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02638762/03/$23.50+0.00 # Institution of Chemical Engineers Trans IChemE, Vol 81, Part A, April 2003

METHANE SEPARATION FROM COAL MINE METHANE GAS BY VACUUM PRESSURE SWING ADSORPTION
A. OLAJOSSY1 , A. GAWDZIK2 , Z. BUDNER 2 and J. DULA2
2

University of Mining and Metallurgy, Cracow, Poland Institute of Heavy Organic Synthesis Blachownia, Ke dzierzyn-Koz le, Poland

he ndings were presented from laboratory investigations and computer calculations for the VPSA (vacuum pressure swing adsorption) process employed to recover methane from coal mine methane gas. The separation process of coal methane gas was carried out at temperature of 278 K under adsorption pressure equal 300 kPa abs., and desorption pressure equal 25 kPa abs. Coal mine methane gas with the CH4 content of 55.2 vol% was enriched into methane-rich gas which contained 9698 vol% CH4. The methane recovery ef ciency reached 8691% with the ratio for re-circulated methane to that introduced with the feed falling within P=F 1.82.12. The methane content in the adsorption ef uent gas was 1115 vol% under those conditions while nitrogen and oxygen were removed at 9698% from the methane-rich gas. That separation level of the coal mine gas can be achieved when the methane sorption wave is brought to the outlet point of the sorption bed at the adsorption phase, and then the methane sorption wave is brought to the entry point of the sorption bed at the counter-current purge phase. Keywords: vacuum pressure swing adsorption; coal mine methane gas; methane separation; nitrogen rejection; computer process simulation; activated carbon.

INTRODUCTION Methane contained in coal mine gas and released from coal beds when the beds are subjected to preconditioning before exploitation makes a valuable energy carrierits value is considerable but still not fully utilized. Its emission to atmosphere would contribute to the greenhouse effect. Coal mine gas is most frequently utilized as a low-energyvalue fuel gas intended for captive use in local heatgenerating plants or thermal-electric power stations. It is also known to be used in gas turbines. An alternative way of utilizing coal mine gas is to convert it into methane-rich gas, containing at least 96 vol% methane, to be then delivered to local natural gas supply systems. Among the known methods for separation of gas mixtures, the PSA (pressure swing adsorption) method can be used in practice to recover methane from coal mine gas. This method has been employed to reject nitrogen from small streams of nitrogen-rich natural gas DAmico et al., 1993; Buras and Mitariten, 1994; Shirley et al., 1996). Interesting embodiments of that method have been presented in patent speci cations (Davies and Gray, 1992; Reinhold and Knaebel, 1998). The rst, and so far the only, pilot plant for the recovery of methane from coal mine gas was built in 1980s in Germany (Pilarczyk and Knoblauch, 1987). A few papers can be found on modelling the PSA process when it is employed to separate CH4N2 mixtures (Baksh et al., 1990; Warmuzin ski et al., 1990; Ba ys et al., 1994). 474

Typical composition of coal mine methane gas is not favourable for the gas separation methods since it is not easy to separate methane from nitrogen and oxygen and to keep the operating costs reasonably low at the same time. It is also for that reason that any discussion on those problems can hardly be found in the papers published so far. When selecting from among the known separation methods for gases, one appears at a conclusion that the pressure swing adsorption technique makes it possible to ef ciently recover methane from coal mine gas. Modi cations of the classical PSA process become important since the gases considered are hard-to-separate components; nitrogen and oxygen have to be separated from methane precisely and both of them at the same time, and the product gas (methane-rich gas) has to contain 96 vol% CH4 at least. The VPSA (vacuum pressure swing adsorption) method with carefully selected sorption materials makes a more promising separation process than the classical PSA process owing to its superior ef ciency and productivity. It does not make a process which would be applicable in effective recovery of methane from coal mine gas. In the suggested VPSA method, CO2 is removed from coal mine gas with help of solid potassium hydroxide. Then the gas undergoes compression and is dried with wide-pore silica gel and activated alumina. The resulting mixture of methane, nitrogen and oxygen is subjected to separation in the VPSA facility under a pressure of about 300 kPa abs. The process comprises the following stages: adsorption;

METHANE SEPARATION FROM GAS counter-current purge; desorption of methane down to the nal pressure of about 25 kPa abs.; and lling. From the quality viewpoint of the separation process of the CH4N2, O2 mixture, the processes should be controlled chie y by the diffusion mechanisms for the gas molecules in the transport pores of the sorption material and by the adsorption equilibrium conditions. Hence, the most important criteria within process engineering for selecting the adsorption agent should be high selectivity at equilibrium for methane against nitrogen and oxygen, as well as high and not much diversi ed values of the diffusion coef cients for those gases in the transport pores of the sorption material. These conditions can be satis ed by suitable activated carbons which are characterized by well-developed transport pores and high capacity of micropores. The purpose of this study is to determine experimentally the basic parameters for the VPSA process employed to recover methane from coal mine methane gas. The activated carbon selected for that purpose should make it possible to convert coal mine gas into methane-rich gas with CH4 content of 96 vol% at least. Also, the study is intended to verify experimentally the computer calculation software. The ndings from laboratory tests and from computer calculations would be utilized to design a pilot plant.

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where molar gas velocity is referred to the internal free area of the adsorber vessel and it is described as: _ C v q C (3)

and gas satis es the perfect gas equation P Rg T (4)

Glu ckauf equation for adsorption kinetics Ri rN i @a rN ki (ai a i) @t bi ci P2 (5)

Langmuir isotherms ai ai 1 where 1 bj cj (6)

j 1

( DHi ) 1 1 bi bi0 exp T T ( 0 ) Rg

(7)

MATHEMATICAL MODEL Coal mine methane gas contains typically 4555 vol% CH4, 78 vol% O2, 23 vol% CO2 and balance nitrogen. Before entering a VPSA unit, coal mine gas is subjected to drying and carbon dioxide is removed. Since adsorption of oxygen in the selected activated carbon is similar to that of nitrogen, the computer calculations for the VPSA process can be simpli ed when the feed gas is assumed to be a twocomponent mixture only: methane and nitrogen. In order to simplify the laboratory-scale process in which thermal effects are negligible, the VPSA-based methane recovery process was assumed to be described by means of an isothermal, non-equilibrium model of two components: methane and nitrogen. However, the thermal effects have to be taken into consideration when modelling a large-scale process. These effects are revealed by, among other things, the existence of the heat de cit zone and lower temperature at the feed inlet. This decreases methane desorption from this zone and hence it lowers the ef ciency of methanenitrogen separation by VPSA. The VPSA process for methanenitrogen separation is described by the following equations: equation for transport of i-component of gas mixture DL @2 @ @ _ yi ) eb (C yi ) Ri 0 (C yi ) (q @ z2 @z @t (1) overall balance equation _i @q @C eb @z @t
2 X j1

and ai 1 constant. The mass transfer is limited by the molecular diffusion (DM) and the Knudsen diffusion (DKi) in transport pores of activated carbon granules (Yang, 1987; Ruthven et al., 1993). The diffusion coef cient for the diffusion in transport pores of the adsorbent is described by the equation: P 1 1 1 t (8) Dpi DKi P0 DM The equation de ning the transport coef cients for the gas components in the activated carbon has the following form: ep Dpi c0i 1e ki O 2 (9) Rp (1 ep ) a0i rN The molecular diffusion coef cient DM can be calculated from the Arnold Gilliland equation while the Knudsen diffusion coef cient can be calculated from the following formula (Yang, 1987): T 1=2 DKi 97:0vp (10) Mi The relation between individual types of adsorbent porosity is given by the equation: e eb (1 eb )ep (11)

The pressure pro les in the VPSA process, for the operations carried out under changing pressure, can be described with the equations: j P(t )l PP,l t l 1 1 (12) PK,l PP,l tl for the operations with rising pressure, and j P(t )l PP,l t l 1 PK,l PP,l tl

(13)

Rj 0

(2)

for the operations with decreasing pressure, where jl is pressure history experimental shape factor.

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COMPUTER SOFTWARE The system of equations (1)(6) was solved by the nite element method. The adsorbent bed was divided into 50 elements of the same volumes. The number of time intervals was calculated separately for each process operation, under equal residence times for unit volumes of gas in unit volumes of the bed. The nal parameters of a unit volume of bed were calculated for the de ned boundary and initial conditions, and for a given unit volume of the bed in a given time interval. The iterative calculation method was used and the unit volume under investigation was considered to make a unit reactor with perfect gas mixing. The nal parameters found for a unit volume of bed make the boundary parameters for the next unit volume of bed, while the parameters for the previous time interval make the initial parameters. The calculations are made for all the bed volumes and all the time intervals within the process operation. Then the calculations are repeated for the next process operation, and then for the next cycle in the VPSA process. The calculations are repeated again and again until stable parameters are arrived at for the gaseous phase, adsorbent phase and the same balance of components in two subsequent cycles. The software for the calculations of the VPSA process, which in fact is a computer simulation of the VPSA process, was given a modular structure. There are modules which describe the adsorption process, modules which characterize the individual process operations, and a supervisory program which provides the initial data for calculations and de nes the structures of the VPSA cycle.

EXPERIMENTAL PLANT The tests were run at a bench-scale stand as shown in Figure 1. Speci cations for adsorber vessels have been provided in Table 1. CO2 was removed from coal mine methane gas in a column lled with solid potassium hydroxide (not shown in the diagram) until its content dropped down to the level of 0.1 vol%. The product gas was compressed in a membrane compressor (K-01) to the pressure of 300320 kPa abs. and dried in a drier (D-02) lled with wide-pore silica gel and activated alumina. Dry gas containing 55.2 vol% CH4 was transferred to a buffer vessel (V-03). Excess gas was recycled by a pressure control valve KV(PC-1) to the compressor inlet line. Compressed gas from the buffer vessel (V-03) was passed to the VPSA module composed of adsorbers (D-04 A, B, C) and solenoid valves. Adsorbers were packed with a properly selected activated carbon, which was employed in the VPSA process to separate the feed gas into nitrogen, oxygen and methanerich gas. The nitrogenoxygen mixture (with low methane
Table 1. Speci cation of adsorber vessels in experimental plant. Internal diameter Height of sorbent bed [G2X7=12] Total height of adsorber vessel Amount of activated carbon in one adsorber vessel Amount of alumina in one adsorber vessel: Bottom layer Top layer 0.069 m 2.4 m 2.5 m 3.9 kg 0.4 kg 0.15 kg

Figure 1. Process diagram for experimental plant. K-01, compressor of coal mine gas; D-02, drier; V-03, buffer vessel; D-04, PSA module; A, B, C, adsorbers; V-05, nitrogen buffer vessel; P-06, vacuum pump; V-07, intermediate buffer vessel; K-08, methane compressor; V-09, methane buffer vessel; KV , solenoid valves; PC, pressure controller; QI, owmeter; FI, rotameter; PI, manometer; A, sampling point; CMM gas, coal mine methane gas; Z, manual control valve.

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METHANE SEPARATION FROM GAS content) was transferred from adsorbers to a buffer vessel (V-05), then it was passed through a volumetric gas ow meter and released to atmosphere. Some part of the nitrogenoxygen mixture was recycled to adsorbers at the re-pressurization step (RR). At the desorption step (D), methane-rich gas was extracted from the adsorbers by means of a membrane vacuum pump (P-06) down to the pressure of about 25 kPa abs. Thus recovered methane was transferred to a buffer vessel (V-07), then it was compressed in a membrane compressor (K-08) to the pressure of about 350 kPa abs. and passed to another buffer vessel (V-09). Some volumes of methane-rich gas were recycled from that vessel to the VPSA module to purge nitrogen and oxygen away. The ow rate of recycled gas was measured by a rotameter (FI). Excess methane-rich gas was carried away by a pressure control valve KV(PC-2) installed in the buffer vessel (V-09). The amount of produced gas was measured by a volumetric meter. Gas samples were taken for analysis from sampling points (A). Individual components of gas samples were analysed by gas chromatography. The amount of CH4 in gas was measured with a Perkin-Elmer chromatograph with ame ionization detector (FID), using a chromatographic column which was loaded with dimethylsulfolane onto Chromosorb P. The amounts of N2, O2 and CO2 were measured with a Perkin-Elmer chromatograph with thermal conductivity detector (TCD), using a column loaded with Carbosiv G activated carbon. The VPSA process was carried out by opening and closing solenoid valves (KV 112), which were operated by a programmable controller. DESCRIPTION OF VPSA PROCESS The VPSA process cycle is composed of the following unit operations: (A) Adsorption stage, duration of 320 s, pressure of 300 kPa abs.feed coal mine methane gas is passed through the adsorber vessel upwards, methane is selectively adsorbed in the bed of activated carbon, and the mixture of nitrogen and oxygen (with small percentage of methane) leaves the adsorber vessel and is sent to the buffer vessel (V-05) from where it is continuously released to the atmosphere. (R) Counter-current rinse, duration of 320 s, pressure of 305 kPa abs.methane-rich gas produced from the desorption phase (D) is subjected to compression and is passed through an adsorber vessel downwards to rinse nitrogen and oxygen out; the ef uent gas is mixed with the feed stream. (D) Desorption phase, duration of 380 smethane-rich gas is evacuated from the adsorber vessel, a vacuum pump is employed for that purpose, the adsorber vessel pressure is lowered down to 25 kPa abs., methane-rich gas is then compressed to 350 kPa abs. and some part of that gas is recycled to the process. (RR) Re-pressurization phase, duration of 20 sthe adsorber vessel pressure is increased to 200 kPa abs., the mixture of nitrogen and oxygen from the buffer vessel (V-05) is charged to the adsorber vessel and it ows in countercurrent to the gas ow direction at the adsorption phase. Trans IChemE, Vol 81, Part A, April 2003

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(AR) Pressurization-with-feed phase, duration of 60 s the adsorber vessel pressure is increased to 300 kPa abs., the feed gas is charged to the adsorber vessel from its bottom and at the same time the mixture of nitrogen and oxygen is let out of the other side of the adsorber vessel and is sent to the buffer vessel. The complete cycle for the VPSA process comprises three sequences while each sequence takes 400 s. Each sequence is composed of all the unit operations as described abovesequences refer to different adsorber vessels. The separation experiments were carried out at the average temperature of 278 K. The ow diagram for gas streams in the VPSA cycle is presented in Figure 2, while the time schedule for the VPSA cycle is shown in Figure 3. Pressure pro les for the adsorber vessel (A) can be found in Figure 4. ACTIVATED CARBON The following criteria were considered when selecting a suitable activated carbon grade: high selectivity for methane adsorption versus nitrogen and oxygen; high adsorption capacity for methane; low difference between possibly high values of diffusion coef cients for methane and nitrogen oxygen in transport pores of the sorption material; price of the activated carbon. A few adsorbents were tested and the activated carbon G2X7=12 from Takeda Industries (Japan) was selected.

Figure 2. Flow diagram for gas streams in VPSA cycle. A, adsorption; R, counter-current rinse; D, desorption; RR, re-pressurization; AR, pressurization with feed; V-05, buffer vessel for N2 O2; P-06, vacuum pump; V-07, intermediate buffer vessel; K-08, methane compressor; V-09, methane vessel; CH4, methane-rich gas; N2 O2, N2 O2 mixture after methane was separated therefrom; CMM gas, coal mine methane gas.

Figure 3. Time schedule for VPSA process. D-04 A, B, C, adsorbers; A, adsorption; R, counter-current rinse; D, desorption; RR, re-pressurization; AR, pressurization with feed; , pause in the process.

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Figure 4. Pressure history for adsorber D-04 A in PSA cycle. A, adsorption; R, counter-current rinse; D, desorption; RR, re-pressurization; AR, pressurization with feed.

Table 2 presents its speci cation. Adsorption isotherms for methane and nitrogen were found with the use of the standard volumetric method, at temperatures of 273 and 298 K. The pro les for those isotherms have been presented in Figure 5. The values for ai 1 , bi0 and (DHi) were calculated from experimental data, with the use of equations (6) and (7). The employed activated carbon offers high adsorption selectivity for methane versus nitrogen what makes it possible to separate ef ciently methane from nitrogen and oxygen in the VPSA process. MASS TRANSFER COEFFICIENT ki Taking advantage of equations (8), (9) and (10), the values of mass transfer coef cients ki were calculated; these were average values for individual process operations. The data for the calculations can be found in Table 3. The value of tortuosity factor for activated carbon was assumed to be t 10, as per the data available in literature (Yang, et al., 1985). The value of O was assumed a priori to be equal to O 15 for all process operations. Table 4 provides the calculated values of ki coef cients for methane and nitrogen as well as the values of jl coef cients for individual process operations. The values of ki coef cients were
Table 2. Speci cation of activated carbon G2X7=12. Pore surface as found by BET=N2 method Pore surface as per Langmuir isotherm Pore volume Average pore diameter Diameter of dominant pores Diameter of transport pores Saturation constant a 1 (273 K) Saturation constant a 1 (298 K) 3 1 Af nity constant (dm mol ): bCH4 (273 K) bCH4 (298 K) bN2 (273 K) bN2 (298 K) KCH4=N2 (273 K) KCH4=N2 (298 K) DHCH4 DHN2
1 1007.2m2 g 1 1343.3m2 g 3 0.4964cm g 1 1.471nm 3.00 nm 1090 nm 1 3.32 mol kg 1 3.30 mol kg

Figure 5. Adsorption isotherms for methane and nitrogen at temperatures of 273 and 298 K. d, experimental points. Solid lines, calculated by equations (6) and (7) with the use of data from Table 2.
Table 3. Data for calculation of transport coef cients ki. DM (278 K, 101.3 kPa) DKCH4 (278 K) DKN2 (278 K) rp t O ep eb e rN
4 2 0.164 10 m s 1 4 2 0.081 10 m s 1 4 2 0.061 10 m s 1 9 20 10 m 10 15 0.33 0.63 0.75 3 500 kg m

calculated for the average pressure and the feed composition at a given process operation. As results from the calculations, the share of the Knudsen diffusion component 1=DKi in the resistance experienced in the mass transport is considerable and it affects the transport processes in every operation, and in particular in the desorption operation. DISCUSSION OF RESULTS AND COMPUTER CALCULATIONS The study made use of coal mine methane gas which, after puri cation, contained: 55.2 vol% CH4, 8.6 vol% O2,
Table 4. Values of calculated transport coef cients ki for individual process operations and values of jl factors [equations (12) and (13)]. Name and symbol of operation Adsorption (A) Rinse (R) Desorption (D) Re-pressurization (RR) Pressurization with feed (AR)
1 kCH4 (s ) 1 kN2 (s )

jl P(t)constant P(t)constant 3 1 2

25.36 12.99 4.11 2.97 6.17 4.38 1 18,100J mol 1 8800 J mol

0.047 0.047 0.075 0.082 0.052

0.094 0.094 0.140 0.151 0.104

The values for the parameters: a 1, bi and (DHi) were calculated on the basis of adsorption isotherms which had been found experimentally.

Values of jl factors were calculated from time pro les for pressures at individual process operations in the VPSA cycle as carried out at the experimental plant.

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METHANE SEPARATION FROM GAS 0.1 vol% CO2 and balance nitrogen. Stable operating conditions for a test stand were obtained after 34 h on-line. Gas samples for analysis were taken 56 h after starting an experiment. At nearly constant gas ow rate from adsorption, falling within QIN 49.750.3 dm3(STP)=S*, we changed the amount of methane recycled to the system. The ratio of recycled methane and methane charged in the feed, P=F, was modi ed in that way. The coal mine gas ow rate at the test plant inlet was adjusted automatically by the pressure control system KV(PC-1) (Figure 1) and it fell within QF 97.6121.9 dm3(STP)=S*, depending on the volume of methane recycled to the process. Pressure control provided by the control system KV(PC-2) (Figure 1) changed the ow rate for methane-rich gas QCH4, which was the difference between the volume of methane produced in the desorption operation (D) and that recycled to the process in the counter-current rinse phase (R). The experimental ndings and computer calculation results are presented graphically in Figures 611. The experiment was carried out at the plant output QCH4 44.7 72.5 dm3(STP)=S*, and the ratio of recycled methane to feed methane was changed within P=F 2.121.12 (Figure 6). At the plant output of QCH4 45 55 dm3(STP)=S*, i.e. with the P=F ratio of 1.82.12 (Figure 6), methane-rich gas was produced which contained YCH4 9698 vol% CH4 (Figure 7). Ef ciency of methane separation under such process conditions falls within ZCH4 8691% (Figure 8), while the inert content (N2 O2) in the adsorption ef uent gas is within 8589% (Figure 9). At the same time, the rejection degree for nitrogen oxygen from the feed gas is high, i.e. ZIN 9698% (Figure 10). Figure 11 presents the inter-

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Figure 7. Product purity YCH4 (vol%) vs plant capacity QCH4 [dm3(STP)=S*]. , Experimental points; solid line, calculated pro le; S*, 400 s (one sequence in PSA cycle).

Figure 6. Recycle ratio for methane P=F vs plant capacity QCH4[dm3(STP)=S*]. , Experimental points; solid line, calculated pro le; S*, 400 s (one sequence in PSA cycle); P=F, recycle ratio QR YCH4 =QF YCH4 F .

Figure 8. Ef ciency of methane recovery ZCH4 (%) vs plant capacity QCH4 [dm3(STP)=S*]. , Experimental points; solid line, calculated pro le; S*, 400 s (one sequence in PSA cycle).

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Figure 9. Content of inerts (N2 O2) in the adsorption ef uent gas YIN (vol%) vs plant capacity QCH4 [dm3(STP)=S*]. , Experimental points; broken line, extrapolation of experimental ndings; solid line, calculated pro le.

Figure 11. Content of inerts (N2 O2) in the adsorption ef uent gas YIN (vol%) vs methane content YCH4 (vol%) in the desorption ef uent gas. , Experimental points; broken line, extrapolation of experimental ndings; solid line, calculated pro le.

Figure 12. Diagram for optimum charging the sorbent material with methane in VPSA process. A, adsorption; R, counter-current rinse; D, desorption. The lines present charging the sorbent material with methane at the end of: A, adsorption operation; R, rinse operation; and D, desorption operation.

Figure 10. Rejection degree for nitrogen and oxygen ZIN (%) vs plant capacity QCH4 [dm3(STP)=S*]. , Experimental points; solid line, calculated pro le; S*, 400 s (one sequence in PSA cycle).

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METHANE SEPARATION FROM GAS dependence of the inert (N2 O2) content in the adsorption ef uent gas (YIN) and the methane content in the methanerich gas (YCH4). When the plant produces the methane-rich gas with the methane content of YCH4 9698 vol% CH4, the methane content in the methane-lean gas discharged from the plant at the adsorption stage falls within 1115 vol% (YIN 8589 vol%). When the methanerich gas is obtained from the plant with a lower methane content, below 94 vol% CH4, the methane content in the methane-lean gas stabilises at the level of 10 vol% (YIN 90%). That optimum separation of coal mine methane gas was found possible when the methane sorption wave was brought to the outlet point of the sorption bed at the adsorption phase, and then the methane sorption wave was brought to the entry point of the sorption bed at the countercurrent purge phase. That was a precondition for optimum separation of methane and nitrogen oxygen. Those conditions of running the separation process are presented in Figure 12. The methane content in the adsorption ef uent gas is principally dependent on the desorption step nal pressure as well as on the kinetics of methane adsorption in the activated carbon bed and on the sorption capacity of the sieve for methane. The dynamics of the VPSA process is inferior here. Reduced volume of methane recycled to the process, and hence reduced P=F ratio, improves the ow of product QCH4. Thus, the methane content in the methanerich gas becomes reduced, YCH4 8694 vol% (Figure 7), ef ciency of methane recovery becomes improved to the level of ZCH4 9093%, and the methane content in the adsorption ef uent gas becomes reduced to 10 vol% CH4 (YIN 90 vol%). Resulting from lower purity of the product gas obtained, elimination of inerts from methane-rich gas is considerably worse (Figure 10). When the calculation results (solid lines in Figures 611) are compared with experimental ndings, good conformity is observed for those two sets of data. The experimental data points in Figure 7 lie 12% below the pro le for calculation. The experimental data points in Figure 8 are placed 13% below the pro le for corresponding calculation. The differences are higher in case of Figure 9, which stems from the simpli cation adopted for the mathematical model. Moreover, when the methane sorption wave is brought to the outlet point of the sorption bed at the adsorption phase, and then when the methane sorption wave is brought to the entry point of the sorption bed at the counter-current purge phase, the gas separation process becomes very sensitive to changes in the gas ow rate in individual operations. Even a slight increase in the ow rate of the methane-lean gas, and hence a slight increase in the ow rate of feed gas, results in moving the methane sorption wave beyond the bed. Thus, the methane content will be increased in the plant ef uent gas at the adsorption phase. Similarly, a slight increase in the ow rate of the methane-rich gas which is recycled to the process in the purge operation will result in moving the methane sorption wave beyond the bed. In effect, higher doses of methane will be introduced to the process in its adsorption phase and this in turn will move the methane sorption wave away from the bed. As a consequence, the methane content will become excessive in the methane-lean gas which leaves the plant at the adsorption phase.The ndings from the research for the VPSA methane recovery process from coal mine Trans IChemE, Vol 81, Part A, April 2003

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gas were employed in designing a pilot plant with capacity 2025 m3(STP)=h of coal mine gas. The pilot plant was built in 2001 and it was used for systematic research of the VPSA process, achieving good results. SUMMARY The ndings from computer calculations for the VPSA methane recovery process from coal mine methane gas correspond satisfactorily to the experimental data obtained from a laboratory. When coal mine gas was used for separation which contained 55.2 vol% CH4, and when the ratio for re-circulated methane to that introduced in the feed was adopted to fall within P=F 1.82.12, methane-rich gas was produced which contained 9698 vol% CH4. The ef ciency gure for methane recovery was 8691%, while the methane content in methane-lean gas released from the adsorption facility was 1115 vol% CH4. The degree for nitrogen and oxygen rejection from methane-rich gas was high and it reached 9698%. A precondition for so good separation of coal mine methane gas is bringing the methane sorption wave to the outlet point of the sorption bed at the adsorption phase, and then bringing the methane sorption wave to the entry point of the sorption bed at the countercurrent purge phase. Under optimum conditions, the VPSA process employed to separate coal mine methane gas becomes very sensitive to changing ow rates of feed gas and recycle (purge) gas. NOMENCLATURE
a i ai ai 1 a0i bi bi0 C ci C yi c0i DL DM DKi Dpi (DHi) ki KCH4=N2 q _ QF QCH4 QIN QR L n P P0 P(t) adsorbed phase concentration for component i, mol kg1 equilibrium adsorbed phase concentration for component i, mol kg1 saturation constant in Langmuir isotherm, mol kg1 equilibrium adsorbed phase concentration for component i at inlet of adsorber vessel (z 0), to initial gas phase concentration (c0i), mol kg1 af nity constant in Langmuir isotherm for component i, dm3 mol1, m3 mol1 af nity constant at basic temperature T0, dm3 mol1, m3 mol1 total concentration of gas phase P=Rg T, mol dm3, mol m3 gas phase concentration for component i, mol dm3, mol m3 gas phase concentration for component i at inlet (z 0), mol dm3, mol m3 axial diffusion coef cient, m2 s1 molecular diffusion coef cient at 273 K, 101.3 kPa, cm2 s1, m2 s1 Knudsen diffusion coef cient for component i, cm2 s1, m2 s1 pore diffusion coef cient for component i, cm2 s1, m2 s1 isosteric heat of adsorption for component i, J mol1 overall mass transfer rate, s1 aCH4 yN2 =aN2 yCH4 , methane=nitrogen equilibrium selectivity molar ow rate, mol dm2 s1, mol m2 s1 feed ow rate, dm3 S*1 (at 273 K, 101.3 kPa), (STP) product ow rate, dm3 S*1 (at 273 K, 101.3 kPa), (STP) inerts ow rate, from adsorption, dm3 S*1 (at 273 K, 101.3 kPa), (STP) recycle ow rate, dm3 S*1 (at 273 K, 101.3kPa), (STP) adsorbent bed height, m number of components, n 2; 1, N2, 2, CH4 pressure, kPa, atm standard pressure 101.3kPa pressure history, equations (12) and (13), kPa, atm

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PK,l PP,l P=F Rg tp S* T T0 t tl v yi YCH4 YCH4 F YIN z Greek symbols jl rN ep eb e t ZCH4 ZIN O

OLAJOSSY et al.
nal pressure in operation l, kPa, atm initial pressure in operation l, kPa, atm recycle ratio QR YCH4 =QF YCH4 F universal gas constant 8.314 J K1 mol1 mean transport pore radius of adsorbent, m sequence of cycle, here 400 s temperature, K basic temperature, here 273 K time, s time of cycle steps, s l A, R, D, RR, AR intersitial gas velocity, dm s1 mol fraction for component i in gas phase methane concentration in product, vol% methane concentration in feed, vol% N2 O2 concentration in gas from adsorption, vol% axial distance, m Buras, R.J. and Mitariten, M.J., 1994, Nitrogen rejection with pressure swing adsorption. Principles design and remote control using expert system, in Proc. 44th Laurence Reid Gas Conditioning Conference, pp 93103. DAmico, J., Reinhold, H. and Gamez, J., 1993, A PSA process for nitrogen rejection from natural gas. Presented at 1993 Laurence Reid Gas Conditioning Conference, Norman, OK. Davies, M.M. and Gray, R.L., 1992, Process for the puri cation of natural gas, United States Patent no. 5,174,796. Pilarczyk, E. and Knoblauch, K., 1987, Separation technology, in Proc. Eng. Found. Conference, Schloss Elmau. Reinhold, H.E. and Knaebel, K.S., 1998, Separation of gases by pressure swing adsorption, United States Patent no. 5,792,239. Ruthven, D.M., Farooq, S. and Knaebel, K.S., 1993, Pressure Swing Adsorption (VCH, Canada). Shirley, A., Porto, J., Ramachandran, R. and Kleinberg, W., 1996, Noncryogenic nitrogen rejection from natural gas, in Proceedings of the Seventy-Fifth GPA Annual Convention, Oas Process Association, pp 6266. Warmuzin ski, K., Buzek, L., et al., 1998, Separacja mieszanin metanu i azotu na we glowym sicie molekularnym metoda adsorpcji zmiennocis _ ynieria Chemiczna i Procesowa, 19.4: 915928. nieniowej. Inz Yang, R.T., 1987, Gas Separation by Adsorption Processes (Butherworths, Oxford, UK). Yang, R.T. and Doong, S.J., 1985, Gas separation by pressure swing adsorption. A pore diffusion model for bulk separation., AIChE J, 31: 18291841.

pressure history experimental shape factor for operation l, equations (12) and (13) adsorbent bulk density, kg m3, kg dm3 adsorbent particle porosity voidage of adsorbent bed total porosity tortuosity factor methane recovery ef ciency, % N2 O2, inerts rejection ef ciency, % Glu ckauf parameter, in equation (9)

ADDRESS REFERENCES
Baksh, M.S.A., Kapoor, A. and Yang, R.T., 1990, A new composite sorbent for methane nitrogen separation by adsorption, Sep Sci Technol, 25(7 8): 845868. Ba ys, M., Buczek, B. and Zie tkiewicz, J., 1994, Modelling study of PSA process for methane recovery from mine gas, Presented at the Silesian International Conference on Coalbed Methane Utilisation, Katowice. Correspondence concerning this paper should be addressed to Professor A. Olajossy, Akademia Go rniczo-Hutnicza im. Stanis awa Staszica, Al. Adama Mickiewicza 30, 30-59 Krako w, Poland E-mail: olajossy@uci.agh.edu.pl The manuscript was received 17 September 2001 and accepted for publication after revision 30 October 2002.

Trans IChemE, Vol 81, Part A, April 2003