PJ BS Bosxiczs so Pakistan Journal of Biological Sciences ANSIez n Network for Scientific Information 308 Lasani Towns Sargodha Road, Faisalabad - PakistanPakistan Joumal of Biological Seienees 7 (8): 1350-1354, 2004 ISSN 1028-8880 ‘© 2004 Asian Network For Slentfie Information. Rice Straw Pulping with Oxide Added Soda-Oxygen-Anthraquinone ‘Ahmet Tutus, ‘than Deniz and “Hudaverdi Eroglu, Department of Forest Industrial Engineering, Faculty of Forestry, Kabramanmaras Suteu Imam University, 46100 Kahramanmaras’Turkey ‘Department of Forest Industral Engineering, Faculty of Forestry. Karadeniz. Technical University, 61080, Trabzon/Turkey "Department of Forest Industrial Engineering, Faculty of Forestry, Zongukdak Karaelmas University, 74100 Bartin /Turkey Abstract: In this study, the effect of oxide added to soda oxygen aniraquinone (SOAQ) pulping process in precipitated onto the pulp of silica in rie stray during pulping was investigated. Oxide added SOAQ pulping. methods was used to increase silica precipitation on pulp by adding 0.5-1.58% metal oxide such as Al,0,, CaO and MgO. As a results of the data obtained, optimum oxide added soda-oxygen-anthraquinone pulping ccanhtion of ie saw were as Follws: Alkali charge en oven dry (o.d) raw material: 158, andaraguinone (AQ) charge (co od raw material: 0.1%, AJ,O, charge (on od raw material: 1.5%, tomperature: 130°C time at max. temperature: 45 min. oxygen pressure: 6 kg em” and liquor to straw ratio: 5/1, Precipitated siliea rates onto pulps were 80.54 and 94.65% for SOAQ and oxide added SOAQ pulping methods, respectively Key words: Rice straw, sil soda-cxyger-anthraquinone, metal oxide, pulp INTRODUCTION Nen-weody fibrous raw materials are the alternative sourees for pulp and paper making in many countries where conventional pulp wood!'s availability is scares Many cereal straws, particularly rice straw, have been ‘wed a8 raw materials for paper production, These raw materials were gradually replueed with wood products after World War Il, However, straw is ill a good souree of raw material in areas where wood availability is extremely limited “The main reasons forthe deoreased use of straw in the paper industry was" using straw pulp in paper machines is harder than using wood pulp. The specific properties of the black liquors resulting, from straw cooking in basic environments, makes them hard to use {n industrial concentration/combustion(generation units ‘These handicaps are primarily duet the presence of large amounts of pentosanes in the pulp and black liquors, which also contain silica, The need to add alkali to reduce or prevent silicate deposits or installa specific devioe toremove silica from the black liquors are factors curently limiting the use of rice o oer cereal straws in paper mills, despite recent widespread progress in the field Most of the non-woody raw materials are cturacerized by high ash an sic content. The ash and Siien content in rice strnw varies between 15-20 and 118% depending on location, species and. ail conction, enpectvely From cereal sts especially rice straw contain substantial proportion of sia where its Tound to be present in two forms -edbered silica which comes Alongurith the raw material ring harvesting, collection the the other form inherent ica whch is present in plat in epithelia el eae sia cel. ‘The silica present in the straw adversely affects such a; the raw material preperation, digesters, brown stock fiers and bleach plant filles, seeing and cleaning ecqupment, chemical recovery system, recasting, tok preperation and paper machine ‘The use of anthraquinone (AQ) in alkaline pulping hus Become ane ofthe mont intensely pursued research topics in recent yeas. Laboratory sities of soda an tot-AQ pulping have found that proces produces cereal straw pulps of inferior strength properties and Ulenchabilty compared with soda-oxygen-AQ pipe” The Toe, open suture and Tow lignin content of cereal straws make it autable to perform sod-enyen- ‘AQ pulping at low temperate and in a shorter ime in ‘Corresponding Author: Dr. Atmmet Tutus, Departnent of Fores Indstial Enginering, Faculy of Foresty, Kahramanmaras Suteu Imam University, 46100 Kaframanmaras Turkey ‘Tek: +90°344 2287666 (Ext. 290) Pax: 490:344 2251442 E-mail: musk edu 1350Pak J. Biol Sei, 7 (8): 1350-1354, 2008 contrast to wood species, Moreover, the lignin of coreal straws are mich more sensible to the action of oxygen and AQ”. Soda pulping, with oxygen and AQ as catalytic additives, iss useful process for production non-wood! pulp. Te appears to give higher yields by stopping the carbohydrate peeling reaction through exidation of the reducing end group to aldonic acid The higher SOAQ pulp yield could be atsibuted to the preservatica of the polvseccharides by tho AQ. The most prominent advantage of AQ is that it els solve the xr problem inkraftmillsItwas also lead to significant reduction in colerin kraft mill effluents” Addition of AQ in soda pulping process increases the screened yield and siliea precipitated on pulp and decreases kappa number and pulp viscosity! With the addition ofmetal oxides such as ALO,,CaO and MaO the reactions take place to produce some well known common filles eg. clay, caleium silicate and tale (Om the other hand, in alkaline processes most of the sili exists as sodium silicate in black liqu!! When examining ash content of oxide added soda-oxygen process under microscope hexagonal clay cnjsals have been observed. The raw material ash was observed to have aan-like structure, whereas oxide added pulps ash was a fine white powder. Fillers inerese optical and printing properties of papers such as brightness, opacity, surface smoothness, ink abseeption and regular burning in cigarette paper ete. With an increas of silica conte in pulp the handshests showed mote rapid rates of water penetration and better image qualities in ink jet printing, The handseets which had higher silica contends ilustated lower sheet dersities”| ‘The development of new technologies and methods for cereal straw pulping isthe only solution to avoid the cuurent inchstrial problems and o put to better use these generally widervalucdl agricultural resowes. 1m this study, soda-cnygerranthraquinone (SOAQ) and oxide added SOAQ method were compared from the viewpoints of silica contents in back liquor and pulps, as ‘well as chemical physical and optical properties of pulps ‘were obtained. MATERIALS AND METHODS ‘The raw material used fortis study was Turkish rice straw (Oryza sativa L., Osmancik) Chemical analyses of rice straw were made acconding tothe TAPP Standant Methoxb!" Fiber propertis were measured with a ‘Vizopat light microscope Rice siraw stalks were cleaned andl eut to length of 6-8 em. Cooking experiments were made in an electically heated laboratory rotary digester of 15 L eapacity and smavirmim pressure of 28 kg om, Al pulps were washed and screened on 018 mm slotted sereen. Sereened plps wore beaten ina valley beater to 20,38 and 50 SR* froonoss levels and handshoots wero made om a Rapid Kothen machine. Physical and optical properties of handsboets were measured according to th TAPPL Standard test methods Int viscosity vals according to SCAN € 16:88" Silica contents of blac liquor and pulps were determined according to TAPPIT 625 em-8S and TAPP! T 244 om-85, respectively leven experiments were pesformed for sod-enygene anthriguinone prooess to determine optimam pulping conditions Nine more experiments were done with oxide added SOAQ based on SOAQ optimum pulping condition. Oxide quantities (ALO, CaO an MgO) were varied a thee levels as (15, Land 5 RESULTS AND DISCUSSION (Chemical composition and fiber properties of rice straw: Table I revealed that average holoeelulose rate of rice straw was 70.85%, Approximately, similar values were found as 720% for Oryza sativa L". Cellulose and lignin content of rice straw are approximately similar to those of Oryza saniva Lin Baypt ‘Tet: Chemica sonpost and ther poperies o we rie {Onzasaivet, CeO sro emal cmon ‘Ave 0 §D.69 Haloshloe nas aloo (at Be) eas Cetose ae Cates a te) 404 Aibceteee $502) Ascetar ate) 3030) Ei 120 iin ee) 1s Pettus 20, a 1400 Sen 1490 Alecot ena alts 332 ‘SaiNvotreaubliy ass twos raat (Cold iley 106 iter lth crm) as kero im 1480, Laren wih) a0 onde wal dee um) be 29 Average ash and silica content of rice straw were determined a8 16.60 and 14.90%, respectively. In a previous study, silica and silicates were reported to be 15-20 and 12-18% for rice straw, respectively!" Aleohol-benzene, 1% NaOH, hot und cold water solubility were found as 3.52, 49.15, 16.24 and 10.65%, respectively. Whereas, solubility in the same solutions 1351Pak J. Biol Sei, 7 (8): 1350-1354, 2008 in the literature were 46, 50.9, 146 and 812% for Orysa sativa. respectively Hligh NaOH solubility rate is due tothe presence of low molecular weight carbobyckates and other alkali soluble matters. Fire length ofrice straw varies betwoon 0.63 and 1.18 mm, average fibre length being © 89 mm. Fire width varies from 12.64 and 17.12 um (Table 1). Effect ofthe pulping conditions on pulp and strength properties of paper sheets Cooking temperature: In the sods-oxyuen- anthraquinone (SOAQ) pulping proves, alkali (NaOH) value, ahracuinone (AQ) value, pulping time and liquor to straw rate were Kept at 15, 0.1%, 45 min and 5/1, respectively. When cooking temperature increased to 110, 130 and 156°C, the effect of temperature at maximum, time on pulp properties and strength properties of sheets produced from rice straw pulps Table 2, Increasing the cooking temperature from 110-150C, while Keeping other pulping. conditions constant has slightly affected soreened yield, silica precipitated on pulps, kappa number and viscosity of ‘pulps. Pulp sontened yield Kappa mumber and pulp viscosity were decreased with increasing the cooking. temperature, hich corresponds to ote alkaline pulping"®. However, there is reduction in kappa number and pulp visoosity duc to the presence of oxygen and AQ. In adiion tot could be assumed thatthe variation in viscosity of the rice staw pls were mainly affected by the hemicellulose content of pulps; the high hemicellulose content resulted in the lv viscosity! It can be observed from the Table 2, highest silica precipitation was SOAQ pulping with 84 56% Whereas, ‘maximum silica precipitation values were 36 30and800% for soda-AQ and soda-oxygen processes, respectively Genorlly, it was observed that siliea precipitation rntex were increased with te inereasing cooking temperature From physical ancl optical properties of SOAQ, breaking Jength and burst index are decreased by increasing pulping temperature, but, tear index inereased slightly ‘The results showed that, highest physical properties were obtained by sode-anthraguinone provess because of the protective effect of anthraquinone on carbohycrate fraction. However, addition of AQ to the soda-onygen process was resulted in improved physical properties such in breaking length, tear inde and burst index. With the addition of AQ to the cooking liquor reduces the cooking time ane temperature and strength properties of pulps conserved to a large extend compared to oxide added sode-oxygen process. Besides, inoreasing cooking temperature from 110-130°C, {noreased brightness from 46.1 to 47196 elrepho Cooking time: In Table 2, alkali (NaOH) valve, anthraquinone (AQ) value, pulping. temperature and Tiquor to straw rate were kept at 15, 0.1%, 130°C and Si, respoctvely. Table 2 shows the effect of eooking time on screened yield, siliea contenis, kappa number and viscosity of pulps. Generally, prolonged cooking time results in higher delignification rate. However, te most convenient cooking time was 30 min. especially for higher pulp yield. On the ether hand, the lowest physical properties are obtained by soda-oxygen pulping, because ofthe degradation effect of xy! ‘When ineveased reaction time to 30, 45 and 60 min, while keeping other pulping conditions constant has slightly affected screened yield, siliea precipitated on pops, Kappa mumber and viacosity of pulps. Pulp soreened yield, kappa number and pulp viscosity were decreased with increasing cooking time. Wheres, silica precipitation rates were inereased with the increasing cooking tine. creasing cooking time from 30 1045 and 1060 min increased" of silica precipitated on pulps from 7798 to 82.89 and to 84.56% and decreased sereened yield from 52.36 to $0.05 and to 48.74% (Table 2) Meanwhile the kappa munber and viscosity of pulps decreased from 19.05 to 18.90 and to 17.14 and fom 673 {0.634 and to 598 om? g” (Table 2), respectively Table 2 shows the effect of cooking time on strength properties of handkbeets, The pulps were beaten to S03 SR° fieeness levels. Regular slightly ‘noroase of breaking length with the inerease of time from 59210617 andto 601 km. (cooking no: 7, 8, 9 Meanwhile, burst index reached maximum value at 30 cooking minutes (390 k Pa mg”), In addition, increasing cooking time from 30 to 60 caused a decrease in teat index from 4.24 103.65 mN m* g~. ‘Acoording to Table 3, in oxide added SOAQ palpi, method, 94.65% silica content is cbtained when ALLO, used. Whereas, maximum silica precipitation value was 80.54% for SOAQ process. Generally, it has been ‘observed that silien precipitation rates were inereased with the increasing addition level of omide. Dut, precipitation mites aro not sufficient for soda and soda-anthraquinone processes" On the other hand, ‘maximum silica precipitation rate was obtained by SOAQ pulping process when 1.5% ALO, aed. ‘When examining Table 3, exe addition, induced a slight decrease in physical properties for all prooesses which is nonnally expected when Filler used. Brightness of oxide added SOAQ pulps are about 3 to 5 points higher than those of SOAQ pulps, Oxide added SOAQ pulps physical (breaking length, tear index and burst index values) properties are slightly less dun dat of SOAQ pulps. In addition, oxide added SOAQ pulps give higher optical properties (brightness) than SOAQ pulps. 1352eset ‘ole2 Chania psc cpl pein le a pulp of ode anima ie tr gue a 5085 Papin cndtes erm Silky Sila Soa'ea Pup Breing Bast AQ Presire Scremed Black peesiated slack yecipiatel Kappa Wsstyletth ipdee__TearindexBihness ooking Na gen) _yiedieo_quepH empapso Nigueto_eopalps —matber _temeg) in) Pune go} mine) Cs Bagh) 2 uo 4s 5335 11901182 308 33 020A. an 461 4 wo Mt Sim tens 4a 16 ta 494 488 5 Bo 4 a) 8 ams 300 2 as GS a eceeeecenaeeea: 524 106? 1882 Soe os 3298 34838. 5 1 LSS SBS 58 10 Giceecameaesac: 4625 10001192 258 oat so 140. 485 483 ‘Tole: Cheial pyc opi arp sien as np of wie ae acceso ice sa pp at 03 Se ‘id ae ‘Sli Silent Svat ala Pulp a Sean) Block prevpted ck" peeiited Kipyo viosly Broking BuntindesTearindes—vighnee Coking. AKO,H) COC) MeOH yielded Ligue pl enplpss) lunes) copa mnter_Cog) teh an) Pung) (atu ge) CxFgh) 1 as si 1018 20 nr er 6x 347 an 485 2 ' sao ‘39% 14s S02 RIS 386 Sh 4 os soe 108 36s 23 © 63 30 Ro. 5 1 oe ‘398 2 Mal Se 62D 37683 a os 4904 10.0 287 204 ot 630 240 404 414 *TRDHE 15% AGO tape 150-Cime 4 mings cy Pe OH and igure ar te: ae cons a ‘Tile Oqiman pulping prperics oSOAQ and oid ed SOAQ pups in $083 ripe Serene ssof ice Kippa Pup Breiner Ter Brie proce peo pepe npulpe — rmber eraty (os) tet Indes pans) decd) sep) SoAQ pres 230 ss 18 oo as 3a a a4 Orie ated SOAQywre: 4914 tes 30s ot so su 30 sul 0 SE-0SE1 :00) L "PS TOE TLPale Biol Soi, 7 (8): 1350-1384, 2004 Increasing cooking temperature and time had a tenlency to inerease silica content of pulp for both SOAQ and oxide added SOAQ pulping, (Oxide added SOAQ paling delignification rate was found toe much more rapid than SOAQ pallping. Shorter cooking time is preferable because of Iess_fitne degradation, its advantages in enesgy saving for the ‘convenience of continous pulping operation, It is interesting to note that brighiness values of ALO, added soda-oxygen-anthraquinone pallps inereased from 48.5 t0 50.1 and 52.4% elrepho (Table 3). This can be casily attributed to the filling action of slien precipitation fs clay on pulps. In fact, when visually observing, raw ‘material aah has sand like struenare, whereas oxide added pulp aah has pure and white powder structure, ‘The same observation can he made for soda and sodaanthraquinone methods, but to a lesser extent because of lower precipitation rate. It ean be easily ‘concluded that oxide added soda-oxygen pulping, beside its other advantages such as environmental clean less and high brightness, largely contributes to the solution of silica problems, tis possible to define an optimum set of parameters ‘of SOAQ (cooking nor 5, Table 2) and oxide added SOAQ (Cooking no: 3 in Table 3) pulping of rice straw and pulp physical and optical properties as indicated in Table 4 tis clear seen that from Table 4 that highest % of silica precipitated on pulpe and brightness are obtained by exide added SOAQ method. Other properties of exide added SOAQ pulps slightly less than SOAQ pulps. ‘Consequently, by using oxide added SOAQ pulping jn straw pulping, the following advantages will be ‘obtained: © Pulp screened yield, kappa oumber and pulp ‘viscosity are decreased with increasing cooking tte and temperature, © Amaddition of AQ to the cooking liquor reduces the ‘cooking time and temperature to reach the desired degree of delignification, Pulp yield and physical [properties of paper are improved on addition of AQ to the sodi-oxygen cooking liquor, © An adkltion of oxygen and metal oxides such as ALO, CaO and MgO to the cooking situation is ‘remarkably increased precipitated silica onto pul. © Higher black liquor concentration is obtained and ‘additional fuel-oil requirement diminished Finally, it can be stated that oxide addition to the SOAQ rice straw pulping process may be economically beneficial due to silica precipitation onto pulp increase ‘and slight stength improvement 1354 REFERENCES Fineman, 1, L. Wagherg X.Zhso, S. Kuang and FN. Li, 1988, Straw Pulp asa Raw Matorial for Oftt Papor-Problams and Solutions. Proegedings of the ‘Conference of Inte. Non Wood Fib. Pu. Pape, Being (Chin), pp: 618-627, Kulkarni, AG, RM, Mathur and A. Panda, 1989. Nsture ‘of Spent Liquors from Pulping of Non-wood Fibrous Raw Material. Teppi Proceedings of the Conference of Inter, Sym on Wood and Pul. Chem, Raleigh (USA), pp. 485-92 Pedersen, SV, 1989, Chemical Recovery. Tappi Prooeedng ofthe Conference, awa (Cand), pp 19-22 Jeyasingam, J.T. 1986, Problems facing non- wood pulp ‘and paper mils de tothe presence of sca, Rat material preparation to the finishing of paper, Non-woed Plant Fier Pulping Prog. Report No 16, TAPP! press, Adan ‘Tums, A. and H.Proplu, 203. A practical solution tothe silica problem instaw pulping, Appia 56: 111-115, Eroplu, H, 1987. Sodu-oxygen-antlraguinone pulping of wheat stv, Non-voed Plant Fibre Pulping Progress Repeet No: 17, Houston, TAPPL press. Springer M.A. 1993. 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Utilization of anmnal plants and ‘great residues for the production of pulp and paper, Non-wood Plant Fiter Pulping Progtess Report No.19 "TAPPL Press, Atlanta, p: 42-70, Jeyasingam, T.1, 1986, Problems facing non wood pulp ‘and paper mills dus to the presence of silica: From raw ‘material prepaation to the Snshing of paper, Non-wood Plant Fire Pulping Progsess Report No. 16, Heaston, Emset, AJ, Y. Pousd nd TF. Clark, 1960, Rice straw for Dleuchod pipers. Tapp J, 43: 49-53 Ero@lu, Hand |. Deniz, 1993, Predesiicted whet stuw With NsOH, Dus Papier, 47: 643