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Journal of Natural Gas Chemistry 12(2003)201–204

A Study on the Kinetics of the Catalytic Reforming


Reaction of CH4 with CO2: Determination
of the Reaction Order
Chunyang Ji, Lihong Gong∗ , Jiawei Zhang, Keying Shi
Chemistry Department of Harbin Normal University, Harbin 150080, China
[Manuscript received May 30, 2003; revised July 25, 2003]

Abstract: The kinetics of the catalytic reforming reaction of methane with carbon dioxide to produce
synthesis gas on a Ni/α-Al2 O3 and a HSD-2 type commercial catalyst has been studied. The results indicate
that the reaction orders are one and zero for methane and carbon dioxide, respectively, when the carbon
dioxide partial pressure was about 12.5–30.0 kPa and the temperature was at 1123–1173 K. However,
when the carbon dioxide partial pressure was changed to 30.0–45.0 kPa under the same temperature range
of 1123–1173 K, the reaction orders of methane and carbon dioxide are one. Furthermore, average rate
constants at different temperatures were determined.
Key words: reforming, methane, carbon dioxide, reaction order, rate constant, kinetics

1. Introduction bed reaction unit (Figure 1). The reactors (No. 4)


included a differential reactor (internal diameter: 3
The catalytic reforming reaction of methane mm) and an integral reactor (internal diameter: 8
with carbon dioxide can produce high concentra- mm). The differential reactor was di-annular and was
tion synthesis gas of carbon monoxide and hydrogen. made from quartz tube, as shown in Figure 2, and it
Comparing with the catalytic reforming reaction of is used for determining the reaction order. The in-
methane with steam, it can greatly reduce the cost tegral reactor is shown in Figure 3, and it was used
of the synthesis gas for about 20% [1]. The HSD-2 for determining the activation energy. The catalyst
type commercial catalyst has high activity and high was reduced for 0.5 h at 973 K by passing H2 before
thermal stability, and is resistance to carbon deposi- the reaction, then the feed gas was introduced, and
tion. In this work, studies are mainly focused on the the reaction was run at assigned temperatures. The
kinetics of catalytic reforming of CH4 with CO2 on a composition of the feed gas and the products were
analyzed by a 102 type gas chromatograph. Super
Ni/α-Al2 O3 and the commercial HSD-2 catalyst. The
relevant kinetic parameters adapted and the results pure Ar was used as the carrier gas, and the flow rate
obtained can provide useful data for experimental in- was 30–40 ml/min. The detector was a thermal con-
vestigations as well as industrial scaling up. ductivity cell, with column temperature and detection
temperature of 383 K and 397 K, respectively.
(1) The percent conversion of the feed gas, the
2. Experimental selectivity and the yield were calculated according to
the method reported in the literature [2–3].
The kinetic experiments were carried out in a
multi-functional fixed bed as well as a suspension XCH4 = (FCH4 ,in − FCH4 ,out )/FCH4 ,in × 100% (1)
∗ Corresponding author. E-mail: gonglihong1967@21cn.com
202 Chunyang Ji/ Journal of Natural Gas Chemistry Vol. 12 No. 3 2003

SH2 = SH2 ,out /2(FCH4 ,in − FCH4 ,out ) × 100% (2) 3. Results and discussion

(2) The activation energy was also calculated ac- 3.1. Determination of the reaction order for
cording to the method of the literature [2]. The the catalytic reforming reaction of CH4 -CO2
activation energy in this paper is an average value
at a certain percent of conversion. From the Ar- A 4.8%Ni/α-Al2 O3 catalyst of 80–100 mesh was
rhenius equation k = Ae−E/RT and R = kC = weighed, then diluted by mixing with α-Al2 O3 of the
Ae−E/RT C = A0 e−E/RT , it can be known that lnR = same sizes as the catalyst. By adjusting the feed to a
−Ea/RT +lnA0. A straight line can be obtained by constant flow of 60 ml/min (the flow rate of CH4 was
plotting lnk to 1/T , and its slope k is −Ea/R, so controlled to be 7.5 ml/min, which could be achieved
Ea = −Rk (k is the slope of the straight line). by varying the flow rate of N2 and CO2 . Similarly,
the flow rate of CO2 could be kept as 7.5 ml/min by
changing the flow rate of N2 and CH4 . Thus, the
reaction order for the reforming reaction of CH4 -CO2
could be determined according to the power law equa-
tion: RCO = kpaCH4 pbCO2 , and the results are shown
in Figure 4 and Figure 5.
It can be seen from Figure 4 and Figure 5 that
the rate of formation of CO increases with the partial
pressure of CH4 from 1123 K to 1173 K, and both of
them have a good linear relationship.
The linearly interrelated parameters of the ex-
Figure 1. Apparatus for studying the kinetics of perimental data shown in Figure 4 at 1173 K is
catalytic reforming of methane and car-
bon dioxide to produce synthesis gas
R2 =0.9926, while it is R2 =0.9988 at 1123 K. This
1—flow gauge, 2—Valve, 3—Six-way valve, 4—Reactor, indicates that the two sets of data have a good linear
5—Ice-water bath, 6—Thermal conductivity cell detector, relationship and the reaction order of CH4 is one.
7—Carried gas
In the partial pressure range of CO2 of 12.5–30.0
kPa, as shown in Figure 5, the reaction order of CO2 is
one. (The linear interrelated parameters of the scat-
tered dots at 1173 K is R2 =0.9426, whilst that at
1123 K is R2 =0.9625). It can be seen that in partial
pressure range of CO2 of 30.0–45.0 kPa, the formation
rate of CO is almost constant, even though the partial
pressure of CO2 increases. This implies that the re-
action order of CO2 is zero. The results are the same
at 1173 K and 1123 K. Therefore, the rate equation
Figure 2. The differential reactor: di-annular and
of CO in the reforming reaction of CH4 with CO2 is:
made from quartz tube
1—Synthesis gas, 2—Feed gas(CH4 , CO2 , N2 ), 3—Thermo-
couple, 4—Catalyst RCO = kpCH4 pCO2 (3)

(The partial pressure range of CO2 : 12.5–30.0


kPa, and the temperature range: 1123–1173 K).

RCO = kpCH4 (4)

(The partial pressure range of CO2 : 30.0–45.0


kPa, and the temperature range: 1123–1173 K).
Our results are similar to that of Takano [4]. A
Figure 3. The integral reactor comparison between our result and those reported in
1—Thermo-couple, 2—Catalyst, 3—Synthesis gas, 4—Feed gas the literature is shown in Table 1.
Journal of Natural Gas Chemistry Vol. 12 No. 3 2003 203

Figure 4. Effect of CH4 partial pressure on CO for- Figure 5. Effect of CO2 partial pressure on CO for-
mation rate mation rate
(1) 1123 K, (2) 1173 K (1) 1123 K, (2) 1173 K

Table 1. Comparison between our experimental results with those of the literature

Catalysts Temperature (K) PCO2 /kPa Reaction order of CO2 Reaction order of CH4 References

4.8%Ni/α-Al2 O3 1123–1173 12.5–30.0 1 1 —

4.8%Ni/α-Al2 O3 1123–1173 30.0–45.0 0 1 —

5%Ni/γ-Al2 O3 773–973 ≥6.0 0 1 [5]

Ni/Al2 O3 873–973 <8.4 1 1 [6]

Ni/Al2 O3 873–973 8.4–67.6 0 1 [6]

3.2. Rate constants at different temperatures It can be seen from Table 2 that the rate con-
stant of the reaction CH4 with CO2 increases with
The rate constants of the reaction of CH4 with the temperature, and at the same temperature the
CO2 at different temperatures illustrated in Figure 4 rate constant increases when the partial pressure of
and Figure 5 are summarized in Table 2. CO2 is increased.

Table 2. Average rate constants at different


4. Conclusions
temperatures

Temperature Rate constant k


pCO2 /kPa The rate equation of CO in the reforming reaction
(K) (mmol/g·s·KPa2 )
of CH4 with CO2 obtained experimentally is
12.5–30.0 1123 12.82
1173 14.99 RCO = kpCH4 pCO2 (3)
30.0–45.0 1123 32.21
1173 38.24 (Partial pressure range of CO2 is 12.5–30.0 kPa,
204 Chunyang Ji/ Journal of Natural Gas Chemistry Vol. 12 No. 3 2003

and the temperature range is 1123–1173 K). [2] Yu Ch Ch, Ding X J, Shen Sh K. Fenzi Cuihua (J Mol
Catal), 1993, 7(2): 151
RCO = kpCH4 (4)
[3] Long Y F, Li Y K, Tang D H et al. Huaxue Shiji (
(Partial pressure range of CO2 is 30.0–45.0 kPa Chem Reagents), 1998, 20(1): 8
and the temperature range is 1123–1173 K). [4] Takano A, Tagawa T,[J]Goto S. Chem Eng Jpn, 1994,
27(6): 723
References [5] Xu Zh, Li Y M, Zhang J Y et al. Cuihua Xuebao
(Chin J Catal), 1997, 18(5): 364
[1] Niels R U, Hansen J B, David C H. Oil Gas J, 1992, [6] Crespin M, leritz P, Gatineau L. J Chem Soc Faraday
9: 62 Trans, 1983, 2: 1181