Breath Hydrogen (H2) and Methane (CH4) Excretion Patterns in ...
EFFECT OF CHANGING CH4 2 RATIO ON HYDROGEN …
Transcript of EFFECT OF CHANGING CH4 2 RATIO ON HYDROGEN …
1
EFFECT OF CHANGING CH4 /CO2 RATIO ON HYDROGEN
PRODUCTION BY DRY REFORMING REACTION FAKEEHA *, A.H. , ALFATISH, A.S., SOLIMAN , M.A. , IBRAHIM A.A.
CHEMICAL ENGINEERING DEPARTMENT,COLLEGE OF ENGINEERING KING SAUD UNIVERSITY ,P.O.BOX 800 ,RIYADH 11421 , SAUDI ARABIA * [email protected] 1. ABSTRACT
Experimental investigation for dry reforming of methane with carbon dioxide was carried out. This
study was aimed to explore the effect of changing the ratio of methane to carbon dioxide in the feed
gas. The experiments were carried out using seven different ratios of methane to carbon dioxide that
range from 0.25 – 4.0, three different temperature 773, 823, 848 K as well as three different total feed
flow rate 10, 15, 20 ml/ min. at atmospheric pressure .The runs were carried out in AMI – 2000 Zeton-
Altimira microreactor. The results indicate that increasing the ratio of methane to carbon dioxide
decreases methane conversion, increases in carbon dioxide conversion and decreases hydrogen yield at
each temperature used. Changing total feed flow rate has no effect on either conversion or hydrogen
yield.
KEYWORDS: Hydrogen Production, Dry Reforming , Synthesis Gas ,CH4 / CO2 Ratio.
2. LITERATURE REVIEW
Steam reforming of CH4 using nickel catalyst has been industrialized for a long time [1]. In
recent years, the carbon dioxide reforming of methane known as dry reforming has gained
increasing importance and rapidly growing interest in the catalytic conversion of CH4 and CO2
to synthesis gas (syngas) because this reaction has many potential incentives with
economical and environmental benefits [2-9]. Reforming equations of methane are given
below:
• Dry reforming reaction:
CH4 + CO2 ↔ 2CO + 2H2 ∆H298° = 247 kJ/mol
• Steam reforming reaction:
CH4 + H2O ↔ CO + 3H2 ∆H298° = 206 kJ/mol
2
Nevertheless, the dry reforming reaction is now being recommended for the chemical energy
transmission system (CETS) to replace steam reforming [3-5].
Fakeeha et.al [6-7] and Al-Fatish [8] peformed comprehensive studies for dry reforming of
methane using nickel based supported catalyst . Their studies concentrated on the effect of
using different supports ( alumina ,silica , TiO2 ,ZrO2) , different promoters ( Co , Ce , Mo
Ca , Sb , Sn ) , calcination temperatures . The prepared catalysts were tested at different
conditions of pressure , temperatures and flow rates . The results indicate that catalyst
prepared with high surface area alumina using Ce as promoter is the best among the tested
catalysts ,it has the highest activity and is stable for at least 98 hours
Gadalla and Sommer [10] studied and characterized an industrial Ni catalyst supported on
CaO – TiO – Al2O3. The catalyst was used for methane reforming with carbon dioxide, and
compared with catalyst containing Ni on other supports. Conversion close to 100% were
achieved during 51 hours on stream for a CO2: CH4 ratio of 2.64:1 using a weight hourly
space velocity of 7.38 h-1 despite the solid state reaction and sintering which decrease the
surface area.
Stagg et al. [11] studied the reforming of CH4 with CO2 at 800 °C over SiO2 and ZrO2
supported Pt-Sn catalyst. Several preparation methods were investigated. It was found that
the Pt/ZrO2 catalyst had much higher activity and stability than the Pt/SiO2 catalyst due to
ability of the ZrO2 to promote CO2 dissociation on this catalyst. The decomposition of CH4 and
the dissociation of CO2 occur via two independent pathways. The long-term activity of the
catalyst is dependent upon the balance between the rate of CH4 decomposition and the rate
of cleaning of carbonaceous deposits. The Co-impregnation of Sn and Pt on the ZrO2 results
in lower activity and stability than the monometallic catalysts. Depending on the reaction
conditions, disruption of the Pt-Sn alloys may occur causing deposition of tin oxide that
inhibits the role of the ZrO2. Special preparation methods can result in the controlled
placement of Sn on the Pt particle minimizing the promoter-support interaction. The catalysts
exhibit higher activity and stability than the monometallic catalyst under severely deactivating
conditions, 800 °C and 3:1 ratio of CH4: CO2. It is possible to deposit Sn onto Pt/ZrO2 catalyst
in manner, which reduces carbon deposition without inhibiting the beneficial role of the
support.
3
Liu and Au [12] reported that investigation for dry reforming has been renewed due to
environmental and commercial reasons. Synthesis gas with a low H2: CO ratio is preferred
for the production of liquid hydrocarbons and oxygenated derivatives. One advantage of CO2/
CH4 reforming is the low H2: CO ratio in syn gas formation; the process opens the possibility
of combining steam reforming, partial oxidation, and dry reforming for the generation of a syn
gas with a desired H2: CO ratio. For environmental protection and to fight against global
warming, it makes sense to study the utilization of CO2 and CH4. Both compounds are
considered as greenhouse gases. In addition, since there is CO2 (≥ 25 vol. %) in field gases,
it is beneficial to utilize CO2 directly in methane, reforming rather than separating it from
methane.
Wargadalm et al. [13] studied methane reforming with CO2 in hot temperature in a thermal
diffusion column reactor. The temperature effect on tungsten, molybdenum and chromel wires
showed molybdenum to be the best wire. As the ratio of CO2: CH4 changes from 1.97 to 0.55,
the CO: H2 ratio changed from 1.56 to 0.74. Accordingly, it may be possible to change the
composition of the synthesis gas to suit the utilization to which it is intended.
Huang et al [14] performed CO2 reforming of CH4 at atmospheric pressure by alternating
current discharge plasma in Y type reactor. The investigators studied the effects of reaction
parameters such as input voltage, total flow rate, mole fraction of methane to carbon dioxide,
selective excitation of either reactant, and micro-arc formation, on product distribution and
energy efficiency. Their result showed the dependence of CH4 and CO2 conversions and
selectivity on the CH4 / CO2 ratio. With an increasing of CH4 / CO2 ratio from 1/9 to 9/1, the
conversion of CH4 (97.3-84.2) and selectivity to hydrogen (74.5-28.6) and to CO (98.9-21.5)
decreased while the conversion of CO2 (22.0-77.5) and to hydrocarbons increased.
The specific objectives of this research is to investigate the effect of changing the percentage
of methane to carbon dioxide in the feed for the production of synthesis gas using nickel
based catalyst at different temperatures and flow rates.
3. EXPERIMENTAL
In this work Ni - base supported catalysts were used . The support used is γ-alumina (SA-
6175) with surface area of (230 – 290 m2/gm) Impregnation of the support was carried out
4
with aqueous solutions of nickel-nitrate. Cerium (Ce) is used as promoter in preparation of
the supported Ni- based catalysts. The resulting catalyst dried in the oven at 110 C for 13
hours then calcined at 600 C in air atmosphere for 5 hour.The reproducibility of the results
was checked during this work period by repeating the experiments under the same
conditions several times.
Experimental Set-up The heart of the experimental setup used in this study is a micro-reactor made by ZETON-
ALTAMIRA ( model AMI 2000) . The whole experimental setup is shown schematically in
Fig. 1. The system is composed of the following sections:
I. Feed Section: The feed section contains three gas cylinders for CO2, CH4 and N2.
Gases coming from the regulators pass through in-line filters then introduced to the
Mass Flow Controllers (MFC), obtained from Brooks. The gases are mixed and passed
to the reaction section. On line samples from the feed gas mixture are directed to gas
chromatograph for analysis.
II. Reaction Section: The micro-reactor overall length is 0.43m, with inside diameter of
6.35x10-3 m made of stainless steel and surrounded by three zones heater. Each zone
temperature can be controlled separately. The temperature in the reactor is measured
by a thermocouple located in the catalyst bed. The outlet from the reactor (bottom end)
is passed through a backpressure regulator (BPR) to control the pressure in the reactor
and the product gases from the BPR were sent to analysis section.
III. Analysis Section: The analysis was carries out by using Varian gas chromatograph
( model 3400 CX ) with TDC detector; the TDC detector is equipped with Hysis column.
Catalysts Characterization:
The BET surface area for selected catalysts are meaured by using equipment model
(ASAP2010) , samples of catalysts were analysized by using Scanning electron micro
scope (SEM) model “ JEOL, JSM – 6360A “ to get pictures for the surface of the catalysts
5
Activation procedure
The activation procedure is as follow:
A. Introduce hydrogen to the reactor at 20 ml/min for 2.5 hr.
B. Then hydrogen is stopped while N2 is introduced at 40 ml/min for one hour
This pretreatment process was found to be essential for the reaction to take place [6-8 ].
Figure .1: Schematic diagram of experimental setup: HV1, HV2 and HV3: Filters, MFC s Mass Flow Controller, PG Pressure Gauge CV1, CV2 and CV3 Shut – off Valves, SV1: Sampling Valve, F: Furnace, R: Reactor, T1 ، T2 and T3: Temperature Measurement location (by Thermocouple), GC: Gas Chromatograph, PCV: Pressure Control Valve.
6
4. RESULTS AND DISCUSSION:
The experimental runs were carried out in order to achieve the objectives of this investigation
by finding the effect of changing the ratio of methane to carbon dioxide in the feed gas .The effect of
changing total feed flow rate were also investigated. To insure reproducibility of the results , the
experiments were repeated under similar conditions several times during the course of this work.
Effect of Changing Methane to Carbon Dioxide Ratio in the Feed:
Seven methane to carbon dioxide ratios were selected during this project:2/8 (0.25), 3/7
(0.43), 4/6 (0.67), 5/5 (1), 6/4 (1.5), 7/3 (2.33), and 8/2 (4). The runs for each set of
experiment were carried out at constant flow rate of 10ml/ min and total pressure of 14.7 psi
and specific temperature. The results for methane conversion, carbon dioxide conversion and
hydrogen yield are shown in figures 2-4. respectively. Three different sets were performed at
three different temperature 773, 823, 848 Kº. For methane conversion, Figure (2) indicates
that as the ratio of methane to carbon dioxide increases at 773 Kº, the methane conversion
decreases sharply up to a ratio of 5/5. Then the conversion decrease reduces slowly up to a
ratio of 7/3 then it become constant after that within our experimental range. The methane
conversion decreased from 30% at a ratio of 2/8 to almost 10% at a ratio of 8/2. The same
trend for the effect of changing methane to carbon dioxide ratio was obtained at 823 Kº, but
with more sharper decrease at the start. The methane conversion decreased from a value of
58% at a ratio of 2/8 to 24% at a ratio of 8/2. Similar behavior was obtained at 848 Kº with
methane conversion decreased from 70% at a ratio of 2/8 to 30% at a ratio of 8/2 methane to
carbon dioxide.
The reasons for the decrease in methane conversion can be explained using the la chatelier
principle.
224 22 HCOCOCH +↔+
At low CH4 / CO2 ratio since CO2 is in excess, it forces CH4 to be converted to CO and H2 (
according to La chatelier principle) . As CH4 / CO2 ratio increased,the CO2 amount
decreased causing lower CH4 conversion. When the ratio increased above 1, CH4 starts to
decomposed to carbon and hydrogen according to the following equation:
CH4 ↔ 2H2 + C
7
This accounts for not continuing the decrease trend in methane conversion. As evidenced by
the increased ratio of H2: CO.
Figure 2 . Effect of changing CH4/CO ratio on CH4 Conversion.
05
1015202530354045505560657075
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 2.2 2.4 2.6 2.8 3 3.2 3.4 3.6 3.8 4
CH 4 / CO2
CH
4 C
onve
rsio
n pe
rcen
t
T=773 ºK T=823 º K T=848 º K
F=10 ml/min , P=14.7 PSI Support( SA-6175)
Figure (3) presented the conversion of carbon dioxide as function of methane to carbon
dioxide ratios at a total flow rate of 10 ml/min, total pressure of 14.7 psi and three different
temperature 773, 823 and 848 Kº.
The trend here is opposite to what obtained for methane conversion, the carbon dioxide
conversion increased as the ratios of methane to carbon dioxide increased. The carbon
dioxide conversion is 15% at 773 Kº for methane to carbon dioxide ratio of 2/8 and increased
to almost 40% at a ratio of 8/2. The carbon dioxide conversion at higher temperatures 823,
848 Kº are 25% and 31% at a ratio of 2/8 and increased to 55% , 65% at a ratio of 8/2
respectively. The increase in CO2 conversion is due to increase in the amount of CH4, which
causes more conversion of CO2 according to Le chatelier principle.
WHEC 16 / 13-16 June 2006 – Lyon France
8/12
Figure 3 . Effect of changing CH4/CO2 ratio on CO2 Conversion .
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 2.2 2.4 2.6 2.8 3 3.2 3.4 3.6 3.8 4
CH 4 / CO2
%C
O2
Con
vers
ion
T=773 ºK T=823 ºK T=848 ºK
The hydrogen yield is shown in Figure (4). From the previously discussed cases, the effect of changing the
ratios of methane to carbon dioxide is similar to that of methane conversion. Three set of results were plotted
with total flow rate of 10ml/min and a total pressure of 14.7 psi and at temperatures of 773, 823, 848 Kº.
Figure 4 . Effect of changing CH4/CO2 ratio on hydrogen yield
05
1015202530354045505560657075
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 2.2 2.4 2.6 2.8 3 3.2 3.4 3.6 3.8 4 CH 4 / CO2
H2
yiel
d %
T=773 ºK T=823 ºK T=848 ºK
F=10 ml/min , P=14.7 PSI support ( SA-6175)
F=10 ml/min , P=14.7 PSI Support ( SA-6175)
WHEC 16 / 13-16 June 2006 – Lyon France
9/12
Effect OF Flow Rate:
Three different flow rate were chosen 10 ml/ min, 15 ml/min and 20 ml/min .The total pressure used was
14.7 psi and methane to carbon dioxide was fixed at 0.25. Three different set of experiments were performed
at these flow rates. Each set was performed at a specific temperature. The temperatures used for these sets
are 773, 823, 848 Kº. The results are shown in Figure 5. and. There is almost no change in hydrogen yield
at each set when flow rate changes within our experimental range. At 773 Kº, 30% hydrogen yield was
obtained. As temperature increased the hydrogen yield increased. At 823 and 848 Kº, the hydrogen yield
are approximately 51% and 64% respectively. The constancy in hydrogen yield with the change in flow rate
indicates that the reaction reaches equilibrium condition.
The BET- surface area of the alumina support , fresh catalyst and used catalyst are 222.5 , 208.5 and 194
m2 / gm. Picture for fresh and used catalyst are shown at figures 6&7.
F igure 5 . E ffec t o f chang ing flow ra te on hydrogen y ie ld
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
10 12 14 16 18 20
Tota l flow ra te ( m l/m in .)
Per
cent
H2 y
ield
T=773 ºK T=823 ºK T=848 ºK
P =14.7 P S I S upport( SA -6175) C H 5/C O 2 = 0 .25
WHEC 16 / 13-16 June 2006 – Lyon France
10/12
Figure 6 . Scanning microscopy of fresh catalyst at 500 magnification
Figure 7. Scanning microscopy of used catalyst at 900 magnification
WHEC 16 / 13-16 June 2006 – Lyon France
11/12
5. CONCLUSION Experimental investigation for the effect of changing the ratio of methane to carbon dioxide in the feed to dry
reforming reaction were carried out in AMI- 2000 Zeton – Altimira micro-reactor. Seven ratios of methane to
carbon dioxide that range from 0.25 –4.0 were selected in this study. Three different temperatures were used
773, 823 and 848 Kº. Similarly three different total feed flow rate were also used 10, 15, 20 ml/min. The
following conclusions could be drawn from the results obtained in this investigation:
• Increasing CH4 / CO2 ratio led to decrease in methane conversion at each temperature used.
• Increasing CH4 / CO2 ratio led to an increase in carbon dioxide conversion at each temperature
used.
• Increasing CH4 / CO2 ratio led to decrease in Hydrogen yield at each temperature used.
• As temperature increased the conversion of both gases as well as hydrogen yield increased.
• No effect on conversion or hydrogen yield was observed by changing total feed flow rate.
6. ACKNOWLEDGEMENT The Principal investigator and research team would like to thank the Saudi Basic Industrial
Cooperation (Sabic), for funding this investigation through the grant given to the University to
support research and the College of Engineering Research Center for accepting this investigation as
project # (14/425) and all supports they provided.
7. REFERENCE [1] G. Barbieri, V. Violante, F.P.Di Mario, A. Criscuoli, and E. Drioli, “Membrane-steam reforming analysis in
a palladium-based catalytic membrane reactor. Ind. Eng Chem Res, 36, pp.336, 1997.
[2] S. Wang and Lu. GQM, “ A comprehensive study on carbon dioxide reforming of methane over Ni/γ-
Al2O3 catalysts”, Ind. Eng Chem. Res., 38, pp. 2615, 1999.
[3] V.R. Choudhary and A.S. Mamman, ““ Simultaneous oxidative conversion and carbon dioxide or
steam reforming of methane to syngas over CoO-NiO-MgO catalysts “, J. Chem. Technol.
Biotechnical , 73, pp. 345 (1998).
WHEC 16 / 13-16 June 2006 – Lyon France
12/12
[4] T. Osaki, T. Horiachi, K. Suzuki, T. Mori, “Suppression of carbon deposition in Carbon dioxide
reforming of methane on metal sulphide catalyst”, Catal. Lett., 35, pp.39, 1995.
[5] Y. Sakai, H. Satio, T. Sodesawa and F. Nozaki, React. Kinet. “Catalytic reactions of hydrocarbon
with carbon dioxide over metallic catalysts.”, Catal. Lett., Vol. 24, No. 3-4, pp.253, 1984.
[6] Fakeeha, A.H., Soliman, M.A. and AL Fatish, A.S., “ The effect of usin different supports on the
production of hydrogen by dry reforming “, proceeding of 1St European Hydrogen Energy
confernce,held at Grenoble , France , during 2-5 September 2003.
[7] Fakeeha, A.H., Soliman, M.A. and AL Fatish, A.S., “ Effect of Promoters on hydrogen production
by dry reforming Reaction“, proceeding of 2nd European Hydrogen Energy conference, held at
Zaragoza , Spain , September 22-25, 2005.
[8] Al-Fatish , A.S. “ Dry reforming of Methane over Supported Nickel Catalysts” , Ms Thesis, King Saud
Univesity,2003.
[9] S. Wang and Lu GQM, “ A comprehensive study on carbon dioxide reforming of methane over Ni / γ-
alumina catalyst “, Ind. Eng. Chem. Res., 38, pp. 2615, (1999).
[10] A.M.Gadalla and M.E. Sommer, “Carbon dioxide reforming of methane on Nickle catalyst”, Chem.
Eng. Sci., 44, pp.2825, 1989.
[11] S.M. Stagg. E. Romeo and D.E. Resasco, “Effect of promotion with Sn on supported Pt catalyst for
carbon dioxide reforming of methane”, J. Catal. 178, pp.137, 1998.
[12] B.S. Liu and C.T. Au. ”Carbon deposition and catalyst stability over La2NiO4/ γ- Al2O3 during carbon
dioxide reforming of methane to syngas”, Appl. Catal. A: General, 244, pp.181, 2003.
[13] V.J. Wargadalam, N.R. Hunter and H.D. Gesser, “The carbon dioxide reforming of methane in a
thermal diffusion column hot wire reactor”, Fuel Processing Technology, 59, No 2-3, pp.201, May
1999.
[14] A. Huang, G Xia, J. Wang, S.L. Suib, Y Hayashi and Hmatsumoto,” CO2 Reforming of CH4 by
Atmospheric pressure ac discharge plasmas”, Journal of Catalysis, 189 , pp. 349, 2000.