Anaerobic Digestion and Methane Generation Potential of Rose Residue in Batch Reactors

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  • This article was downloaded by: [Lahore University of Management Sciences]On: 18 October 2014, At: 00:30Publisher: Taylor & FrancisInforma Ltd Registered in England and Wales Registered Number: 1072954 Registered office: MortimerHouse, 37-41 Mortimer Street, London W1T 3JH, UK

    Journal of Environmental Science and Health, PartA: Toxic/Hazardous Substances and EnvironmentalEngineeringPublication details, including instructions for authors and subscription information:http://www.tandfonline.com/loi/lesa20

    Anaerobic Digestion and Methane GenerationPotential of Rose Residue in Batch Reactorssmail Tosun a , M. Talha Gnll b & Ahmet Gnay ba Department of Environmental Engineering , Suleyman Demirel University , Isparta,Turkeyb Department of Environmental Engineering , Yildiz Technical University , Besiktas,Istanbul, TurkeyPublished online: 06 Feb 2007.

    To cite this article: smail Tosun , M. Talha Gnll & Ahmet Gnay (2004) Anaerobic Digestion and Methane GenerationPotential of Rose Residue in Batch Reactors, Journal of Environmental Science and Health, Part A: Toxic/HazardousSubstances and Environmental Engineering, 39:4, 915-925, DOI: 10.1081/ESE-120028402

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  • JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH

    Part AToxic/Hazardous Substances & Environmental Engineering

    Vol. A39, No. 4, pp. 915925, 2004

    Anaerobic Digestion and Methane Generation Potentialof Rose Residue in Batch Reactors

    _IIsmail Tosun,1,* M. Talha Gonullu,2 and Ahmet Gunay2

    1Department of Environmental Engineering,

    Suleyman Demirel University, Isparta, Turkey2Department of Environmental Engineering,

    Yildiz Technical University, Besiktas, Istanbul, Turkey

    ABSTRACT

    In the study, anaerobic digestion of residues from rose oil industry was

    investigated by using a laboratory scale completely mixed batch reactor in

    volume of 10L and 4 small reactors in volume of 400mL. Ten liters reactor

    isolated with a water jacket and 0.4L reactors settled into a water bath were

    operated at 35 1C. The study supplies biochemical methane potential ofhydrolyzed and original residues. Experimental results showed that hydrolyzed

    rose residue produced a bit more methane than original residue. Methane

    production results were analyzed with first-order and Chen&Hashimotos

    models, and Chen&-Hashimotos model was found to be more suitable than

    first-order kinetic model.

    Key Words: Anaerobic digestion; Hydrolysis; Isparta; Rose residue; Kinetics.

    *Correspondence: _IIsmail Tosun, Department of Environmental Engineering (MMF, Cerre

    Muh.), Suleyman Demirel University, 32260, Isparta, Turkey; Fax: +90-246-2370859;

    E-mail: ismailt@mmf.sdu.edu.tr.

    915

    DOI: 10.1081/ESE-120028402 1093-4529 (Print); 1532-4117 (Online)

    Copyright & 2004 by Marcel Dekker, Inc. www.dekker.com

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    INTRODUCTION

    Rose (Rosa Damascena Mill.) is a species being used to produce attar of rose by

    distilling volatile oils from flowers. It is also consumed for the production of rose

    concrete, absolute and water as fragrance and flower agents for the perfume,

    cosmetic, pharmaceutical and food industries.Turkey has an important role among the countries that are world rose oil

    producers. The rose oil is heavily produced in Isparta province of Turkey. The yearly

    amounts of rose flower harvested for rose oil production in Turkey have been varied

    as shown in Fig. 1. One unit of rose flower milled gives about two units of residue in

    wet weight basis. The content of solids in wet residue is around 10% that is consisted

    of 90% organics. Due to the putrescible aspects of the residues, a substantial

    environmental problem is caused for a short season period between May and June

    months; especially for aquatic bodies that some of them are used for supply potable

    water.Todays World is in an intensive investigation of alternative sources of energy as

    well as environmental considerations. Biogas production through anaerobic

    fermentation from agricultural and animal wastes has been looked upon as a

    promising energy source, especially for developing countries. By this way, the crop

    residues have had been converted to a clean, readily useable and high-energy

    contented fuel (methane). The advantages of anaerobic process are high degree of

    waste stabilization, low production of waste biological sludge, low nutrient

    requirements, reduction in pathogens, no oxygen requirements, and production of

    biogas as a useful end product. Biogasification also stabilizes the wastes while

    providing environmental and cost-effective benefits. Mata-Alvarez et al.[1] reported

    that biogas production could reach over 15-millionm3 d1 of methane throughout

    Europe.Only the biodegradable fraction of organics has a potential for bioconversion.

    Anaerobic bacteria do not easily degrade the refractory organics such as lignin, and

    complete degradation requires a long period. Table 1 gives anaerobic digestion

    experience data produced for some waste types.[24]

    0

    5000

    10000

    15000

    20000

    25000

    30000

    1985 1990 1995 2000

    Years

    Ros

    e fl

    ower

    pro

    duct

    ion

    (t)

    Figure 1. The amounts of rose flower harvested in Turkey cities. i Isparta; Turkey.

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    The main objective of this study is to find out biochemical methane potential ofresidues from rose oil industry by using five laboratory scale completely mixed batchreactors. The study also supplies kinetic analysis of experimental findings obtainedfrom hydrolyzed and original residues.

    MATERIAL AND METHODS

    Reactors

    Totally five reactors were used for the study; one reactor (Reactor A) in 10L andthe others (R1 to R4) in 0.4 L in operating volumes. Reactor A was isolated withwater jacket to keep reactor temperature at 35 1C. In order to get the completelymixing conditions, Reactor A was equipped by a speed adjustable verticalmechanical mixer (Fig. 2). Reactors R1 to R4 were placed in a thermostat controlledwater bath to keep reactor contents at 35C, and agitated by magnetic stirrer.Physical and operational properties of all reactors are outlined in Table 2.

    The Reactor A was operated for 3 sequential feedings: 90 g, 90 g and 270 g VSfeedings were made on 1st, 11th and 36th days, and terminated on 75th day.

    Materials

    Chemical specifications of the samples supplied from a rose oil factory(Gulbirlik) located in Isparta City in Turkey are given in Table 3. Original residuesample was fed into Reactor A as slurry without any pretreatment. On the otherhand, slurry preparations obtained from dried and grinded residues (0.3mm) wereused for Reactors R1 to R4. Seed sludge supplied from Pas abahce Alcohol Factoryin Istanbul, was mixed in 15% volumetrically with the slurry. Just after feedingsubstrate and seed material, gases in the dead volume above the mixed liquor wasswept away by nitrogen gas. Two of four small reactors (R1 and R2) were used tofind out the effect of hydrolysis of wastes on anaerobic decomposition. Hydrolysiswas carried out in 0.1N NaOH, in an autoclave (1 atm, 121C, 2 h in). After

    Table 1. Anaerobic digestion experience data dealing with some waste types.

    Organic substance

    Methane prod.

    (m3 (kg-VS)1)

    Methane content

    ( %) Reference

    Agricultural residues 0.337 58.6 Badawi et al.[2]

    Village waste 62.5 Badawi et al.[2]

    MSW 0.24 59.6 Badawi et al.[2]

    MSW 0.2 Chynoweth et al.[3]

    85%-MSW15% sludge 0.290.23 5753 Szikriszt[4]

    Anaerobic Digestion and Methane Generation Potential of Rose Residue 917

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    Figure 2. Digestion process apparatus. 1. Reactor, 2. Feeding, 3. Outlet, 4. Thermostated

    water bath, 5. pH and temperature probes, 6. Mixer, 7. H2S trap, 8. Gas collection vessel.

    (View this art in color at www.dekker.com.)

    Table 3. Chemical specifications of rose oil residue (dry basis).

    Constituent Unit Value Metal Unit Value

    Water content % 90.5 Mn mgkg1 171

    Volatile solids % 91.3 Cu mgkg1 12.2

    TOC % 50.6 Zn mgkg1 85

    TOC/OM 0.60 Ni mg kg1 4.0

    TKN % 3.7 Na % 0.1

    C/N 13.6 K % 2.4

    pH 5.1 Ca % 1.6

    Tot. P (PO4P) mg kg1 990 Mg % 0.5

    Fe % 0.2

    Table 2. Properties of the reactors used in the experiments.

    Small reactors

    Reactor A R1 R2 R3 R4

    Operating vol. (L) 10 0.4 0.4 0.4 0.4

    Mixer Paddle Stirrer Stirrer Stirrer Stirrer

    Temperature (C) 35 1 35 1 35 1 35 1 35 1Feed manner Sequential

    batch

    Only once

    pouring

    Only once

    pouring

    Only once

    pouring

    Only once

    pouringFeed rate (gVSL1) 9927 11.25 22.5 11.25 22.5

    Pre-treatment Hydrolysis Hydrolysis

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    neutralizing the pH, material was poured into the reactors. The other two of thereactors (R3 and R4) were filled up with no hydrolyzed material.

    Test Chemicals and Analysis

    Analytical grade chemicals in accordance with Standard Methods realized allchemical analysis for Water and Wastewater[5] and Methods of Soil Analysis.[6]

    Heavy metals were determined by atomic absorption spectrometer (UNICAM 929).Alkali and earth alkali metals were determined by flame photometer (Jenway PFP7).Daily fermentation gas production was measured by liquid displacement method. AnOrsat-type gas analyzer measured the composition of decomposition gas.

    EXPERIMENTAL RESULTS

    Reactor A Results

    Before and after each feeding the Reactor A, supernatants of reactor contentswere analyzed and the results obtained were given in Table 4. These data point thatrequired nutrients for an adequate fermentation are exist in the residue of roseflowers, it is more than advised ratio (COD:N:P 400:7:1) by Henze andHarremoes.[7] Ammonia nitrogen being a product of degradation was found aquite low level. Other essential parameters such as pH and alkalinity were adequatefor anaerobic decomposition.

    As can be seen from Fig. 3, methane formation starts and accelerates almostimmediately after feeding, and reaches a maximum rate in a few days. This explainsthat the residue has capabilities of convenient decomposition and readilyacclimation. Decomposition rates decrease drastically through first 5 days andkeep on almost a stable rate after 10th day.

    After each feeding step, total methane formation was determined as 0.19, 0.37,and 0.22L methane (g VSadded)

    1, respectively. Average total methane formationwas found to be 0.25L methane (g VSadded)

    1. This value obtained for the residueshows a close similarity with other types of wastes given in Table 1.

    Average methane content in the decomposition gas was 72%. Figure 4 showschange of methane percent vs. overall operation time. The methane percent obtainedfor the rose residue is found relatively higher than that for organic municipal solidwaste (MSW) having typically 5570% as reported by Braber.[8] It is noted that eachton residue in dry basis gives higher amount of biogas (310m3) than organic MSWbiogas production (100200m3).

    Reactor R1 to R4 Results

    The results of decomposition experiments conducted in Reactor R1 to R4 tocompare the hydrolysis effect on the substrate were illustrated in Figs. 5 and 6. The

    Anaerobic Digestion and Methane Generation Potential of Rose Residue 919

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    gas measurements for about 40 days showed that hydrolyzed material produced 8%

    more biogas than original material. Cumulative methane productions for original

    and hydrolyzed materials were 0.26 and 0.28L methane (g VS)1, respectively. These

    results showed that reactors with original materials (Reactor A, R3 and R4) almost

    0,00

    0,05

    0,10

    0,15

    0,20

    0,25

    0 5 10 15 20 25 30 35 40 45

    Time (day)

    Cum

    ulat

    ive

    met

    hane

    (l (

    g-V

    S)-1

    )

    0,000

    0,005

    0,010

    0,015

    0,020

    0,025

    0,030

    Dai

    ly m

    etha

    ne (

    l (g

    VS

    day)

    -1)

    Figure 3. Daily and cumulative methane production in step 3 for Reactor A. s Cumulative

    methane; ^ Daily methane.

    50

    60

    70

    80

    90

    100

    0 10 20 30 40 50 60 70 80

    Met

    hane

    (%

    )

    Time (day)

    FeedingFeeding

    Figure 4. Methane percent in decomposition gas of Reactor A.

    Table 4. Initial and final parameters for each step in Reactor A.

    Feeding step pH

    Alkalinity

    (mgL1)

    COD

    (mgL1)

    TKN

    (mgL1)

    NH3-N

    (mgL1)

    P

    (mgL1)

    1st Initial 7.4 1650 2950 390 275 41

    Final 7.1 1860 1010 358 265 34

    2nd Initial 7.2 2100 3200 487 320 43

    Final 7.1 2200 1800 473 310 35

    3rd Initial 7.3 2200 6500 415

    Final 7.2 2250 4350 410

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    produced same amount of methane values. However, contents in R1 and R2Reactors with hydrolyzed material produced a bit more methane in comparison withother reactors with original materials. As it can be seen from Fig. 6, methaneproduction increased with decreasing organic loading rate.

    Kinetic Analysis

    Anaerobic digestion is a bacterial fermentation process and essentially its kineticreflects growth of bacterial species. In this study the experimental results wereanalyzed for kinetic models given below.

    0

    0,02

    0,04

    0,06

    0,08

    0 10 20 30Time (day)

    l CH

    4 ( g

    VS-

    d)-1

    (a)

    00,010,020,030,040,05

    0 10 20 30Time (day)

    l CH

    4 (g

    VS

    -d)-1

    (b)

    Figure 5. Daily methane production: a) hydrolyzed, b) original residues. s R1; i R2.

    0,0

    0,1

    0,2

    0,3

    0,4

    R1 R2 R3 R4 Reactor A

    CH

    4

    (l (

    g V

    S in

    itia

    l)-1

    )

    Figure 6. Methane production of hydrolyzed and original material. X Hydrolyzed; Original.

    Anaerobic Digestion and Methane Generation Potential of Rose Residue 921

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    First-Order Kinetic Model

    Anaerobic digestion is generally described by first-order reaction kinetic:

    Y Ymax 1 ek1t

    1

    in which;

    Y is the methane yield (L CH4 (gVS)1),

    k1 is first-order reaction rate coefficient (day1),

    Ymax is maximum methane yield (L CH4 (gVS)1).

    Chen and Hashimotos Model

    Chen and Hashimotos model is expressed as follows:

    Si

    S0 k

    HRTmax k 12

    where,

    Si: outlet substrate concentration (mgL1),

    S0: inlet substrate concentration (mgL1),

    HRT: hydraulic retention time (days),k: Chen and Hashimoto kinetic constant,max: maximum specific growth rate of microorganisms (day

    1).

    Substrate concentration is measured by means of COD in common. CODremoval is an indicator of biogas production in anaerobic processes:

    Si

    S0 Ymax Y

    Ymax3

    for this reason, Eq. (2) could be expressed, in terms of biogas yields, as follows:

    Y Ymax 1k

    HRTmax k 1

    4

    which can be converted to:

    Ymax

    Ymax Y HRTmax

    k 1 1

    k5

    Ymax/(YmaxY ) against hydraulic retention time will lead to a straight line with theslope max/k and the intercept 1 1/k.

    The critical retention time for when washout takes place the following value:

    tc 1

    max6

    Thus, the shorter this time is, the better the reactor will operate.

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    In order to compare the fitness degree of kinetic equations, the root mean square

    (RMS) of the normalized residuals was calculated by

    RMS

    ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiPYexp Y calc2

    N

    s7

    where; N is number of data points.In Fig. 7, biogas production capability data simulated by means of each model

    was compared to experimental data. Kinetic parameters obtained by using first-

    order model and Chen&Hashimotos model for hydrolyzed and original materials

    are listed in Table 5.The comparisons of models with the data are presented in Fig. 7 and Table 5.

    The experimental results showed that Chen&Hashimotos model is found to be more

    suitable than first-order kinetic for expressing the microbial kinetics of anaerobic

    decomposition of rose residue by taking into consideration the RMS of the

    normalized residuals.

    0,0

    0,1

    0,2

    0,3

    0 10 20 30 40

    Time (day)

    l CH

    4 (

    gVS

    )-1

    R1

    R2

    (a)

    0,0

    0,1

    0,2

    0,3

    0 10 20 30 40

    Time (day)

    l CH

    4 (

    gVS

    )-1

    R3

    R4

    (b)

    Figure 7. Comparison of the theoretical and experimental CH4 production for biochemical

    methane potential experiments: a) hydrolyzed; b) original residues. s R1-Exp.; f R2-Exp.;- - - First order; Chen&Hashimoto.

    Anaerobic Digestion and Methane Generation Potential of Rose Residue 923

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    CONCLUSIONS

    The following conclusions can be drawn from the experimental results: Rose

    residue can be treated under anaerobic conditions, found to be a quite feasible

    method for a possible stabilization process, leading to production of biogas in

    significant amounts. This was succeeded with a seed sludge supplied from an alcohol

    factory in a short acclimation period of only a few days.The pretreatment of the residue was supplied a few more increment on methane

    production in comparison with original residue. Anaerobic methane generation from

    hydrolyzed and original rose residue was found to be 0.28 and 0.26L CH4 (g VS)1,

    respectively. High methane content (average 72%) was observed by anaerobic

    bioconversion of rose residue. Original and hydrolyzed residues have become stable

    in 20 and 10 days at 35C, respectively. Chen & Hashimotos model was moreadequate than first-order kinetic to describe experimental data on methane

    production by anaerobic decomposition of rose residue.

    ACKNOWLEDGMENTS

    The work was supported by Research Fund of Yildiz Technical University

    (Project No: 22-05-02-01).

    REFERENCES

    1. Mata-Alvarez, J.; Mace, S.P.; Llabres, P. Anaerobic digestion of organic solid

    wastes: an overview of research achievements and perspectives. Bioresource

    Technology 2000, 74, 316.

    Table 5. Values of kinetic parameters.

    Loading rate

    (gVSL1)

    Hydrolyzed Original

    11.25 22.5 11.25 22.5

    First order

    k1 0.287 0.274 0.176 0.185

    Ymax 0.289 0.225 0.279 0.214

    RMS 0.018 0.016 0.015 0.012

    Chen&Hashimoto

    max 1.819 1.973 1.044 1.048K 5.200 5.688 5.350 5.271

    tc 0.550 0.507 0.958 0.954

    Ymax 0.325 0.250 0.336 0.260

    RMS 0.016 0.014 0.008 0.007

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    2. Badawi, M.A.; Blanch, F.C.; Wise, D.L.; El-Shinnawi, M.M.; Abo-Elnaga, S.A.;

    El-Shimi, S.A. Anaerobic Composting with Methane Recovery from

    Agricultural and Village Wastes. Proceedings of the Industrial Waste

    Conference, 1991, 727.3. Chynoweth, D.P.; Owens, J.M. Biochemical methane potential of municipal

    solid waste components. Water Science Technology 1993, 27, 114.4. Szikriszt, G. Full Scale Demonstration Plant for Anaerobic Digestion of Sorted

    Municipal Solid Waste; Swedish Environmental Research Institute: Stockholm,

    Sweden, 1992.5. American Public Health Association. Standard Methods for the Examination of

    Waste and Wastewater, 19th Ed; Water Environment Federation: Alexandria,

    VA, 1995.6. Methods of Soil Analysis: Chemical Methods, Part 3; Soil Science Society of

    America, Inc.: Wisconsin, USA, 1996.7. Henze, M.; Harremoes, P. Anaerobic treatment of wastewater in fixed film

    reactorsa literature review. Wat. Sci. Tech. 1983, 15 (89), 101.8. Braber, K. Anaerobic digestion of municipal solid waste: a modern waste

    disposal option on the verge of breakthrough. Biomass and Bioenergy 1995,

    9 (1/5), 365376.

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