3 Clay blend experiments. The most effective parameter sets for the clay/Coastal
blend are 200 psi, 100℃, and 36 mL/min with a breakthrough time of 36 hours followed
closely by 100 psi, 100℃, and 36 mL/min and 200 psi, ambient, and 36 mL/min with a
breakthrough time of 35 hours. Of these three runs, the two runs at 100℃ and 36 mL/min are
reaction dominant with pressure not having a noticeable effect on removal. The higher
temperature provided the required energy to meet the activation energy for reaction. Due to
no apparent pressure dependency, it can be assumed that the H2 S reaction is a 0th order
reaction at these conditions. The next two most effective runs were the runs at ambient
temperature and low flow rate. These two runs are adsorption dominant rather than reactive.
While the higher pressure run is comparable to the first two runs, there is a noticeable drop
when the pressure is lowered from 200 psi to 100 psi. Like other runs discussed earlier,
pressure is the major factor in removal via adsorption due to surface contact and pore
penetration. Flow rate had a drastic effect on H2 S removal in this catalyst set at the lower
53
In the methyl mercaptan reactions, the most effective parameter set is 200 psi,
ambient, and 36 mL/min followed closely by all other parameters that use 36 mL/min.
Shown in Figure 28, it is noticed that upon initial breakthrough from 100% removal
efficiency, the reactions still operate ranges from 50-80% removal efficiency for several
more hours before trending to a steady accumulation until the catalyst is completely spent. It
is possible that the competing reactions and adsorption sites on the catalyst along with
pressure inconsistencies throughout the run had an impact on removal for the larger
compounds. In regards for methyl mercaptan, adsorption was the more effective route by
utilizing the higher pressure, lower flow rate and ambient temperature for maximum removal.
54
Figure 28: Clay Methyl Mercaptan Breakthrough vs Time
The ethyl mercaptan data for the clay blend shows that no sign of breakthrough at any
point through 52 hours for three parameters sets: 200 psi, ambient and 36 mL/min; 100 psi,
ambient, and 50 mL/min; and 100 psi, ambient, and 36 mL/min. The data for this particular
filler could possibly be warped due to sensitivity limitations for ethyl mercaptan with the GC
analysis method that was used. As per the Method section, the model gas was fed through the
empty reactor bed and into the GC for calibration runs between all runs utilizing the catalysts
and fillers. During the clay runs, there was little to no response for ethyl mercaptan due to an
outside change made to the GC method and detection limits. This sensitivity issue was
resolved in later runs. In the case of there being no detection issues, the adsorption process
showed more promise for ethyl mercaptan removal rather than a catalytic reaction. None of
the ambient temperature runs showed breakthrough during the duration of run times while all
three runs operated at 100℃ showed breakthrough between 20-30 hours. The lower pressure
seemed adequate for ethyl mercaptan removal at both flow rates to ensure 100% removal,
suggesting that clay has a favorable surface chemistry for ethyl mercaptan adsorption. There
55
was no data found in the literature with clay’s performance in regards to ethyl mercaptan
removal.
immediate in all cases for each compound except for the 100 psi, 100℃, and 50 mL/min
56
experiment. This happened during duplicate experiments as well. The surface area and pore
volume along with powdered structure upon breaking the Sulfatreat are certainly the reasons
for poor performance. The reason for the effect seen in all three graphs associated with the
100 psi, 100℃, and 50 mL/min experiment is most likely due to blockage of the mass flow
controller downstream of the reactor and which was cleared out later near 13 hours into the
experiment. This is verified by immediate breakthrough shown for all three compounds at
this time.
5.2.5 Anthracite blend experiments. For the Anthracite blend, the most effective
parameter variation for H2 S and methyl mercaptan removal via breakthrough time was 200
psi, 100℃, and 36 mL/min with breakthrough occurring at 29 and 16 hours, respectively. As
stated earlier, the higher temperature provided the needed energy to break the activation
energy barrier for the reaction to occur. It can be seen that doubling the pressure from 100 psi
to 200 psi at 100℃ approximately doubles the removal rate. This shows that the pressure is
57
directly proportional to the reaction rate, making this a 1 st order reaction. This is shown as
follows:
where k is the rate constant and CH2 S is the concentration of H2 S. The next most effective
parameter set is 100 psi, 100℃, and 36 mL/min followed closely by 200 psi, ambient, and 36
mL/min. At the 200 psi, ambient, and 36 mL/min variation, adsorption is the dominant
process and is roughly 33% more effective for H2 S removal than the 100 psi, ambient, and 36
mL/min variation.
58
Figure 33: Anthracite Methyl Mercaptan Breakthrough vs Time
The ethyl mercaptan breakthroughs for the clay blend shown in Figure 34 are almost
identical to the other two compounds with the exception of 100 psi, ambient, and 50 mL/min.
This experiment showed no breakthrough for ethyl mercaptan. The other runs follow the
same trend. Theoretically, the 100 psi, ambient, and 50 mL/min run should have been the
first experiment to show breakthrough when compared to the graphs of the other blends.
There is no explanation for this effect at this time other than to adjust the sensitivity of the
GC-MS scans for ethyl mercaptan and redo the experiment at that variation.
59
Figure 34: Anthracite Ethyl Mercaptan Breakthrough vs Time
In Figures 35-52 comparing the blends at specific parameter variations show that clay
was the most effective filler for H2 S, methyl mercaptan, and ethyl mercaptan removal when
compared to the commercially available Sulfatreat among all experiments. The next most
viable filler was anthracite followed by graphite. All three fillers were more effective when
compared to Sulfatreat with the exception of variation 100 psi, 100℃, and 50 mL/min;
however, this result is likely due to a blockage of catalyst downstream of the reactor and
upstream of the GC-MS unit. It is observed that the pore volume and surface area for clay,
anthracite and graphite are generally indicative of how well a filler adsorbent will perform.
Clay had the highest surface area and pore volume followed by anthracite and then graphite.
Sulfatreat had a lower pore size and volume when compared to graphite but a surface area
between anthracite and graphite. Since the initial Sulfatreat pellet was broken apart to utilize
in the reactor, this low pore volume and size hinder sulfur removal to just surface reactions.
While there are discernable differences between the three fillers’ effectiveness, there is a
large gap in performance between these and the Coastal catalyst. The most effective
60
parameter for all four catalysts was 200 psi, 100℃, and 36 mL/min. At this variation, it is
observed that clay came the closest to reaching the Coastal catalyst’s potential when used in
a 9:1 blend followed by anthracite with graphite having the greatest hindrance in aiding
removal. When comparing H2 S removal time ratios between the Coastal catalyst and the
three fillers, clay had the smallest ratio of 8:1. Anthracite had a removal time ratio of
approximately 10:1 while graphite’s was 35:1. Comparisons of breakthrough times for
methyl and ethyl mercaptans between these catalyst and fillers showed similar results.
H2 S, methyl mercaptan, and ethyl mercaptan removed per respective catalyst’s surface area
are shown in Tables 7-9. The Coastal catalyst showed the highest removal for all three
compounds, which were 1.47 g/m2 H2 S at 200 psi, 100℃, and 36 mL/min, 0.13 g/m2
methyl mercaptan at 200 psi, ambient, and 36 mL/min, and 0.13 g/m2 ethyl mercaptan at
200 psi, ambient, and 36 mL/min. Among the fillers, anthracite showed the highest removal
per square meter for hydrogen sulfide and methyl mercaptan while graphite showed the
highest removal per square meter for ethyl mercaptan. The highest H2 S removal for
anthracite occurred at 200 psi, ambient, and 36 mL/min calculated to be 1.25 g H2 S /m2 . The
other two highest removals occurred at 200 psi, 100℃, and 36 mL/min with removals of
0.067 g methyl mercaptan per square meter and a minimum of 0.073 g ethyl mercaptan per
When compared to the literature removals for H2 S, the Coastal catalyst was at least an
order of magnitude more effective while Sulfatreat was subpar. Out of the three fillers,
anthracite and clay showed the highest removal per gram of catalyst and these were
comparable, if not better, to adsorbents in the literature such as the AC modified variations
61
and zeolites. When compared to modified activated carbons derived from oil-palm shell (Guo
et al., 2007) where it was reported that the various adsorbtion capacities ranged from 46-76
mg H2 S/g, all three fillers showed higher removal capacities with the lowest being graphite.
Cu-ZnO supported on mesoporous silica showed adsorption capacities ranging from 9-80 mg
S/g sorbent (Elyassi et al., 2014). In a study regarding methyl mercaptan removal, it was
observed that virgin AC performed the worst whereas Ni-AC and Cu-AC performed the best
with 100% conversion after 180 minutes followed by Al-AC with 95% conversion, Zn-AC
with 92% conversion and then Fe-AC with 89% conversion. Virgin AC showed less than
45% conversion after only 80 minutes. No removal capacities were included in the published
methyl mercaptan of 500 ppm balanced in nitrogen (Zhao et al., 2015). Removal efficiencies
for Ni-Ac and Cu-AC remained 100% through 180 minutes. Al-AC dropped to 95%
efficiency through 180 minutes while Zn-AC and Fe-AC dropped to approximately 92 and
90% efficiency by this time. Virgin AC fell to 45% removal efficiency by 80 minutes into the
experiment. As the Coastal catalyst is mainly an iron-based catalyst and only dealt with
1/10th of the methyl mercaptan load, it is possible that it is not as efficient when compared to
other metal modified ACs found in the literature. There could also be complications due to
the competing reactions of the three sulfur compounds studied in this work that the other
catalysts did not have. These modified ACs were more effective at removing methyl
mercaptan than the three filler materials when comparing loading weight. A study regarding
the removal of hydrogen sulfide and methyl mercaptan utilizing light expanded clay
aggregates (Leca) showed an affinity for removing these two compounds. Dry Leca showed
removal at 50 mL/min and 180 mL/min for 28 and 20 hours respectively with inlet
62
concentrations of approximately 900-1000 ppb for both compounds, comparable to the clay
and anthracite fillers studied in this work (Tabase, Liu, & Feilberg, 2013).
63
Figure 37: Ethyl Mercaptan Breakthrough at 100 psi 100℃ 50 mL/min
64
Figure 39: Methyl Mercaptan Breakthrough at 100 psi 100℃ 36 mL/min
65
Figure 41: H2 S Breakthrough at 100 psi Amb 50 mL/min
66
Figure 43: Ethyl Mercaptan Breakthrough at 100 psi Amb 50 mL/min
67
Figure 45: Methyl Mercaptan Breakthrough at 100 psi Amb 36 mL/min
68
Figure 47: H2 S Breakthrough at 200 psi Amb 36 mL/min
69
Figure 49: Ethyl Mercaptan Breakthrough at 200 psi Amb 36 mL/min
70
Figure 51: Methyl Mercaptan Breakthrough at 200 psi 100℃ 36 mL/min
71
Table 7: Maximum removal of H2 S
100 psi 1.29 g/𝐦𝟐 0.20 g/𝐦𝟐 0.15 g/𝐦𝟐 0.81 g/𝐦𝟐 0.34 g/𝐦𝟐
100 ℃
50 mL/min
100 psi 1.27 g/𝐦𝟐 0.041 g/𝐦𝟐 0.26 g/𝐦𝟐 0.65 g/𝐦𝟐 0.58 g/𝐦𝟐
100 ℃
36 mL/min
200 psi 1.32 g/𝐦𝟐 0.051 g/𝐦𝟐 0.26 g/𝐦𝟐 0.72 g/𝐦𝟐 0.58 g/𝐦𝟐
Ambient
36 mL/min
100 psi 0.94 g/𝐦𝟐 0.18 g/𝐦𝟐 0.20 g/𝐦𝟐 0.02 g/𝐦𝟐 0.29 g/𝐦𝟐
Ambient
36 mL/min
100 psi 0.91 g/𝐦𝟐 0.059 g/𝐦𝟐 0.16 g/𝐦𝟐 0.38 g/𝐦𝟐 0.27 g/𝐦𝟐
Ambient
50 mL/min
200 psi 1.47 g/𝐦𝟐 0.15 g/𝐦𝟐 0.30 g/𝐦𝟐 1.25 g/𝐦𝟐 0.15 g/𝐦𝟐
100 ℃
36 mL/min
72
Table 8: Maximum Removal of Methyl Mercaptan
Mercaptan
100 psi 0.1 g/𝐦𝟐 0.03 g/𝐦𝟐 0.015 g/𝐦𝟐 0.045 g/𝐦𝟐 0.021 g/𝐦𝟐
100 ℃
50 mL/min
100 psi 0.09 g/𝐦𝟐 0.005 g/𝐦𝟐 0.011 g/𝐦𝟐 0.042 g/𝐦𝟐 0.049 g/𝐦𝟐
100 ℃
36 mL/min
200 psi 0.13 g/𝐦𝟐 0.004 g/𝐦𝟐 0.022 g/𝐦𝟐 0.050 g/𝐦𝟐 0.044 g/𝐦𝟐
Ambient
36 mL/min
100 psi 0.08 g/𝐦𝟐 0.013 g/𝐦𝟐 0.020 g/𝐦𝟐 0.0017 g/𝐦𝟐 0.020 g/𝐦𝟐
Ambient
36 mL/min
100 psi 0.08 g/𝐦𝟐 0.006 g/𝐦𝟐 0.016 g/𝐦𝟐 0.041 g/𝐦𝟐 0.027 g/𝐦𝟐
Ambient
50 mL/min
200 psi 0.1 g/𝐦𝟐 0.014 g/𝐦𝟐 0.018 g/𝐦𝟐 0.067 g/𝐦𝟐 0.063 g/𝐦𝟐
100 ℃
36 mL/min
73
Table 9: Maximum Removal of Ethyl Mercaptan
Mercaptan
100 psi 0.089 g/𝐦𝟐 0.035 g/𝐦𝟐 0.044 g/𝐦𝟐 0.058 g/𝐦𝟐 0.041 g/𝐦𝟐
100 ℃
50 mL/min
100 psi 0.095 g/𝐦𝟐 0.0057 g/𝐦𝟐 0.026 g/𝐦𝟐 0.052 g/𝐦𝟐 0.058 g/𝐦𝟐
100 ℃
36 mL/min
200 psi 0.13 g/𝐦𝟐 0.0029 g/𝐦𝟐 0.046 g/𝐦𝟐 0.059 g/𝐦𝟐 0.054 g/𝐦𝟐
Ambient (minimum)
36 mL/min
100 psi 0.081 g/𝐦𝟐 0.022 g/𝐦𝟐 0.037 g/𝐦𝟐 0.059 g/𝐦𝟐 0.049 g/𝐦𝟐
Ambient (minimum)
36 mL/min
100 psi 0.080 g/𝐦𝟐 0.0043 g/𝐦𝟐 0.038 g/𝐦𝟐 0.22 g/𝐦𝟐 0.054 g/𝐦𝟐
50 mL/min
200 psi 0.11 g/𝐦𝟐 0.010 g/𝐦𝟐 0.025 g/𝐦𝟐 0.069 g/𝐦𝟐 0.073 g/𝐦𝟐
100 ℃
36 mL/min
74
5.3 Economics
Figure 53: Natural Gas Price Trends (U.S. Energy Information Administration, 2019)
used to prepare a preliminary economic analysis. Trending natural gas data from 1985-2019
was used to estimate the cost to reform natural gas from the wellhead to industry use. While
the last published wellhead price was in December 2012, the wellhead data follows the other
two data trends from 2000 to 2019 for commercial and industrial prices. As such, it was
assumed that the latest wellhead price will be approximately $1.5/Mcf less than the industrial
price. This difference is used as the cost to reform sour natural gas to cleaner natural gas that
can be used in industry that has not been marked up like the commercial sale price.
$ catalyst
=$ (32)
MCF Q ∗ t b ∗ conv ∗ 1000
75
Where Q is the volumetric flowrate of the treated gas in mL/min, t b is the breakthrough time
and the cost is adjusted per 1000 ft 3 . Each parameter was costed and is shown in Table 10.
The costs for clay, anthracite and graphite were $77/ton, $93.17/ton, and $1,050/tonne,
respectively (U.S. Energy Information Administration, 2018), (Focus Graphite Inc., 2015) (T.
Wang, 2019).
76
Table 10: Material cost per 1000 ft 3 treated gas (Mcf) at each variation
100℃
50 mL/min
100℃
36 mL/min
Ambient
36 mL/min
100℃
36 mL/min
Ambient
50 mL/min
Ambient
36 mL/min
77
Based on cost per treated gas, the cheapest of the five materials is clay followed
closely by anthracite. Graphite should be excluded due to the poor removal and its high price
per volume of treated gas. It is higher than all except for Sulfatreat. The Coastal material
should still be prioritized over clay and anthracite due to the high amount of gas it treated
when compared to the other two materials. Even though it is more expensive, it outperforms
these two materials to the point where it is still cheaper to operate with a smaller amount of
Coastal catalyst vs the amount of clay or anthracite to achieve the same removal. These three
options are more favorable than the trended data for reforming wellhead natural gas to
industrial grade natural gas while Sulfatreat and graphite would cost more to achieve this
78
Chapter 6: Conclusions
The surface chemistry of the unreacted catalysts and surface chemistry and
compositions of the spent catalysts were explored and defined using various analytical
methods such as FTIR, PIXE, BET, and TGA. The breakthrough times of H2 S, methyl
mercaptan, and ethyl mercaptan using the Coastal catalyst, Sulfatreat, clay blend, anthracite
1. The Coastal catalyst without fillers was the most effective in removing H2 S, methyl
mercaptan, and ethyl mercaptan were 276.5 hr, 243 hr and 245 hr, respectively, and
the maximum amounts removed were 296.24 g H2 S, 26.25 g methyl mercaptan, and
2. The catalyst effectiveness for sulfur removal followed the order from highest to
lowest: Coastal > clay > anthracite > graphite > Sulfatreat.
3. The most effective operating conditions with the six variations used in terms of
longest breakthrough time and highest sulfur removal was 200 psi, 100℃, and 36
mL/min followed closely by 200 psi, ambient, and 36 mL/min and 100 psi, 100℃,
and 36 mL/min.
4. The Coastal catalyst does regenerate in the presence of oxygen, producing a highly
exothermic reaction. This opens up the possibility of multiple uses of the same
5. While clay and anthracite are the cheapest of the five materials, much more of these
two materials are needed to compete with the effective runtime of the Coastal
79
catalyst. These three materials are cheaper to operate when compared to the trended
80
Chapter 7: Recommendations and Future Works
• Run additional experiments of all parameter variations to verify the initial one run
results.
• Add a manual sampling port downstream of the reactor and upstream of the GC-MS
to build in redundancy. Manual samples can be taken and run in a second GC-MS to
verify that there are not any complications with the primary GC-MS and its sampling
control valve.
comprehensive mechanism.
• Determine a full mechanism that covers all species of the Coastal catalyst and which
• Scale-up reaction experiments to observe if flow regimes and mass transfer effects
• Test clay, anthracite, and graphite without the Coastal blend to determine the
• Study possible regeneration and the effects on catalyst activity after regeneration of
• Study the effects on pretreating the catalysts such as heat treating, removing volatiles
81
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Appendix A
Due to the information size and number of calculations, the data tables are enclosed
86
Conerly, Jerry F., III. Bachelor of Science, Mississippi State University, Spring 2015; Master
of Science, University of Louisiana at Lafayette, Fall 2019
Major: Engineering, Chemical Engineering concentration
Title of Thesis: Removal of Sulfur Contaminants in Natural Gas Streams
Thesis Director: Dr. Rafael Hernandez
Pages in Thesis: 97; Words in Abstract: 214
Abstract
primary pollutant of concern is hydrogen sulfide (H2 S) due to toxicity, corrosion, and
to a common industrial catalyst for sulfur removal, Sulfatreat, particularly for H2 S, methyl
and ethyl mercaptans. The effects of dispersing the proprietary catalyst in a 1:9 ratio among
three different fillers: anthracite, graphite, and clay, were studied along with variations on
temperature, pressure, and flow rate. The catalyst was characterized using Brunauer-Emmett-
Teller (BET) analysis, proton induced X-ray emission (PIXE) analysis, Fourier transform
infrared spectroscopy, and thermogravimetric analysis (TGA). The reaction results were
observed and generated using gas chromatography-mass spectrometry (GC-MS) and showed
that the optimal operating parameters in terms of breakthrough time were at 200 psi, 100℃,
and 36 mL/min for all catalysts and blends used. When compared to the industrial standard
Sulfatreat, all three blends with the proprietary catalyst showed higher performance. Of the
three blend materials, clay showed the most removal effectiveness of H2 S, methyl mercaptan,
and ethyl mercaptan. Anthracite was the next most effective followed by graphite.
Economically, clay and anthracite are both desirable to use as a filler material to offset the
cost of exchanging Sulfatreat for a 1:9 ratio proprietary catalyst dispersed in filler.
87
Biographical Sketch
Jerry Conerly III was born in McComb, Mississippi, on March 25, 1992, and grew up
Lafayette in Fall 2015. He completed his M.S. degree at the University of Louisiana at
88
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