11
Indian Journal of Chemical Technology Vol. 17, January 2010, pp. 60-70 Bio-soda pulping of lignocellulosic residues of palma rosa grass: An attempt towards energy conversion Dharm Dutt * , C H Tyagi , S Agnihotri, A Kumar & Siddarth 1 Department of Paper Technology, Indian Institute of Technology Roorkee, Saharanpur Campus, Saharanpur, India 1 National Institute of Fashion Technology, Bangalore 560 071, India Email: [email protected] Received 8 May 2009; revised 14 September 2009 The lignocellulosic residues (LCR) of Cymbopogon martini after steam distillation had 13.6% lignin, 74.4% holocellulose and 25.4% pentosan. Phanerochaete chrysosporium degraded 30.11% of lignin, 62.25% of pentosan and 18.60% of holocellulose of the original value of LCR of C. martini after 28 days at 40°C in solid-state culture with a higher in vitro dry matter digestibility. The steam distillation and Phanerocheate chrysosporium treatment of LCR of C. martini abated the mass transfer problem and facilitated the faster penetration of cooking liquor. The pulp yield was mitigated by 0.63% with insignificant decrease in kappa number and 0.81% with 1.32 units decrease in kappa number for bio-soda and bio-soda-O 2 pulping processes respectively when cooked at 11% alkali dose compared to soda pulping (active alkali14%) with a saving of 3% cooking chemicals. Keywords: Cymbopogon martini, Lignocellulosic residues, Phanerochaete chrysosporium, Biodelignification, Soda pulping World demand for paper and paperboard is expected to grow from the current production of 300 million tonnes to over 420 million tonnes by the year 2010 with an average growth rate of 2.8% per annum 1 . In India, the annual current production gap is 0.7 million tonne and will become 1.5 times greater during 2010- 15. In India, forest and woodlands occupy around 20%, agricultural land 50% and uncultivated, non- agricultural and barren land 30% respectively of a total land area of 328.8 million ha 2 . Many fast growing annual and perennial plants have been identified, cultivated and studied for their suitability for pulp and paper manufacture 3 . Cymbopogon martini (commonly known as palma rosa) is used to extract essential oils of commercial importance by steam distillation method and LCR of C. martini is mainly used for land filling and a fraction is burnt to generate steam for the stripping; the rest is left in the fields where natural biodegradation occurs 4 . This hitherto unexploited source of fibres from C. martini was successfully utilized for the production of bleachable grade pulp 5 . The openness of the pile, the heterogeneity of the tissues and the vast exposed surface area favour the growth and colonization of a multitude of micro organisms 6 in the waste material. The present study has been undertaken to study the bio-delignification of LCR of C. martini with P. chrysosporium followed by soda delignification in order to produce bleachable grade pulp. Experimental Procedure Raw materials collection Cymbopogon martini was collected from Punjab Agriculture University Jalandhar (India) at the start of the rainy season. The freshly cut C. martini was hand- chopped and sun-dried for 20 days and then palma rosa oil was extracted by steam distillation in crude iron direct-fired stills having false bottom, over which the C. martini is charged. The LCR after extraction were air dried and kept in ventilated polythene bags. Morphology and proximate chemical analysis In order to get more accurate results, three samples from each stalk/branch were taken at 10% (base), 50% (middle) and 90% (top) of its height/length respectively, an approach similar to that followed by Dutt 7 . For fibre length determination, small slivers were obtained and macerated with 10 mL of 67% HNO 3 and boiled in a water bath (100±2°C) for 10 min 8 . The slivers were then washed, placed in small flasks with 50 mL distilled water and the fibre bundles were separated into individual fibres using a

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  • Indian Journal of Chemical Technology

    Vol. 17, January 2010, pp. 60-70

    Bio-soda pulping of lignocellulosic residues of palma rosa grass: An attempt

    towards energy conversion

    Dharm Dutt*, C H Tyagi, S Agnihotri, A Kumar & Siddarth

    1

    Department of Paper Technology, Indian Institute of Technology Roorkee, Saharanpur Campus, Saharanpur, India

    1National Institute of Fashion Technology, Bangalore 560 071, India

    Email: [email protected]

    Received 8 May 2009; revised 14 September 2009

    The lignocellulosic residues (LCR) of Cymbopogon martini after steam distillation had 13.6% lignin, 74.4%

    holocellulose and 25.4% pentosan. Phanerochaete chrysosporium degraded 30.11% of lignin, 62.25% of pentosan and

    18.60% of holocellulose of the original value of LCR of C. martini after 28 days at 40°C in solid-state culture with a higher

    in vitro dry matter digestibility. The steam distillation and Phanerocheate chrysosporium treatment of LCR of C. martini

    abated the mass transfer problem and facilitated the faster penetration of cooking liquor. The pulp yield was mitigated by

    0.63% with insignificant decrease in kappa number and 0.81% with 1.32 units decrease in kappa number for bio-soda and

    bio-soda-O2 pulping processes respectively when cooked at 11% alkali dose compared to soda pulping (active alkali14%)

    with a saving of 3% cooking chemicals.

    Keywords: Cymbopogon martini, Lignocellulosic residues, Phanerochaete chrysosporium, Biodelignification, Soda

    pulping

    World demand for paper and paperboard is expected

    to grow from the current production of 300 million

    tonnes to over 420 million tonnes by the year 2010

    with an average growth rate of 2.8% per annum1. In

    India, the annual current production gap is 0.7 million

    tonne and will become 1.5 times greater during 2010-

    15. In India, forest and woodlands occupy around

    20%, agricultural land 50% and uncultivated, non-

    agricultural and barren land 30% respectively of a

    total land area of 328.8 million ha2. Many fast

    growing annual and perennial plants have been

    identified, cultivated and studied for their suitability

    for pulp and paper manufacture3. Cymbopogon

    martini (commonly known as palma rosa) is used to

    extract essential oils of commercial importance by

    steam distillation method and LCR of C. martini is

    mainly used for land filling and a fraction is burnt to

    generate steam for the stripping; the rest is left in the

    fields where natural biodegradation occurs4. This

    hitherto unexploited source of fibres from C. martini

    was successfully utilized for the production of

    bleachable grade pulp5. The openness of the pile, the

    heterogeneity of the tissues and the vast exposed

    surface area favour the growth and colonization of a

    multitude of micro organisms6

    in the waste material.

    The present study has been undertaken to study the

    bio-delignification of LCR of C. martini with

    P. chrysosporium followed by soda delignification in

    order to produce bleachable grade pulp.

    Experimental Procedure

    Raw materials collection

    Cymbopogon martini was collected from Punjab

    Agriculture University Jalandhar (India) at the start of

    the rainy season. The freshly cut C. martini was hand-

    chopped and sun-dried for 20 days and then palma

    rosa oil was extracted by steam distillation in crude

    iron direct-fired stills having false bottom, over which

    the C. martini is charged. The LCR after extraction

    were air dried and kept in ventilated polythene bags.

    Morphology and proximate chemical analysis

    In order to get more accurate results, three samples

    from each stalk/branch were taken at 10% (base),

    50% (middle) and 90% (top) of its height/length

    respectively, an approach similar to that followed by

    Dutt7. For fibre length determination, small slivers

    were obtained and macerated with 10 mL of 67%

    HNO3 and boiled in a water bath (100±2°C) for 10

    min8. The slivers were then washed, placed in small

    flasks with 50 mL distilled water and the fibre

    bundles were separated into individual fibres using a

  • DUTT et al.: BIO-SODA PULPING OF LIGNOCELLULOSIC RESIDUE OF PALM ROSA GRASS

    61

    small mixer with a plastic end to avoid fibre breaking.

    The macerated fibre suspension was finally placed on

    a slide (standard, 7.5 × 2.5 cm) by means of a

    medicine dropper9. For fibre diameter, lumen

    diameter and cell wall thickness determination, cross-

    sections were obtained from the same height/length as

    mentioned above and were stained with 1:1 aniline

    sulphate–glycerine mixture to enhance cell wall

    visibility (cell walls retain a characteristic yellowish

    colour). All fibre samples were viewed under a

    calibrated microscope; a total of 25 randomly chosen

    fibres were measured from each sample for a total of

    75 fibre measurements from each stalk/branch. Three

    derived values were also calculated using fibre

    dimensions: slenderness ratio (fibre length/fibre

    diameter), flexibility coefficient (lumen diameter/fibre

    diameter) ×100 and Runkel ratio (2×fibre cell wall

    thickness/lumen diameter)10,8

    . The hand-chopped

    culms of C. martini before and after steam distillation

    were milled separately into powder in a laboratory

    Wiley mill and a fraction passing through −48 mesh

    size but retained on +80 mesh size was used for

    analysis of water solubility (T 207 cm-99), 1% NaOH

    solubility (T 212 om−98), alcohol-benzene solubility

    (T 204 cm−97), holocellulose (T 249 cm−00), lignin

    (T 222 om−02), ash (T 211 om−93) and pentosan

    (T 223−cm-01) content as per Tappi Standard Test

    methods: 2000.

    Inoculum preparation

    P. chrysosporium was isolated from decaying

    wood and confirmed as xylanase producer when

    cultured on xylan rich culture medium. The fungus

    was sub-cultured on medium having 2% wheat bran

    and 2% agar (w/v) without any nutrient salt at 40°C

    for 4-6 days and maintained at 4°C until used.

    Streptopenicilline (185 µg/mL) was aseptically added

    to check any bacterial growth. The inoculum was

    produced under submerged fermentation in a medium

    having 2% wheat bran powder and 40 mL of nutrient

    salt solution having KH2PO4, 1.5; NH4Cl, 4; MgSO4 0.5; KCl, 0.5 and yeast extract 1 g/L in distilled water

    with trace elements solution (0.04 mL/L) having

    FeSO4.7H2O, 200; ZnSO4.7H2O, 180 and

    MnSO4.7H2O, 20 µg/L. Desired pH of the solution

    was adjusted with 1.0 N NaOH /H2SO4. Two discs

    of 8 mm diameter from 5 day old culture of

    P. chrysosporium were aseptically inoculated in each

    of the flasks. These flasks were incubated at 100 rpm

    and 40°C and harvested after 8th day. The contents

    were centrifuged at 15000 x g (Sigma centrifuge:

    model 2K15) and 4°C and the filtrate was analyzed

    for xylanases and CMCase activity11

    , and lignin

    peroxidase activity12

    . In order to observe the growth

    of fungus, the pellets were re-suspended in 10 mL of

    1 M NaOH and boiled for 20 min12

    . 1 mL of

    homogeneous solution was taken and centrifuged at

    10,000 x g for 2 min. The protein concentration of the

    cleared supernatant was determined13

    . Incubation

    period, pH, and temperature with different carbon

    sources (glucose/lactose) and complex nitrogen

    sources (corn steep liquor/yeast extract) were

    optimized to get maximum biomass production with

    higher enzyme activity.

    Bio-pulping

    The LCR of C. martini was chopped into small

    pieces of 2 to 2.5 cm long. Erlenmeyer flasks of

    capacity 2 L each were filled with 50 g of LCR of

    C. martini (oven dry weight basis). In each flask 100

    mL of distilled water was added and autoclaved at 15

    Pa for 15 min14

    . Inoculum prepared under optimized

    conditions was inoculated aseptically in each flask.

    The flasks were incubated at 400C and were examined

    everyday to check the fungal growth. The fungal

    treated LCR of C. martini was analyzed for lignin

    (T 222 om−02), pentosans (T 223−cm-01),

    holocellulose (T 249 cm−00) and α-cellulose (T 203

    cm-99) as per Tappi Standard Test Methods: 2000. Chemical pulping

    The LCR of C. martini before and after treatment

    with P. chrysosporium were cooked in WEVERK

    rotary electrically heated digester of capacity 0.02 m3

    by soda pulping process. The effect of AQ and O2 on

    kappa number and screened pulp yield during soda

    pulping was also studied. After completion of

    cooking, the pulp was washed on a laboratory flat

    stationary screen having 300 mesh wire bottom for

    the removal of residual cooking chemicals. The pulp

    was disintegrated and screened through WEVERK

    vibratory flat screen with 0.15 mm slits and the

    screened pulp was washed, pressed and crumbled.

    The pulp was evaluated for kappa number (T 236 cm-

    85), screened pulp yield and screening rejects as

    per Tappi Standard Test Methods: 2000.

    P. chrysosporium treated C. martini was cooked by

    soda and soda-O2 cooking processes and comparisons

    of screened pulp yield, screening rejects and kappa

    number of LCR of C. martini with soda and alkali-O2 pulping processes was done.

  • INDIAN J. CHEM. TECHNOL., JANUARY 2010

    62

    Results and Discussion Morphological characteristics reveal that the

    average fibre length of C. martini is 0.96 mm, while

    fibre diameter, cell wall thickness, and lumen

    diameter are 30.53, 6.42 and 20.58 µm, respectively,

    which resemble to those of hard woods15

    (Table 1).

    The fibres are tapered at one end and cell cavity is

    wide and nearly empty. The steam distillation process

    reduces the hot water soluble from 15.90 to 0.1%

    which indicates that palma rosa oil is leached out

    along with extraneous components, such as inorganic

    compounds, tannins, gums, sugars, colouring matters

    and starches. The alcohol-benzene soluble, which is

    5.4%, remains unaffected after steam distillation. The

    reduction in 1% NaOH soluble from 37.9 to 27.5% is

    attributed due to the leaching of water soluble

    materials along with some low-molecular-weight

    carbohydrates, like starches etc. C. martini contains

    13.67% lignin, 25.38% pentosan and 74.51%

    holocellulose. It indicates that C. martini produces

    high pulp yield at milder cooking conditions. The

    silica contents are slightly higher i.e. 2.2%.

    Figure 1 reveals the impact of incubation period on

    protein concentration and xylanase and peroxidase

    activities of P. chrysosporium using 2% wheat bran,

    NSS 10 mL, pH 6.5 and temperature 400C. On wheat

    bran, the production of xylanase by P. chrysosporium

    increases with increasing incubation period and the

    maximum xylanase activity of 21.79 IU/mL is

    observed on 8th day of incubation while peroxidase

    activity (0.32 IU/mL) increases with increasing the

    incubation period up to 14th day of incubation

    (Fig. 1A). It is because the ligninolytic activity

    induces in the secondary phase of growth when the

    culture medium is deficient of carbon, sulphur and

    Fig. 1A−Optimzation of incubation period

    Table 1―Morphological characteristics and chemical

    composition of C. martini

    Morphological characteristics

    Parameters Test values

    Fibre length (L) (mm) 0.96±0.07

    Fibre width (D) (µm) 30.53± 2.6

    Lumen diameter (d) (µm) 20.58±2.9

    Cell wall thickness (w) (µm) 6.42± 0.6

    Flexibility coefficient, [(d/D) x 100] 67.4

    Slenderness ratio (L/D) 31.4

    Runkel ratio (2 w/d) 0.6

    Chemical composition

    Before steam

    distillation

    After steam

    distillation

    Cold water soluble (%) 12.2±0.1 —

    Hot water soluble (%) 15.9±.08 0.1±0.02

    Alcohol-benzene soluble (%) 5.4±.06 5.3±.003

    1% NaOH soluble (%) 37.9±.05 27.5±.004

    Lignin (%) 13.67±.07 13.5±0.06

    Pentosan (%) 25.4±.09 25.38±0.07

    Holocellulose (%) 74.51±0.1 74.4±0.02

    Ash (%) 4.5±0.04 4.4±0.03

    Silica (%) 2.2±0.02 2.2±0.01 ±refers to standard deviation

  • DUTT et al.: BIO-SODA PULPING OF LIGNOCELLULOSIC RESIDUE OF PALM ROSA GRASS

    63

    nitrogen16

    . Both protein biomass (0.303 mg/mL) as

    well as xylanase production start to decline after 12th

    day of incubation. It suggests that the enzyme

    production is dependent on biomass but only during

    exponential phase of growth of fungi. On onset of

    death phase, the protein biomass as well as the

    enzyme activity decreases17

    . Thus, their harvesting

    time must be correlated to their production25

    .

    Metabolic enzymes like, proteases and

    transglycosidases might also affect xylanase yield26

    .

    Figure 1B reveals that variation in pH from 5.0-7.0,

    and keeping other factors same as described above,

    enhances the enzyme production and the optimum

    enzyme activity of 24.12 IU/mL is observed at

    pH 6.5. The maximum protein concentration of

    0.38 mg/mL and peroxidase activity 0.33 IU/mL is

    observed at pH 6.0.The peroxidase activity is

    observed higher in acidic than alkaline pH. However,

    the mycelial biomass is slightly less at pH 7.5, but the

    xylanase activity is quite comparable to the optimum

    value. There are two pH optima, one at 6.5 and other

    at 7.5. It is known that pH dependent unavailability of

    inorganic elements affects the production of

    enzyme18,19

    . It may also be possible that these may be

    multiple isoforms of the enzyme, which are produced

    at different pH optima with different activities. The

    pH exerts a regulatory effect on production of both

    primary and secondary metabolites20

    . Any enzyme

    mediated reaction is affected by culture pH which

    might cause changes in productivity. Structures like,

    membranes in contact with external environment, can

    also undergo chemical changes in response to pH.

    Microorganisms may need to adapt their function to

    cope up with pH change. If this change is too abrupt,

    response of microbes might lag behind or overshoot.

    The pH may also determine solubility of some media

    components. Thus, pH change might cause some

    micronutrients to precipitate and impossible to

    assimilate21

    .

    At 25°C, P. chrysosporium yields the lowest

    enzyme activity, which increases with increasing

    temperature up to 400C and thereafter, it decreases to

    half at 50°C (Fig. 2). It may be possible due to lower

    transport of substrate across the cells at lower

    temperature causing lower yield of the product. At

    higher temperature, maintenance energy requirement

    of cellular growth is high due to thermal denaturation

    of enzymes of the metabolic pathway resulting in

    lower production of the metabolites22

    . Optimum

    xylanase activity of P. chrysosporium (23.14 IU/mL

    at 40°C) suggests that the fungus is slightly

    thermophilic and of commercial use because the

    industrialists prefer thermophilic microorganisms for

    the production of the biocatalysts as the cost of

    maintenance at higher temperature is cheaper than

    that at lower temperature. The maximum supernatant

    protein concentration at 40°C is 0.38 mg/mL and

    peroxidase activity is 0.28 IU/mL.

    Fig. 1B−Optimzation of initial pH

  • INDIAN J. CHEM. TECHNOL., JANUARY 2010

    64

    The effect of different carbon sources i.e. glucose

    and lactose on protein concentration and xylanase and

    peroxidase activities of P. chrysosporium using 2%

    wheat bran, 10 mL NSS, 15 mL yeast extract, pH 6.5

    and incubation period and temperature 8 days and

    40°C respectively has been studied. Glucose is found

    to be the better additional carbon source for biomass

    production (Fig. 3A). The possible explanation is that

    xylan is a complex substrate and addition of glucose

    as a carbon source may facilitate the initial growth of

    the fungus, which may then utilize bulk of wheat bran

    easily. In case of lactose (Fig. 3B), enzyme activity

    Fig. 2−Optimization of incubation temperature

    Fig. 3 A−Effect of glucose concentration on protein concentartion, xylanase and peroxidase activity

  • DUTT et al.: BIO-SODA PULPING OF LIGNOCELLULOSIC RESIDUE OF PALM ROSA GRASS

    65

    and mycelial biomass is lesser compared to glucose. It

    suggests that the fungus preferably consume the

    simplest carbon source (glucose) than lactose. Lactose

    is reported a poor source of carbon for the growth of

    fungi23

    . In both the cases, additional supply of

    glucose/lactose as carbon source shows adverse effect

    on the production of xylanases. The concentration of

    glucose (>1.0 g/L) acts as a repressor23,24

    . Xylanase

    repression in the presence of easily metabolizable

    carbon sources in the growth medium, suggested that

    enzyme synthesis is controlled by transition state

    regulators and catabolite repression25

    . Xylanase

    induction, in general, is a complex phenomenon and

    the level of response to an inducer varies with the

    organisms26

    .

    Corn steep liquor is better complex nitrogen source

    (29.53 IU/mL) than yeast extract (22.49 IU/mL) for

    mycelial biomass and xylanase production under

    submerged fermentation condition (Fig 4 A, B). The

    additional supply of corn steep liquor/yeast extract in

    the medium shows positive effect on xylanase

    production and mycelial biomass but peroxidase

    activity decreases in presence of additional supply of

    nitrogen sources. It is also reported by several

    Fig. 3 B−Effect of lactose concentration on protein concentartion, xylanase and peroxidase activity

    Fig. 4A−Effect of yeast extract concentration on protein concentartion, xylanase and peroxidase activity

  • INDIAN J. CHEM. TECHNOL., JANUARY 2010

    66

    researchers that, nitrogen compounds act as a

    repressor of ligninolytic activity27

    . It suggests that

    corn steep liquor/yeast extract is consumed by fungus

    in limited amount and is probably utilized only in

    early stage of growth because in lag phase, fungus

    synthesizes its protein and nucleic acid components

    for growth and development28,23,24

    . Bakri et al.23

    reported that yeast extract was the best source for

    xylanase production by Penicillium canescens while

    Technapun et al.29

    reported that yeast extract had

    negative effect on xylanase production in

    Streptomyces species. Thus, the present investigation

    supports the earlier observations that additional

    supply of organic nitrogen enhances the enzyme

    production to certain extent. Figure 5A reveals that initially fungus attacks the

    pentosan followed by holocellulose and α-celluloses

    respectively, and lignin is utilized by the fungus only

    in final stage of bio-pulping on 18th day of incubation.

    As lignin is not degraded due to primary growth of P.

    chrysosporium, so it does not induce ligninolytic

    activity5.

    Fig. 4B−Effect of corn steep liquor concentration on protein concentartion, xylanase and peroxidase activity

    Fig. 5A−Effect of incubation period on bio-chemical composition of C. martini after treatment with P. chrysosporium

  • DUTT et al.: BIO-SODA PULPING OF LIGNOCELLULOSIC RESIDUE OF PALM ROSA GRASS

    67

    Figure 5B reveals that pentosan, holocellulose and

    α-celluloses degrade fast compared to lignin beyond

    incubation temperature of 40°C. Therefore, 40°C may

    be considered as an optimum temperature for

    biopulping of C. martini with P. chrysosporium. The

    favourable tropical conditions, the openness of the

    pile, the heterogeneity of the tissues and the vast

    exposed surface area favour the growth and

    colonization of the fungus on the distilled waste of

    C. martini. Therefore, it requires less incubation

    period compared to softwood as well as for

    hardwood30

    . In 28 days at 40°C, P. chrysosporium

    degrades 30.11% of lignin, 62.25% of pentosan and

    18.60% of holocellulose from LCR of C. martini;tThe

    ranges of experimental weight loss observed for

    Cymbopogon citratus, 8-42% and for Cymbopogon

    winterianus are 1.6 to 37%31

    . Antai and Crawford30

    have shown, for instance, that in 10 weeks at 28°C,

    C. versicolor degraded more dry matter, 63.8% in

    grasses than in hardwoods or softwoods (about 40%).

    Somewhat higher weight losses have been reported

    for cereal straws and some specific white-rot32-35

    .

    Table 2 reveals the experimental conditions and

    results of soda pulping of LCR of C. martini at

    different alkali doses i.e. 10 to 18% (as Na2O) while

    keeping other conditions constant as mentioned. The

    results indicate that the screened pulp yield increases

    with increasing alkali dose from 10 to 14% when

    C. martini is delignified at H-Factor 553.21. Further,

    on increasing alkali doses screened pulp yield

    decreases from 44.73 to 42.8%, whereas, kappa

    number drops from 22.12 to 20.6 and thereafter

    insignificant decrease is noticed. In the initial stage of

    cooking rapid solublization of bulk of lignin occurs

    and beyond an alkali dose of 14% slow solublization

    of residual lignin occurs. The bulk delignification

    corresponds to the removal of easily assessable lignin

    present in the middle lamella and residual lignin

    corresponds to the removal of lignin present in the

    primary wall, secondary wall layers and inter-

    connection cavities. The delignification of wood in

    alkaline pulping is also associated with the

    solublization of significant amount of hemicelluloses36

    .

    The results of effect of temperature on pulp yield and

    kappa number during soda pulping indicate that the

    screened pulp yield increases from 41.98 to 44.73% up

    to H- factor 553.21 and kappa number drops from

    28.42 to 22.12. Further, on increasing H-factor from

    1212.24 to 3033.98 screened pulp yield drops sharply

    while kappa number decreases slowly. In other words,

    at the transition point, lower pulp lignin contents were

    obtained at 150°C. Beyond a temperature of 150°C,

    degradation of carbohydrates contents occurs due to

    peeling reactions37,38

    . Therefore, it is not sensible to

    cook C. martini beyond a temperature of 150°C. Table

    2 also reveals the effect of cooking time on pulp yield

    and kappa number during soda pulping of LCR of C.

    martini while keeping other variables constant as

    mentioned. The results indicate that the screened pulp

    yield increases from 40.56 to 44.73% up to H- factor

    553.21 and kappa number drops from 32.45 to 22.12.

    Beyond that screened pulp yield drops sharply while

    kappa number remains almost constant. The lignin

    content associated with middle lamella decreases

    Fig. 5B−Effect of incubation temperature on bio-chemical composition of C. martini after treatment with P. chrysosporium

  • INDIAN J. CHEM. TECHNOL., JANUARY 2010

    68

    sharply up to a reaction time of 3 h. It means that the

    bulk delignification phase is over up to this transition

    point and it is not economical to continue pulping

    reaction beyond this particular reaction time. The bulk

    delignification phase is converted into residual

    delignification beyond a reaction time of 3 h at 150°C.

    Table 3 shows the effect of AQ and O2 during soda

    pulping of LCR of C. martini. The addition of 0.1%

    AQ at optimum cooking condition of soda-AQ

    process reduces kappa number by 1.12 units and

    increases pulp yield by 0.72%. Similarly, an O2

    pressure of 5 kg/cm2 improves pulp yield by 1.07%

    and mitigates kappa number by 1.65 units compared

    to soda pulping process. The lignin of C. martini is

    much more susceptible to the action of oxygen and

    results a pulp with higher delignification. There is no

    diffusion problem of dissolved oxygen because of its

    more open and loose structure and low specific

    gravity39

    .

    Figure 6 shows a comparison between soda, bio-

    soda, soda-O2 and bio-soda-O2 pulping processes. The

    pulp yield of bio-soda pulp is slightly less (0.63%)

    due to removal of xylan when cooked at the same

    kappa number as that of soda pulp with a chemical

    savings of 3%. The bio-soda-O2 pulp shows a

    decrease in pulp yield by 0.81% and kappa number

    reduction by 1.32 units with a chemical savings of 3%

    compared to soda-O2 pulp.

    Table 2―Effect of NaOH, cooking temperature and cooking time on pulp characteristics of LCR of C. martini during soda pulping

    aEffect of NaOH dose (%) (as Na2O) Parameters

    12 14 16 18

    Screened pulp yield (%) 43.4±0.3 44.7±0.2 43.6±0.3 42.8±0.3

    Screening rejects (%) 2.8±0.10 1.9±0.15 0.6±0.01 0.3±0.01

    Unscreened pulp yield (%) 46.2±0.4 46.7±0.2 44.3±0.2 43.2±0.2

    Kappa number 26.2±0.2 22.1±0.3 21.5±0.3 20.6±0.4 bEffect of cooking temperature (0C)

    140 150 160 170

    Whole cycle H-factor 223.42 553.21 1212.24 3033.98

    Screened pulp yield (%) 41.98±0.3 44.73±0.2 42.74±0.3 38.88±0.3

    Screening Rejects (%) 3.78±0.15 1.98±0.10 0.98±0.01 0.50±0.01

    Unscreened pulp yield (%) 45.76±0.2 46.71±0.3 43.72±0.3 39.38±0.2

    Kappa number 28.42±0.1 22.12±0.2 21.34±0.3 18.72±0.1 cEffect of cooking time (h)

    2.0 2.5 3.0 3.5

    Whole cycle H-factor 327.96 470.54 553.21 635.69

    Screened pulp yield (%) 40.56±0.3 43.73±0.2 44.73±0.1 40.88±0.2

    Screening rejects (%) 4.78±0.41 2.10±0.10 1.98±0.02 0.62±0.01

    Unscreened pulp yield (%) 45.34±0.3 45.83±0.2 46.96±0.3 41.15±0.1

    Kappa number 32.45±0.10 26.30±0.10 22.12±0.10 19.12±0.15 ±refers to standard deviation.

    aLiquor to raw material ratio 5:1, temperature raising time 1.5 h, max cooking

    temperature 1500C, temperature keeping time 3.0 h and H-factor 553.2

    bLiquor to raw material ratio 5:1, NaOH charged 14% (as Na2O), temperature raising time 1.5 h and temperature keeping time 3.0 h

    cLiquor to raw material ratio 5:1, NaOH charged 14% (as Na2O), temperature raising time 1.5 h and max cooking temperature 1500C

    Table 3―Effect of AQ and O2 pressure on pulp characteristics of

    LCR of C. martini during soda pulping

    AQ dose (%) (o d wood basis) Parameters

    00 0.05 0.10 0.20

    Screened pulp

    yield (%)

    44.73±0.1 45.05±0.1 45.45±0.2 45.12±0.3

    Screening rejects

    (%)

    1.98±0.01 1.07±0.02 1.02±0.01 0.40±.01

    Unscreened pulp

    yield (%)

    46.71±0.2 46.12±0.3 46.47±0.4 45.52±0.3

    Kappa number 22.12±0.1 21.50±0.1 21.00±0.2 18.45±0.2

    O2 pressure ( kgf/cm2)

    00 05 08 10

    Screened pulp

    yield (%)

    44.73±0.2 45.80±0.3 45.30±0.1 44.23±0.1

    Screening rejects

    (%)

    1.98±0.03 1.32±0.01 0.98±0.01 0.50±0.01

    Unscreened pulp

    yield (%)

    46.71±0.2 46.12±.2 46.28±1 44.73±0.2

    Kappa number 22.12±0.1 20.47±0.1 19.23±0.2 18.50±0.1

    ±refers to standard deviation.

    Cooking conditions: Liquor to raw material ratio 5:1, temperature

    raising time 1.5 h, max cooking temperature 1500C, temperature

    keeping time 3.0 h and H-factor 553.2

  • DUTT et al.: BIO-SODA PULPING OF LIGNOCELLULOSIC RESIDUE OF PALM ROSA GRASS

    69

    Conclusions

    Both steam distillation and P. chrysosporium

    treatment makes LCR of C. martini suitable for

    chemical pulping by abating the mass transfer

    problem of O2 and facilitates the faster penetration of

    cooking liquor. Thus, LCR left after steam distillation

    is renewable, alternative and hitherto unexploited

    source of fibers for paper industry. After 28 days at

    40°C, P. chrysosporium degrades lignin, pentosan and

    holocellulose by 30.11, 62.25 and 18.60%

    respectively of the original value of C. martini. The

    optimum pulping conditions for soda pulping are:

    maximum cooking time and temperature 3 h and

    150°C respectively, alkali dose 14 % (as Na2O) and

    liquor to LCR ratio 5:1. The addition of 0.1% AQ

    improves pulp yield by 0.72% and reduces kappa

    number by 1.12 units and an O2 pressure of 5 kg/cm2

    with AQ improves pulp yield by 1.07% and reduces

    kappa number by 1.65 units compared to soda pulp.

    The bio-soda and bio-soda-O2 pulping processes save

    3% alkali compared to soda pulping, when LCR of C.

    martini was cooked to get the same kappa number as

    that of soda pulp. Bio-soda and bio-soda-O2 processes

    mitigate the pulp yield by 0.63 and 0.81% but kappa

    number reduction is 1.32 units for bio-soda-O2

    process.

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