Table of Contents

1.Introduction .................................................................................................................................. 2
1.1.CNG…………………………………………………………………………………………………………………………………………… 2

1.2.Composition of CNG…………………………………………………………………………………………………………………. 2

1.3.Advantages of CNG…………………………………………………………………………………………………………………… 4

1.4.Adverse effect of methane……………………………………………………………………………………………………….. 5

1.5.Actions to reduce CH4 emissions…………………………………………………………………………………………….... 5

2.General preparation methods for supported catalysts………………………………………………………………6

2.1. Incipient wetness method…………………………………………………………………………………………………….... 6

2.2.Wet impregnation method……………………………………………………………………………………………………….. 6

2.3.Deposition precipitation method………………………………………………………………………………………………. 6

2.4.Citric acid sol-gel method………………………………………………………………………………………………………….. 6

3.Catalysts preparation and their operating parameters in brief………………………………………………….7

3.1.Nobel Metal catalysts………………………………………………………………………………………………………………… 7

3.2.Gold-Based catalysis………………………………………………………………………………………………………………….. 8

3.3.Base Metal catalysts………………………………………………………………………………………………………………….. 9

3.4.Cobalt based catalyst……………………………………………………………………………………………………………….. 11

3.5.Perovskites………………………………………………………………………………………………………………………………. 13

4.Conclusion………………………………………………………………………………………………………………………………14

References………………………………………………………………………………………………………………………..15

1
Catalytic abatement of methane emission from CNG
vehicles
Srijan Tiwari, Lenin Mahiya

Indian Institute of Technology (B.H.U), Varanasi

1. Introduction
1.1 Compressed natural gas (CNG)

CNG is a readily available alternative to petrol and diesel that’s made by compressing natural gas to less
than 1% of its volume at standard atmospheric pressure. Consisting mostly of methane, CNG is odorless,
colorless and tasteless. It's drawn from domestically drilled natural gas wells or in conjunction with crude
oil production. Worldwide, there were 22.7 million NGVs by 2015, led by China (4.44 million),
Iran (4.00 million), Pakistan (3.70 million), Argentina (2.48 million), India (1.80 million),
and Brazil (1.78 million). The average growth rate in the world is blooming with 30.6% per year.

1.2 Composition of CNG

Fig. 1 Composition of CNG

Natural gas is a naturally occurring gas mixture, consisting mainly of methane. While the gas from
different sources has a similar analysis, it is not entirely the same. The table below outlines the typical
components of natural gas on the Union Gas system and the typical ranges for these values (allowing for
the different sources).

2
Note that there is no guarantee of the following composition at your location or as an overall system
average. Since the different gas supplies enter the Union Gas system at different locations, the exact
composition at any site will vary among the different regions. The system average heating value will
depend on the mix of gas supplies (which is increasingly controlled by our customers), and therefore can
vary from the typical value listed below.

Table 1. Composition of CNG

Component Typical Analysis Range

(mole %) (mole %)
Methane 95.0 87.0 - 97.0
Ethane 3.2 1.5 - 7.0
Propane 0.2 0.1 - 1.5
iso - Butane 0.03 0.01 - 0.3
normal - Butane 0.03 0.01 - 0.3
iso - Pentane 0.01 trace - 0.04
normal - Pentane 0.01 trace - 0.04
Hexanes plus 0.01 trace - 0.06
Nitrogen 1.0 0.2 - 5.5
Carbon Dioxide 0.5 0.1 - 1.0
Oxygen 0.02 0.01 - 0.1
Hydrogen trace trace - 0.02
Specific Gravity 0.58 0.57 - 0.62

Gross Heating Value (MJ/m3), dry 38.0 36.0 - 40.2

basis *

* The gross heating value is the total heat obtained by complete combustion at constant pressure of a unit
volume of gas in air, including the heat released by condensing the water vapour in the combustion
products (gas, air, and combustion products taken at standard temperature and pressure).

Sulphur: In the Union Gas system, the typical sulphur content is 5.5 mg/m3. This includes the 4.9 mg/m3
of Sulphur in the odorant (mercaptan) added to gas for safety reasons.

Water: The water vapor content of natural gas in the Union Gas system is less than 80 mg/m3, and is
typically16 to 32 mg/m3.

3
1.3 Advantages of CNG

 Natural gas is significantly less expensive than gasoline. The cost of natural gas can go as low as
$0.64 a GGE or Gasoline Gallon Equivalent. In some areas, natural gas costs as low as a third of
the cost of gasoline, on average.
 CNG is eco-friendlier than gasoline. Natural gas produces far fewer harmful emissions and
hydrocarbons than gasoline.
 Using CNG makes the engine cleaner and more efficient. Unlike gasoline, CNG
minimizes harmful carbon deposits when combusted. This results to a cleaner and more efficient
engine as well as longer lasting spark plugs. Oil changes are also minimized because of carbon
deposits that contaminate the oil is eliminated.
 CNG is not abundant in India but it is much cheaper than other fuels. Switching to CNG can help
ease the country’s dependence to other fuels.
 CNG has higher Octane levels averaging over 120 Octane.


Fig. 2 Cost comparison of natural gas vs other fuels

4
1.4 Adverse effect of methane

 Methane emissions adversely affect humans and environment. It has drastic effects on nature as
GHP and hence climate change.

Effects on humans

In normal circumstances, methane is not toxic to humans. It causes asphyxiation by displacing oxygen.
However long-term exposure of methane to humans can cause loss of consciousness, depression,
suffocation, emotional upset, fatigue, nausea or even death can occur.

Effects on nature

Methane is also the most abundant reactive trace gas in the troposphere and its reactivity is important to
both tropospheric and stratospheric chemistry. The oxidation of CH4 by hydroxyl (OH) in the troposphere
leads to the formation of formaldehyde (CH2O), carbon monoxide (CO), and ozone (O3), in the presence
of sufficiently high levels of nitrogen oxides (NOx). Along with CO, methane helps control the amount of
OH in the troposphere. Methane affects the concentrations of water vapor and ozone in the stratosphere,
and plays a key role in the conversion of reactive chlorine to less reactive HCl in the stratosphere.

1.5 Actions to reduce CH4 emissions

It is likely that the emission legislation will be more stringent in the near future, since the current limits
lead to unacceptable emissions from a health point of view. As emissions are a result of many parameters
and these parameters can be optimized in order to reduce or meet the stringent legislations. There are two
principal approaches for decreasing CH4 emission from internal combustion engines.

1. Optimization of the combustion process, fuel modification or fuel additives, modification to motor
engines.

2. Cleaning of exhaust gases: catalytic oxidation using catalytic convertor.

5
The present review is primarily concerned with catalytic convertor used in exhaust of vehicles, hence
emphasis is on various catalysts used in the catalytic convertor

2. General preparation methods for supported catalysts

Mn-Co/γ-Al2O3 samples were prepared using Co(NO3)2.6H2O , C4H6MnO4.4H2O and Al2O3 . The
compositions are expressed in mass percent throughout the paper. Only manganese loading is varied on
18 mass % Co/Al2O3.

2.1 Incipient wetness method

The required manganese and cobalt precursor salts were dissolved in doubly distilled water ensuring that
the formed volume should not be greater than the total pore volume of the alumina particles. This solution
was poured onto the alumina support and the ageing proceeded for 5 h at 30 ̊C. The impregnates were
dried overnight in an oven at 110 ̊C. The samples were further calcined for 4h in a muffle furnace at
550 ̊C.

2.2 Wet impregnation method

The stoichiometric amounts of manganese acetate as well as the alumina and cobalt nitrate salts were
dissolved in doubly distilled water. The solution formed was heated at 80°C with constant stirring until
dryness appears. The samples formed were further dried in an oven overnight at 110 °C and calcined for 4
h in a muffle furnace at 550°C.

2.3 Deposition precipitation method

The required amount of alumina (Al2O3) support was added to an aqueous mixture of manganese acetate
and cobalt nitrate. This solution was then added drop wise to 0.1 mole/liter aqueous sodium carbonate
solution with constant stirring at 100 ̊C maintaining pH of 9. The resulting precipitate was aged for 1 h,
washed with distilled water two times and littered using Whatman liter paper (Ash less). The resulting
sample was dried overnight in an oven at 110 ̊C. The solid formed was calcined in a muffle furnace for 4h
at 550 C
̊ .

2.4 Citric acid sol-gel method

The metal salts were dissolved in distilled water according to the stoichiometric amount required and
citric acid was added as a complexing agent with of acid to metals ions 1.3:1 ratio. The amount of
polyethylene glycol added was 10 % of the citric acid used above. The blended solution was mixed with
continuous stir- ring at 80°C till a gel was formed. The latter was dried overnight in oven at 110°C and

6
calcined in the muffle furnace for 4 h at 550°C.

3. Catalysts preparation, operating parameters in brief

3.1 Noble Metal Catalysts

Catalyst Prep. Method Exp. operating parameters Remark Ref.

monolith catalysts of
1.5 vol% CH4 in air SV=250000 5 wt% Pd//Al2O3 shows [2]
5 wt% Pd//Al2O3; 1:1 molar ratio of
Pd:Co, Rh, Ir, Ni, Pt, Cu, Ag, Au,//Al2O3; h-1 good results with T50=600°C
Ni//Al2O3; 2.5 wt% Pd//Al2O3; Pt//Al2O3 andT90=850°C
Co-impregnation, Calc. temp. of 1000 °C
CH4 (1 vol.%), O2 (20 vol.%),
Pd/SnO2, Impregnation method,Calc. 1 wt.% Pd/SnO2 shows [3]
H2O (0–20 vol.%), and N2, SV=
temp. of 600-1000°C 48000 h-1, quartz tube T50=350°C, T100=450°C

Pd/ZrO2, wet impregnation,

50 mg, alumina tubular reactor, Effect of water vapor studied, [4]
Calc. temp. of 600 °C
CH4=1%, O2=4%, He=95%. Shows T50=650°C, T90=800°C

Pd/Al2O3, Pd/SiO2, Pd/Al2O3- 0.01g, Pyrex glass, 100 mL/min The stabilized, activity of the [30]
SiO2Impregnation, Calc. temp. 500 °C of gas mixture of 10%CH4, 20% palladium follows SiO2>
O2, 70%N2. A1203> SiO2-A12O3

Ce0:67Zr0:33O2, Pt/Ce0:67Zr0:33O2, 0.50 g catalyst, 1 vol% CH4, 4 Activity varies [32,33

Pd/Ce0:67Zr0:33O2, Pptn, Calc. temp. vol% O2, and N2, flow rate=6.4 Pd/Ce0:67Zr0:33O2 > ]
700 °C. L/h Pt/Ce0:67Zr0:33O2 >
Ce0:67Zr0:33O2, where
Pd/Ce0:67Zr0:33O2 T50=300
,T100=550°C

Pd/SiO2, sol-gel, Calc. temp. 500 °C. 200mg, 1 vol% CH4, 2 vol% O2, Pd/SiO2 shows T50=650, [5]
balance He. T100=800°C

Pd/Co3O4, Impregnation, Calc. temp. 280 horizontal quartz tubular, 1.2% 10 wt.% Pd/Co3O4 exhibits [28,29
°C CH4, 12% O2,balance N2, flow T50=250°C, T100=300°C ]
rate= 33 ml/min

7
Pd/[SO42-ZrO2, MgO, SiO2-ZrO2, SiO2, 100 mg, conventional flow, Pd/SiO2 shows T50=625°C, [7]
SiO2-Al2O3, ZrO2], impregnation, Calc. (CH4+ O2 + He), flow rate= 200 T90=850°C
temp. 500 °C cm3/ min.

3.2 Gold-Based Catalysts

Catalyst, Prep. Method Exp. Operating Parameters Remark

Au/TiO2, Au/SiO2, Au/CeO2, Quartz tubular fixed bed, 50 mL/min. Au/TiO2 shows T80= 400°C,
Au/ZrO2, Au/Al2O3, Deposition Ppt, (20% CH4 and 5% O2 rest is He. whereas Au/Al2O3
Calc.temp. 400 °C showsT20=400°C.

Co3O4/CeO2 and Co3O4/CeO2–ZrO2 Quartz U-shaped, 0.3 vol.% of CH4 + Co3O4/CeO2 shows T100= 800°C
co-ppt, Calc. temp. 650 °C 4.8 or 0.6 vol.% O2, in He. 50 mL/min
(STP), WHSV of 12000 or 60000
mL/g h.

Au/CoOx, Au/MnOx co-ppt, 50 mg, fixed-bed S. S. tubular flow, Au/CoOx Shows T100= 350 °C.
Calc. temp. 400 °C 50 mL/min., GHSV = 15,000 h-1,
alkane/air ( molar ratio) of 0.5/99.5

AgMnLa, Co-ppt, Calc. temp. of 0.15 g, 2 vol% CH4 in air, 300 Catalyst with 0.3 % mole
800 °C cm3/min, SV=120,000 cm3/(h gcat), fraction of Ag shows T50=600°C
and T100=700°C

Au/Co3O4–CeO2 co-ppt, Calc. temp. 50 mg, U-shaped quartz, 0.3 AuCeO2 shows T100=750°C.
600 °C. vol.%CH4, 2.4 vol.%O2 in He.
WHSV=60,000 mL/ gh.

Au/MgO, Impregnation, Calc. temp. 200 mg, microreactor of quartz glass, Enhanced activity when gold
850 °C. CH4 (46%, O2 8%, He 46%. was employed
GHSV=750 h-1.

Au–Pt/Co3O4 co-ppt technique 0.10 g, fixed bed microreactor, 1 Activity of Au/Co3O4 enhanced
Calc. temp. 400 °C. vol.% CH4, 5 vol.% O2, and rest N2., when Pt, e.g. 0.2 wt.% was
hourly space velocity of 10,000 per added, and conv. Temp.
hour decreased by 50°C.

8
Au/MOx/Al2O3 where M is Cr, Mn, lab-scale fixed-bed, 0.8 vol.% CH4 Au/MnOx/Al2O3 shows T100 =
Fe, Co, Ni, Cu, and Zn, and 3.2 vol.% O2 in He, 30 mL/min. 25°C for CO. whereas
homogeneous deposition ppt, Calc. MnOx/Al2O3 shows T80= 375°C
temp.400°C

CoxMny co-ppt, Calc. temp. 400 °C 0.5 g, fixed-bed quartz, 1 vol.% CH4, Co5Mn exhibits good result with
10 vol.% O2 and N2 balance gas, T50=290°C T90=320°C
flowrate =150 mL/min,WHSV= T100=400°C
36,000mL/hg.

Au/Fe2O3 Deposition ppt, 0.1 g, fixed bed quartz, 1 vol.% CH4 Au/Fe2O3 prep. By HDP shows
in air, flow rate=100 mL/min, GHSV T50=375°C, T100=500°C.
= 51,000 h-1.

AuOx/Ce0.6Zr0.3Y0.1O2 Co-ppt, Calc. 0.12 mL, quartz fixed-bed Catalyst with 6% AuOx shows
temp. 700 °C microreactor, 5% CH4/95% He (v/v, T50=590°C T100=680°C
40 mL/min) + O2 (8 mL/min) + He
(52 mL/min), SV= 50,000 h-1.

3.3 Base Metal Catalysts

Catalyst, Prep. Method Exp. Operating Parameters Remark Ref.

Cu, Mn-BaAl12O19, Sol gel, Calc. 0.50 g, Quartz Cu sites are intrinsically more active [12]
temp. 1200 °C microreactor, 1 vol.% CH4, 4 than Mn sites, BaMn3 shows
vol.% O2 and 95 vol.% N2 , T50=600, T100=800, Where BaCu
SV= 20000–25000 h-1 shows T50=700, T100=800

Co-Mg/Al, prepared by calc. of 0.5 g, a mixture of 1% vol of catalysts with molar ratio of 1.5 of [13]
CoxMg3−x/Al hydrotalcites, ppt at CH4 in air, total flow rate of Co/Al, shows T50=540 °C, T100=800
800 °C. 400 mL/min, GHSV= 50,000 °C.
h-1.

MnOx–CeO2, Co-ppt, 500 °C, 150 mg, fixed-bed reactor, Ppep. T50%(°C) T80% T100% [14]
20% CH4 and 40% O2 in Ar, (°C) (°C)
Plasma, Modified co-ppt. and SV=40,000 mL/g h.
MP 350 360 480

CP 410 480 NA

9
 PP 380 410 NA

oxides of cobalt/manganese, sol– 0.1 g, quartz tubular reactor, CoOx shows good results with [11]
gel, Calc. temp. 850 flow rate of 100 mL/min, CH4 T50=425 °C and T100=550 °C.
(0.5 vol.%), O2 (0–8 vol.%),
°C water vapor (5 vol.%) and
argon.

CuO/AI2O3, Wet impregnation, 500 mg, quartz micro reactor, 4.8% CuO shows T50=450 °C, [15]
Calc. temp. 500 °C 1 % CH4, 4% 02, and 95% N2, T100=570 °C
flow rate 6.41 h-1

CeO2,ZrO2,HfO2,Ce0.8Zr0.2 quartz micro reactor, CH4 Ce0.8Zr0.2O2 shows T50=520 °C, [16]
and Ce0.8HfO2Ppt, co-ppt, (l%), O2(4%) and He, T100=670 °C
temp. 920 °C SV=34000 h-1.

Co/MgO, Wet Calc. 0.05 g, quartz reactor, 2% CH4, Cobalt exhibit good activity when [17]
impregnation, temp. 800 8% O2 and N2, SV=480,000 h- MgO employed
1
°C. .

MnOx–NiO, coppt, 200 mg, quartz tubular flow MnOx(0.13)–NiO exhibits [8,31]
Calc. temp. 500 °C. micro reactor, 1.0 vol.% CH4, T50=360 °C and
19 vol.% O2, and balanced T100=525 °C.
argon,WHSV= 32 000 mL/gh.

CoCr2O4, co-ppt , Calc. temp. 700 250 mg, 2000 ppm CH4, 10 Catalyst containing 5% Ce, shows [10]
°C. vol.% O2, and N2, GHSV= T50=375 °C and T100=525 °C.
36000 mL/h g.

CoxCry ,Co-ppt, Calc. temp. 700 500 mg, 2000 ppm CH4, 10 Co/Cr=0.5 shows, T50=400 °C and [9]
°C. vol.% O2, 10 vol.% and N2, T100=550 °C.
flow rate= 300 mL/min,
GHSV= 36000 mL/h g.

Co3O4/CeO2 and Co3O4/CeO2– 0.3% of CH4 + 4.8% of O2 in Catalyst with 30% Co3O4 shows [1]
ZrO2, co-ppt, impregnation, He, WHSV= 12,000 mL/ gh, T50=400 °C, T100=700 °C
Calc.temp. 750°C. SV= 60000 mL/ g h

Cerium-chromium/γ-Al2O3 300 mg, stainless-steel fixed 3 wt.% Ce displayed T50=375°C, [18]

incipient wetness impregnation, bed, 2.0 vol.% CH4, 8 vol.% T100=475 °C
Calc. temp. 500, 800 °C. O2, 90 vol. % N2, MHSV=
20,000 mL/g h.

CeO2-ZrO2, urea hydrolysis, Calc. 100 mg, differential quartz Ce0.75Zr0.25O2 calcined at 500 °C [19]
temp. 500-900 °C. tube microreactor, 2.0 vol.% shows good activity with T50=550
CH4, 21 vol.% O2 and He,

10
 flow rate= 100 mL/min. °C, T100=650 °C

CeO2-ZrO2, Ppt, Calc. temp. 700 500 mg, Microreactor, 1 CeO2 shows T50=575 °C, T100=750 [20]
°C. vol.% CH4, 4 vol.% O2 °C
diluted in N2, Flow rate=6.4 l
h-1, GHSV=20 000 h-1.

CuO/ZrO2, Wet impregnation, 200 mg, continuous flow ZrO2- 5% CuO shows T50=400 °C [21]
Calc. temp. 600 °C fixed-bed, 20 vol.% CH4, 40 T90=425 °C
vol.% O2, 40 Ar.

3.4 Cobalt based catalyst

Cobalt Nickel mixed oxide catalysts
A series of cobalt nickel mixed oxide catalysts with the varying ratios of Co to Ni, prepared by co-
ppt method, were applied to methane combustion. Among the various ratios, cobalt nickel mixed oxides
having the ratios of Co to Ni of (50:50) and (67:33) demonstrate the highest activity for methane
combustion. Structural analysis obtained from X-ray diffraction (XRD) and extended X-ray absorption
fine structure (EXAFS) evidently demonstrates that CoNi (50:50) and (67:33) samples consist of
NiCo2O4and NiO phase and, more importantly [35], NiCo2O4spinel structure is largely distorted, which is
attributed to the insertion of Ni2+ions into octahedral sites in Co3O4spinel structure. [29] The structural
disorder in cobalt nickel mixed oxides enhances the catalytic performance for methane combustion. Thus,
it is concluded that a strong relationship between structural property and activity in cobalt nickel mixed
oxide for methane combustion exists and, more importantly, distorted NiCo2O4spinel structure is found to

11
be an active site for methane combustion.

Fig3. Light-off curves of methane combustion on cobalt nickel mixed oxides with various Co/Ni
ratios[35]

Temperature where methane combustion conversion reaches 90% (T90) can be regarded as the

criterion of the catalytic activity for methane combustion. T 90 of cobalt oxide and nickel oxide is 506◦C

and 505◦C, respectively. T90 of most cobalt nickel mixed oxides is lower than 500◦C. Therefore,

catalytic activity of cobalt nickel mixed oxides more significantly improved than that of single oxides.
Methane combustion activity of various Co/Ni ratio catalysts increases with increasing nickel content up
to the level of CoNi (50:50) catalyst. Especially, CoNi(50:50) and CoNi (67:33) catalyst reach T90 at 466

◦C and 468◦C,both of which show the highest activity among the cobalt nickel mixed oxides. Fig. 5

clearly indicates that descending order of activity is as follows: CoNi (50:50) ≈ CoNi (67:33) >

CoNi(75:25) > cobalt oxide ≈ nickel oxide > CoNi (33:67).

12
Fig4. Light-off curves of methane combustion on several catalysts.[35]

3.5 Perovskites
Catalyst, Prep. Method Exp. Op. parameters Remark Ref.

Pd/ZrO2, Pd/LaMnO32ZrO2 0.1 g, U-shaped quartz tube, Pd/LaMnO32ZrO2 Shows [22]

Solution combustion synthesis 50 cm3/min, CH4 (2%), O2 T50=375°C T90=425°C,
(SCS), Calc. temp. 900 °C (14%) and He (balance) T100=475°C

La0.9FeO2.85, La0.8FeO2.70, 400 mg, tubular continuous At temp. of 748 La0.9FeO2.85 [23]
La0.7FeO2.55, LaFeO, low- flow, 30mL/min,CH4 and O2 shows T34, La0.8FeO2.70 shows T30,
temperature thermal (ratio 1:6) La0.7FeO2.55 shows T25, LaFeO
decomposition, Calc. temp. 473 K shows T20

LaMnO3 , LaMnO3·17MgO 0.05 g, quartz reactor, 2% CH4, LaMnO3·17MgO shows T50= 526 [24]
combustion synthesis 8% O2 and N2. °C, LaMnO3 shows 461°C

Ce1-xLaxO2-x/2/ Al2O3/FeCrAl, quartz flow reactor, 2 vol.% CH4 Ce1-xLaxO2-x/2/ Al2O3/FeCrAl [25]
monolith catalysts, where x varies in air, SV= 7802, 15,604 and shows T50=550 °C, T100=700 °C.
from 0 to 1. Calc. temp. 500 °C 31,208 mL/g

13
LaAl1-xFexO3(0<X<1), citerate, 0.4 g, 0.4% CH4, 10% O2, and N2 Catalyst with x=0.6 shows [26]
calc. temp. 800 °C as balance, SV= 40,000 cm3 STP T50=800 °C, T100=950 °C.
h-1 g-1

LaFeO3, LaFe0.5Co0.5O3, La0.7 Sr (or 0.1 g, quartz micro-reactor, 4 La0.7Sr (or Ag)0.3Fe0.5Co0.5O3 [27]
Ag)0.3FeO3 and La0.7Sr (or mol% methane in air, SV= 51 and La0.7 Sr (or Ag)0.3FeO3 shows
Ag)0.3Fe0.5Co0.5O3 Co-ppt, Calc. 000 cm3/g h. T100=700 °C
b/w 750-900 °C.

LaMnO3 La2O3/Al2O3MgO 30%
LaMnO3/(5% La2O3/Al2O3) 20%
LaMnO3/MgO 30% LaMnO3/(5%
La2O3/Al2O3) 20% LaMnO3/MgO,
Calc. temp. of 800 and 1100 °C
quartz down flow reactor, 0.4 30% LaMnO3/(5%La2O3/Al2O3) [28]
vol% CH4 and 10 vol.% O2 shows T100=650 °C whereas 20%
remaining gas being nitrogen, LaMnO3/MgO exhibits T100=625
Flow rate 0.09 g s/N cm3 °C

4.Conclusion
An increased interest in the use of natural gas as an alternative fuel in mobile and stationary
applications is apparent. Some of the main reasons are its relative high abundance, lower cost compared
to other fuels and most importantly the urge to meet targets for the reduction of greenhouse gas
emissions. Methane emissions and total hydrocarbons (including methane) are capped by regulations
globally including the US EPA greenhouse gas legislation and Euro VI, requiring vehicles to use
methane emissions control after treatment. The obvious path for natural gas is via methane for
stationary and mobile applications, where it can be used in the form of either CNG or LNG. With
further improvement in natural gas fuelling infrastructure and an increase in the number of natural gas
engines, the rate of uptake of natural gas vehicles can be enhanced to a greater extent. Pd- Rh TWC
under stoichiometric conditions, while Pd-Pt catalyst under lean conditions are used to deal with
methane combustion. High methane combustion can be achieved at lower temperatures by altering
the pgm loading and through engine calibration depending on the regional legislation requirements.
However, these might make the technology rather expensive. Further challenges include the issues
with catalyst deactivation due to sulfur (from lubricant), water, thermal ageing and methane slip at
low temperatures. These need to be addressed quickly so that this technology is readily available to
meet the current and upcoming stricter legislation and challenges. There are researches all over the
to find new catalyst. Recent researches are going on Cobalt based catalyst whether Co mixed with

14
 Ni, Pd supported by Co and some cobalt oxides like Co3O4. Using nanoparticle highly active catalyst
are being made but still they are costly. But we can see cheap and highly active catalyst in near future.

References
[1] Liotta L. F., Carlo G. Di, Pantaleo G, Deganello G. Co3O4/CeO2 and Co3O4/CeO2–ZrO2 composite
catalysts for methane combustion: Correlation between morphology reduction properties and catalytic
activity. Catal. Comm..2005, 6 (5), 329-336.
[2] Persson K, Ersson A., Jansson K., Iverlund N., Järås S. Sven. Influence of co-metals on bimetallic
palladium catalysts for methane combustion. J. Catal. 2005, 231(1), 139-150.
[3] Sekizawa K., Widjaja H., Maeda, S., Ozawa, Y., Eguchi K. Low temperature oxidation of methane
over Pd/SnO2 catalyst. Appl. Catal. A: General. 2000, 200(1), 211-217.
[4] Muto K. I., Katada, N., Niwa M. Complete oxidation of methane on supported palladium catalyst:
Support effect. Appl. Catal. A: General. 1996, 134(2), 203-215.
[5] Pecchi, G., Reyes, P., Concha, I., Fierro J. Methane Combustion on Pd/SiO2 Sol Gel Catalysts. J.
Catal. 1998, 179 (1), 309-314.
[7] Yoshida, H., Nakajima, T., Yazawa, Y., Hattori T. Support effect on methane combustion over
palladium catalysts. Appl. Catal. B: Environmental. 2007, 71(1), 70-79.
[8] Zhang Y., Qin Z., Wang G., Zhu H., Dong M., Li S. Wang J. Catalytic performance of MnOx–NiO
composite oxide in lean methane combustion at low temperature. Appl. Catal. B: Environ. 2013, 129,
172-181.
[9] Chen J., Zhang X., Arandiyan H., Peng Y., Chang H., Li J. Low temperature complete combustion of
methane over cobalt chromium oxides catalysts. Catal. Today. 2013, 201, 12-18.
[10] Chen J., Shi W., Li J. Catalytic combustion of methane over cerium-doped cobalt chromite catalysts.
Catal. Today. 2011, 175(1), 216-222.
[11] Li Weibin, Ying Lin, Yu Zhang. Promoting effect of water vapor on catalytic oxd. of methane over
cobalt/manganese mixed oxides. Catal. today. 2003, 83 (1), 239-245.
[12] Artizzu D. P., Brullé Y., Gaillard F., Garbowski E., Guilhaume N., Primet M. Catalytic combustion
of methane over copper-and manganese-subs. barium hex aluminates. Catal. Today. 1999, 54(1), 181-
190.
[13] Jiang, Z., Yu J., Cheng J., Xiao T., Jones M.O., Hao Z., Edwards P.P. Catalytic combustion of
methane over mixed oxides derived from Co–Mg/Al ternary hydrotalcites. Fuel Proc. Tech. 2010, 91(1),
97-102.
[14] Shi Limin, Wei Chu, Fenfen Qu, Shizhong Luo. Low-temperature catalytic combustion of methane
over MnOx–CeO2 mixed oxide catalysts: Effect of preparation method. Catal. Lett. 2007, 113 (1), 59-64.
[15] Marion, Marie C.; Edouard, Garbowski; Michel, Primet. Physicochemical properties of copper oxide
loaded alumina in methane combustion. J. Chem. Soc., Faraday Trans. 1990, 86 (17), 3027-3032.
[16] Leitenburg, Carlaáde. CeO2-based solid solutions with the fluorite structure as novel and effective
catalysts for methane combustion. J Chem. Soc., Chem. Commun. 1999, 9, 965-966.

15
[17] Ulla M.A., Spretz R., Lombardo E., Daniell W., Knözinger H. Catalytic combustion of methane on
Co/MgO: characterisation of active cobalt sites. Appl. Catal. B: Environ. 2001, 29 (3), 217-229.
[18] Yuan Xingzhou, Chen Shaoyun, Chen Heng, Zhang Yongchun. Effect of Ce addition on Cr/γ-Al2 O3
catalysts for methane catalytic combustion. Catal. Commun. 2013, 35, 36-39.
[19] Sitthiphong P., Meeyoo V., Rirksomboon T., Bunyakiat K. Catalytic oxidation of methane over
CeO2-ZrO2 mixed oxide solid solution catalysts prepared via urea hydrolysis. Appl. Catal. A: Gen. 2002,
234 (1), 221-233.
[20] Bozo C., Guilhaume N., Garbowski E., Primet M. Combustion of methane on CeO2–ZrO2 based
catalysts. Catal. Today. 2000, 59 (1), 33-45.
[21] Qu F. Fen, Wei Chu, Li M. Shi, Mu Chen H., Jin Y.Hu. Catalytic combustion of methane over nano
ZrO2-supported copper-based catalysts. Chin. Chem. Lett. 2007, 18(8), 993-996.
[22] Civera A., Negro G., Specchia S., Saracco G., SpecchiaV. Optimal compositional and structural
design of a LaMnO3/ZrO2/Pd-based catalyst for methane combustion. Catal. today. 2005, 100 (3), 275-
281.
[23] Delmastro,A., Mazza D., Ronchetti S., Vallino M., Spinicci R., Brovetto P., Salis M.
Syn. characterization of non-stoich. LaFeO3 perovskite. Mater. Sci. Eng., B. 2001, 79(2), 140-145.
[24] Civera A., Matteo P., Saracco G., Specchia V., Comb. synthesis of perovskite-type catalysts for
natural gas combustion. Catal. Today. 2003, 83(1), 199-211.
[25] Fengxiang Y, Shengfu J., Biaohua C, Zhongliang Z, Hui L., Li Chengyue. Catalytic comb. of CH4
over Ce1-xLaxO2-x/2/Al2O3/FeCrAl catalysts. Appl. catal. A. 2006, 310, 164-173.
[26] Ciambelli P., Cimino S., Lasorella G., Lisi L., Rossi S. De, Faticanti M., Minelli G., Porta P. CO
oxidation and CH4 comb. on LaAl1− xFexO3 perovskite solid solut. Appl. Catal. B, Environ. 2002, 37 (3),
231-241.
[27] Choudhary V.R., Uphade B.S., Pataskar S.G. Low temperature complete combustion of methane
over Ag-doped LaFeO3 and LaFe0.5Co0.5O3 perovskite oxide catalysts. Fuel. 1999, 78 (8), 919-921.
[28] Cimino S., Lisi L.. Pirone R, Russo G., Turco M. Methane comb. on perovskites-based structured
catalysts. Catal. today, 2000, 59 (1), 19-31.
[29] Hu W., Jinggang L., Yun G., Xiao-Ming C., P. Hu. Origin of Efficient Catalytic Comb. of CH4 over
Co3O4(110): Active Low-Cord. Lattice Oxygen and Coop. of Multiple Active Sites. ACS
Catal., 2016, 6 (8), 5508–5519
[30] Adamowska M., Costa D.P. Structured Pd/γ-Al2O3 Prepared by Washcoated Deps. on a Cerm.
Honeycomb for CNG. Appli. J. Nanopart. 2015, 601941, 9
[31] Yagang Z., Zhangfeng Q., Guofu W., Huaqing Z., Mei D., Shuna L., Zhiwei W., Zhikai L.,
Zhonghua W., Jing Z., Tiandou H., Weibin F., Jianguo W. Catalytic performance of MnOx–NiO
composite oxide in lean methane combustion at low temp. Appl. Catal. B: Environ. 2013, 129 172–181
[32] Tianyu G., Jianping D., Jinting W., Jinping L. Palladium catalyst supported on stair like
microstructural CeO2 provides enhanced activity and stability for low conc. CH4 oxidation. Appl. Catal.
A: 2016, 524, 237–242

16
[33] Shaohua X., Yuxi L., Jiguang D., Xingtian Z., JunY., Kunfeng Z., Han Z, Dai H. 3-D ordered
macroporus CeO2 supported Pd/CO nanoparticles: catalyst for CH4 oxidation. J. Catal. 2016, 342, 17–26
[34] Munde G., Dalu R.S. CNG as an Alternative Fuel for Spark Ignition Engine: A Review. Int. J. Eng.
Innov. Tech. 2012, 2(6), 92-96
[35] Lima T.H., Chob S.J., Yangc H.S., Engelhardd M.H, Kima D.H. Effect of Co/Ni ratios in Co-Ni
mixed oxide catalysts on CH4 combustion. Appl. Catal. A: General 2015, 550, 62–69

17