Removal of Acetone and Methyl Isopropyl Ketone in a Composite Bead Biofilter Wu-Chung Chan and Kang-Hong Peng Department of Civil Engineering and Engineering Informatics Chung-Hua University No.707, Sec. 2, Wufu Rd., Hsinchu City 300, Taiwan (R.O.C.) Tel.: +886-3-5186725 Fax.: +886-3-5372188 Email: wcchan@chu.edu.tw Abstract Removal of acetone and methyl isopropyl ketone (MIPK) in a composite bead biofilter was investigated. Both microbial growth rate kg and biochemical reaction rate kd would be inhibited at higher inlet concentration. For the microbial growth process, the kg value of MIPK was greater than that of acetone and the inhibitive effect for MIPK was more sensitive than that for acetone in the average inlet concentration range of 100-150 ppm. The kg value of acetone was greater than that of MIPK and the inhibitive effect was almost the same sensitivity for two ketone compounds in the average inlet concentration range of 200-300 ppm. The zero-order kinetic with the diffusion rate limitation was regarded as the most adequate biochemical reaction model. For the biochemical reaction process, the kd value of acetone was greater than that of MIPK and the inhibitive effect for MIPK was more sensitive than that for acetone in the average inlet concentration range of 100-300 ppm. The maximum elimination capacity of acetone and MIPK were 54.68 and 35.18 gC h-1 m-3 bed volume, respectively. The compound with less number of carbons or no side group in the main chain was easier biodegraded by the microbial. Keywords: acetone; methyl isopropyl ketone; microbial growth rate; biochemical reaction rate; composite bead biofilter 1. dioxide). Biofiltration involves the passage of a Introduction The removal of volatile organic compounds (VOCs) from a polluted air stream using a biological process is highly efficient and has low installation and operation/maintenance costs. Biofiltration technology offers environmental advantages: it does not generate undesirable byproducts by converting many organic and inorganic compounds into harmless oxidation products (e.g., water and carbon polluted air stream through a packed bed containing microorganisms immobilized within a biofilm attached to the bed-packing material. Contaminants are transferred to the interface between the gas and biofilm and are subsequently absorbed into the biofilm. Contaminants are then used as carbon and/or energy sources for the microorganisms within the biofilm. The solid filter material provides a nutrient source and matrix for the attachment of process. in the biofiltration process in our previous works [6, Therefore, the filter material property is an important 7]. The diffusivity of nutrient within this filter factor to obtain optimal pollutant removal. The material would be an important control factor for optimal filter material should have the following achieving good biofilter performance. microorganisms in the biofiltration characteristics: high moisture holding capacity, Acetone, methyl ethyl ketone (MEK), methyl porosity, available nutrients, and pH buffer capacity isobutyl ketone (MIBK) and methyl isopropyl ketone [1]. (MIPK) are widely used industrial chemicals. These A wide range of filter materials including ketone compounds were designed high-priority toxic compost, peat, and soil have been studied and found chemicals. to be effective bed material for specific contaminants compounds are released into the atmosphere during and gas streams [2-4]. However, these natural manufacturing processes every year, leading to the materials appear cracking and compaction as the endangerment of air quality and public health. Some filter bed is operated over a period of time. These reports phenomena cause a rise in the bed’s head loss and compounds. MEK biodegradation by Pseudomonas uneven flow distribution to reduce the efficiency of sp. KT-3 was suppressed as the addition of MIBK or the removal of VOC. Carbon, nitrogen, and acetone in liquid culture. The phenomenon was due phosphorus for to the solubility of acetone was higher than that of microbial growth and metabolism. Carbon can be MEK, and MIBK and MEK could compete with each provided by the VOCs in the air stream, but both other for enzyme binding [8]. MEK degradation by nitrogen and phosphorus must be provided by the using biofilters with a pure strain of Rhodococcus sp. filter material. Nitrogen is a major constituent of or a mixed culture of microbes showed no advantage microorganism proteins and nucleic acids because it of a pure culture; and the mass-transfer mechanism is can make up approximately 15% of microbial cell dry macropore controlled in both the granular activated weight [5]. Consequently, nitrogen can be a limiting carbon and compost media [9]. The maximum nutrient if adequate amounts are not available in the elimination capacity achieved were 50g/m3-h for biofilter material. Inorganic nitrogen (i.e., ammonia, MEK and 20g/m3-h for MIBK at the inlet nitrate, or nitrite) is water-soluble and can be concentration of two pollutants mixture 300 mg/m3 considered for MEK and 330 mg/m3 MIBK [10]. Although the lag microorganisms. Inorganic nitrogen is generally not phase for MIBK removal was shorter than that for initially present in the filter material. It is formed by MEK removal, the biodegradation rate of MEK was the mineralization of organic nitrogen in the filter significantly higher than that of MIBK. Both MEK material and by recycling nitrogen through the and MIBK biodegradation rates were reduced as mineralization of cells. Granular activated carbon MEK was pulsed into the air stream containing MEK (GAC) has large surface area and porosity, so adding and MIBK mixtures, but both rates were not GAC into the biofilter would enhance the adsorption influenced as MIBK was pulsed [11]. Various capacity, moisture holding capacity, and porosity of responses were observed when hexane, acetone, filter alcohol 1-propanol and MIBK were introduced in a step pulse was manner to biofilter degrading MEK. Hexane was prepared and was proven suitable as a filter material neither adsorbed to the packing nor biodegraded to a are as material. three the important available A spherical (PVA)/peat/KNO3/GAC nutrients nitrogen polyvinyl composite bead Large concerned volumes the of these biofiltration of ketone ketone significant extent. Acetone was subject to important operating and design on the biofiltration. However, sorption and well degraded. 1-Propanol was better details of the kinetic of such biodegradation removed even though the biofilter had never been processes in biofilter are scant in the relevant exposed to 1-propanol vapors before the experiment. literature. This article investigates the biochemical MIBK showed the most inhibitive effect on the kinetic behaviors of ketone compounds in a degradation of the base feed of MEK [12]. The composite bead biofilter. The ketone compounds are maximum elimination capacity of MEK was 5.82 kg acetone and MIPK. The composite bead is the /m3day. backwashing and spherical PVA/peat/KNO3/GAC composite bead. The long-term stable relationships between the microbial growth rate and removal efficiency over 99% was retained for loading biochemical kinetic rate with ketone compounds and COD starvation/stagnant Using strategies, 3 rate up to 3.52-5.63 kg COD/m -day [13]. The maximum elimination capacity of MIBK was 4.82 kg COD /m3-day. Combination of backwashing and inlet VOCs concentration are also investigated. 2. Experimental intermittent operations, long-term stable removal Peat (industrial grade from KekkilaOyj, Tuusula, efficiency over 99% was retained for loading rate up Finland) was dried at 105℃ before use. It has a dry to 5.43 kg COD/m3-day. The pseudo-first-order density of 90 kg m-3, a pH of 5.5, a pore volume of removal rate constant decreased with increase in 96%, and an organic substance content of 91%. Boric volumetric loading rate for MEK and MIBK [14]. acid, sodium monobasic phosphate, sodium dibasic The biofilter performance was evaluated under phosphate, potassium nitrate, acetone and methyl interchanging the feed VOCs in the sequence MEK, isopropyl ketone (extra pure grade from Union toluene, MIBK and styrene, and then back to MEK. Chemical, Hsinchu, Taiwan) were used as received. The biofilter provided high removal efficiency within Poly(vinyl alcohol) (PVA) powder (industrial grade the critical loading of each VOCs. The biofilter easily from Chung Chun Petrochemical, Hsinchu, Taiwan) acclimated to the oxygenated compounds (MEK and and granular activated carbon (GAC) (industrial MIBK), but re-acclimation was delayed for the grade from Taipei Chemical, Hsinchu, Taiwan) were aromatic compounds (toluene and styrene). The also used as received. destructed aromatic compounds were eliminated The procedures for preparing exclusively by aerobic biodegradation; however, the PVA/peat/GAC/KNO3 composite beads and the destructed oxygen compounds were eliminated by apparatus and operation of the biofilter system were aerobic biodegradation and possible denitrification described in our previous work [7]. Acetone and [15]. methyl isopropyl ketone were used as VOCs. Acetone Recently, we had indicated that the process for and metyl isopropyl ketone were individually in each degradation of VOCs in a composite bead biofilter air stream which flowed through the biofilter column could be divided into lag, log growth and maximum in downward mode. Before packing, the filter stationary three phases, and the log growth and material was immersed in 0.384 M KNO3 aqueous maximum stationary phases were important for solution to adsorb KNO3 and to reach equilibrium controlling the removal efficiency of biofilter [6,7]. (approximately 12 h). The bead moisture content was Therefore, studies the kinetic of log growth and humidified to more than 1.5 g water g-1 dry solid and maximum stationary phases was very important for the seeding was performed with activated sludge. The VOCs concentration in the inlet and exit air streams Both phase II and III are important for controlling the of each section was taken by auto-sampling and removal efficiency of biofilter, so the effect of inlet analyzed using gas chromatography (GC) (Model concentration and type of ketone compounds on the GC-8A from Shimadzu, Tokyo, Japan). The VOCs microbial growth rate and biochemical reaction rate removal efficiency was calculated by the difference was studied. of the VOCs concentration between the inlet and exit air streams. The relative standard deviation and relative error of the experimental measurements were less than 2% and 5%, respectively. 3. 3.1 Microbial growth In the log growth phase (phase II), the microbial growth rate increased exponentially and was represented by the following equation [17]. Results and discussion dX/dt = kg X (1) The variation in the percentage of removed where X is the number of viable cells per unit volume, VOCs over operation time in an air stream with flow kg is the microbial growth rate and t is the operation rate 0.102 m3 h-1, two ketone compounds average time. More amount of viable cell per unit volume in inlet concentration in the range of 100 to 300 ppm, an the bed could consume more amount of contaminant operation temperature 30℃ and a relative humidity because contaminant degradation was the result of of more than 95 % through a composite bead filter microbial activity. Therefore, the concentration of bed is shown in Figure 1. (only the average inlet VOCs in the exit stream (C) was inversely concentration of 200 ppm is shown because the data proportional to the number of viable cells per unit for the other concentrations were visually similar). volume in the bed. The kinetic of contaminant degradation is closely related to the kinetics of 100 microbial growth [1], so Eq. 1 can be converted into Percentage of removed VOCs, % III II dC/dt = – kg C 80 Integration of Eq. 2 yields 60 I ln(C/C0) = – kg t 40 (3) where C0 is the concentration of VOCs in the inlet air stream. A plot of ln(C/C0) versus t should correspond 20 0 (2) to a straight line and kg can be determined. Therefore, 0 50 100 150 200 250 300 Operation time, t , h the microbial growth rate kg of two ketone compounds at various inlet concentrations was Figure 1. Percentage of removed VOCs over operation time (t) for the biofilter at the average inlet concentration 200 ppm: (■) acetone, (▲) methyl isopropyl ketone. calculated from the data in phase II and Eq. 3. The calculated kg values were listed in Table 1. The variations of the kg values with average inlet concentration C0 for two ketone compounds are shown in Figure 2. It was found that the kg value It is found that the variation in the percentage of decreased with increasing average inlet concentration removed VOCs over operation time appeared in three in the concentration range of 100-300 ppm. An phases: lag phase (phase I), log growth phase (phase increase in the inlet concentration generally would II) and maximum stationary phase (phase III) [6, 16] enhance the transfer rate of the VOCs from the gas phase to the biofilm. This phenomenon leads more atm-m3 mol-1, respectively [19], so the amount of microorganisms to participate in the biodegradation acetone dissolved in the biofilm was greater than that activity. of MIPK dissolved. Thus, the result indicated that Table 1. The values of kg (h-1) at various average inlet concentrations and compounds Average inlet such amount of acetone would produce toxic effect to the microorganism at the average inlet concentration 100 ppm. To compare the order of kg value between Compounds concentration, ppm Acetone Methyl isopropyl ketone 100 0.0558 0.1634 150 0.0347 0.0498 200 0.0262 0.0134 250 0.0204 0.0103 300 0.0150 0.0024 two compounds, it was found that the order of kg value was MIPK > acetone in the average concentration range of 100-150 ppm, it was acetone > MIPK in the average concentration range of 200-300 ppm, and it was a transition region in the average concentration range of 150-200 ppm. The kg value decreased from 0.0558 to 0.0347 However, high concentrations of some recalcitrant VOCs may produce inhibitive effects on the metabolic activity of the microbial population [18]. Therefore, the result indicated that the inhibitive effect predominated and the microbial growth rate was inhibited at higher inlet concentration. h-1 for acetone, and from 0.1634 to 0.0498 h-1 for MIPK as the average inlet concentration increased from 100 to 150 ppm. The slope of the linear profiles in this concentration range for acetone and MIPK were 0.42x10-3 and 2.27x10-3 h-1ppm-1, respectively. These results indicated that the inhibitive effect, resulting from increased inlet concentration, for MIPK was more sensitive than that for acetone in this 0.2 concentration range. The kg value decreased from 0.0262 to 0.0150 h-1 for acetone, and from 0.0134 to kg, h -1 0.0024 h-1 for MIPK as the average inlet concentration increased from 200 to 300 ppm. The 0.1 slope of the linear profiles in this concentration range for acetone and MIPK were 1.12x10-4 and 1.10x10-4 h-1ppm-1, respectively. The result indicated that the 0.0 0 100 200 300 Average inlet concentration, C0, ppm Figure 2. The variations of kg with average inlet concentration (C0) for two ketone compounds: (■) acetone, (▲) methyl isopropyl ketone. inhibitive effect, resulting from increased inlet concentration, for two ketone compounds was almost the same sensitivity in this concentration range. 3.1 Biochemical reaction In the maximum stationary phase, the The kg value of acetone was much smaller than population of viable cells was at a relatively constant that of MIPK about 65.8% at the average inlet value. Under the steady-state conditions, the substrate concentration 100 ppm. The Henry’s law constant of utilization rate by microbial was proposed by acetone and MIPK was 5.5320x10-5 and 9.2561x10-5 Ottengraf [1]. Three situations may be encountered in a biochemical reaction system. These corresponding equations could be derived from the Michaeilis-Menten relationship to express the rates of biochemical reaction for each situation as follows: derived from the Michaelis-Menten equation [17] (C0-C)/ln(C0/C) = Vm (θ/ln(C0/C)) - Ks (8) where Ks is half-saturation constant and Vm is 1. First-order kinetic maximum reaction rate. A plot of (C0-C)/ln(C0/C) ln(C/C0) = – k1θ (4) 2. Zero-order kinetic with reaction limitation versus θ/ln(C0/C) should correspond to a straight line, and Ks and Vm can be determined. The plot of C0-C = k0θ (5) 3. Zero-order kinetic with diffusion limitation 1/2 2 C = C0 [1-θ(a k0De /2mC0δ) ] (C0-C)/ln(C0/C) versus θ/ln(C0/C) for two ketone compounds is shown Figure 4. (6) where a is the interfacial area per unit volume, De is the effective diffusion coefficient, m is the distribution coefficient of the component, θis the empty bed residence time (EBRT), δ is the biofilm thickness, k0 is the zero-order reaction rate coefficient with reaction limitation and k1 is the first-order reaction rate coefficients. However, for convenience of use, it is necessary to define a new parameter, kd = (ak0De/2mC0δ)1/2. It can be seen that kd is a function of the operating conditions of the biofilter system, and kd is constant under steady-state conditions. Therefore, Eq. 6 can be rewritten as 1-(C/C0)1/2 = kdθ (7) where kd is the zero-order reaction rate coefficients with diffusion limitation. The plots of ln(C/C0) versusθ, C0-C versusθand 1-(C/C0)1/2 versusθcalculated from the data in phase III are shown in Figure 3 (only the average inlet concentration 200 ppm of acetone is shown since the data for other concentrations and compounds were visually similar). It was found that three plots had high correlation coefficient. The correlation Figure 3. Plots of (a) C0-C versus θ, (b) ln(C/C0) coefficient values for linearized profiles developed versus θ, (c) 1-(C/C0)1/2 versus θ for acetone at the from three kinetic models for acetone and MIPK average inlet concentration 200 ppm. were range from 0.9373-0.9930, and 0.9253-0.9998, respectively. Therefore, all three plots almost follow a linear relationship. In order to verify the biochemical reaction kinetic model, assume there was a plug air flow in the biofilter column and the following equation was The calculated Ks for acetone and MIPK were 26.80 and 22.96 ppm, respectively. The calculated Vm for acetone and MIPK were 8.55 and 7.55 g-C h-1 kg-1 packed material, respectively. According to the Michaelis-Menten concept, (I) as the substrate concentration was very low (Ks >> faster than that of MIPK in this concentration range. The variation of kd with average inlet C0), the reaction rate expression could be simplified to first-order kinetic; substrate concentration C0 for two ketone compounds is shown concentration was very high (Ks << C0), the reaction in Figure 5. It was found that the kd value decreased rate expression could be simplified to zero-order with increasing average inlet concentration in the kinetic; (III) as the substrate concentration C0 was concentration range of 100-300 ppm. The result comparable with Ks, the reaction rate expression indicated that the biochemical reaction rate was also could not be simplified and it was followed inhibited at the higher inlet concentration. The result fractional-order was closely corresponding to the result reported that kinetic (II) as as Eq.7 the derived by Ottengraf’s diffusion limiting model [20]. the pseudo-first-order removal rate constant decreased as the employed loading rate increased for the removal of MEK from waste gas in a trickle-bed air filter [13]. 0 .0 6 kd, s -1 0 .0 4 0 .0 2 Figure 4. Plot of (C0-C)/ln(C0/C) versus θ/ln(C0/C) 0 .0 0 for two ketone compounds: (■) acetone, (▲) methyl 0 50 100 150 200 250 300 A verage inlet concnetration, C 0 , ppm isopropyl ketone. The ratio of C0/Ks for acetone and MIPK were Figure 5. The variations of kd with average inlet 3.73-11.2 and 4.36-13.07, respectively. Therefore, concentration (C0) for two ketone compounds: (■) zero-order kinetic with diffusion rate limitation could acetone, (▲) methyl isopropyl ketone. be regarded as the most adequate biochemical reaction kinetic model because the values of Ks and C0 were comparable for two ketone compounds in this study. The result was corresponding to the result reported that biodegradation of acetone follows zero order kinetics with mass transfer resistance in a compost biofilter [21]. Thus, the kd value of two ketone compounds at various inlet concentrations could be calculated from Eq. 7 and was list in Table 2. The kd value of acetone was approximately 1.07-5.14 times greater than that of MIPK in the average inlet concentration range of 100-300 ppm. The result indicated that the biodegraded rate of acetone was The kd value decreased from 0.0512 to 0.0279 s -1 for acetone, and from 0.0472 to 0.0137 s-1 for MIPK as the average inlet concentration increased from 100 to 200 ppm. The slope of the linear profiles in this concentration range for acetone and MIPK were 2.33x10-4 and 3.35x10-4 s-1ppm-1, respectively. The result indicated that the inhibitive effect, resulting from increased inlet concentration, for MIPK was more sensitive than that for acetone in this concentration range. The kd decreased from 0.0279 to 0.0216s-1 for acetone, and from 0.0137 to 0.0042 s-1 for MIPK as the average inlet concentration increased from 200 to 300 ppm. The slope of the linear profiles capacity will eventually be reached. This maximum in this concentration region for acetone and MIPK overall elimination capacity is independent of -5 -5 -1 -1 were 6.30x10 and 9.50x10 s ppm , respectively. contaminant concentration and residence time within These results indicated that the inhibitive effect, a reasonable range of operating conditions [1]. The resulting from increased inlet concentration, for relationship of elimination capacity (EC) of biofilter MIPK was also more sensitive than that for acetone versus load for two ketone compounds is shown in in this concentration range. Thus, the inhibitive effect Figure 6. It was found that elimination capacity for MIPK was more pronounced in the concentration increased and tended towards a constant value with range of 100-300 ppm. increasing inlet load. The maximum elimination Table 2. The values of kd (s-1) at various average inlet concentrations and compounds. Average inlet capacity of actone and MIPK were 54.68 and 35.18 g C h-1m-3 bed volume, respectively. The result indicated that the maximum elimination capacity of Compounds concentration, ppm Acetone Methyl isopropyl ketone 100 0.0512 0.0472 150 0.0381 0.0355 200 0.0279 0.0137 250 0.0257 0.0103 300 0.0216 0.0042 acetone was greater than that of MIPK. Thus, the compound with less number of carbons or no side group in the main chain was easier biodegraded by the microbial. This result was closely corresponding to the result reported that the maximum elimination capacity (50 g m-3 h-1) of MEK was larger than that (20 g m-3h-1) of methyl isobutyl ketone (MIBK) [10]. 3.3 Elimination capacity 60 EC, g-C h m bed volume Elimination capacity (EC) is the mass of contaminant degraded per unit mass of filter material 40 -3 per unit time and is always equal to or less than the 50 -1 load. Elimination capacity and load could be expressed as EC = Q (C0-C)/V Load = Q C0/V (9) 0 where Q is the flow rate of inlet air steam and V is 100% of the removal efficiency. By increasing the reached. Beyond that point the removal efficiencies will be less than 100%. This point is typically called the critical elimination capacity. As the load continues to increase, a maximum overall elimination 50 100 150 200 250 300 350 -3 Load, g-C h m bed volume Figure 6. The variations of elimination capacity (EC) with load for two ketone compounds biofilters: (■) acetone, (▲) methyl isopropyl ketone. load on a system, a point where the overall load will exceed the overall elimination capacity will be 0 -1 the volume of filter material as packed. Under low equals the load and the system is calculated to be at 20 10 (10) load conditions, the elimination capacity essentially 30 4. Conclusions The biochemical kinetic behaviors of acetone and methyl isopropyl ketone (MIPK) in a composite bead biofilter were investigated. Both microbial growth rate kg and biochemical reaction rate kd would be inhibited at higher inlet concentration. For the [2]. Williams, T.O., Miller, F.C., Biofilters and microbial growth process, the order of kg value was facility operations, Biocycle, Vol. 33 pp. 75-79 MIPK > acetone and the inhibitive effect for MIPK (1992). was more sensitive than that for acetone in the [3]. Hodge, D.S., Tahatabai, F., Winer, A.M., average inlet concentration range of 100-150 ppm. Treatment of hydrocarbon fuel vapors in The order of kg value was acetone > MIPK and the biofilters, inhibitive effect for two ketone compounds had pp.655-662 (1991). almost the same sensitivity in the average inlet Environ. Technol, VOl. 12, [4]. Bohn, H.L., Biofiltration: design principles and The pitfalls, in: Proceedings of the 86th Annual half-saturation constant Ks values of acetone and Meeting & Exhibition of the Air & Waste MIPK were 26.80 and 22.96 ppm, respectively. The Management Association, Denver, Coloado, maximum reaction rate Vm values of acetone and (1993). concentration range of 200-300 -1 ppm. -1 MIPK were 8.55 and 7.55 gC h kg packed material, [5]. Carlson, D.A., Leiser, C.P., Soil beds for the respectively. The zero-order kinetic with the diffusion control of sewage odors, J. 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