Gas Chromatography Analysis of Resin and Fatty Acids from Laboratory Generated Bleach Plant Effluent

研究论文Gas Chromatography Analysis of Resin and Fatty Acidsfrom Laboratory Generated Bleach Plant EffluentsChhaya Sharma' S. Mohanty2 S. Kumar' N.J. Rao'(1. Department of Paper Technology,lIT-Roorkee,India; 2. Gas Authority of India Ltd.,. Calcutta, India;3. JP Institute,Gunna, India)SUMMARY:Laboratory generated spent bleached liquor from the chlorination, causticextraction stage of mixed wood kraft pulp processing has been analyzed both qualitativelyand quantitatively for various resin & fatty acids by using GC. A number of resin acids,saturated and unsaturated fatty acids, chloro fatty and resin acid have been detected andtheir concentrations are estimated. The results are compared with results on differentagriculture residue/hardwood pulps, which were reported earlier. The concentrations ofvarious compounds detected have also been compared with their reported LCso values.Key words: gas chromatography; resin acid; fatty acid ; bleach efuentChhaya SharmaIT-Roorkee,IndiaCLC number: TS71*3; 0657.7*1 Document code:A Aticle ID: 0254-508X<(2007)05-0029-05chhaya 1964@rediffmail.comThe major pollutant in chlorinationacids in C and E stage effluents formedbleaching efluent related to RFA is by bleaching of mixed wood pulp. The :unsaturated fatty acids, monochloro &results are compared with those on someINTRODUCTIONdichlorodehydro-abietic acid, 9,10 epoxy-agro-residues and straw pulps reportedResin & fatty acids (RFA) are thestearic acid and 9,10-dichloro-stearicearlier"-8. The concentrations of RFA areextractive components of wood and occuracid. The concentrations of chlorinatedcompared to know whether they are belowin parenchyma cells of commerciallyresin & fatty acids in kraft chlorination &or above the reported LC5o values. Theimportant coniferous wood speciescaustic extraction effluents are probablyLCso values indicate that unsaturated fatty(softwood). A major difference in therelated to the eficiency with which the acids, resin acids, chorinated resin acidsextractives content between hardwoodunbleached pulp is washed free of pulpingand chlorinated fatty acids are toxic inand softwood is that the former doesliquor before it enters the bleachingnature.not contain resin acids. Though aprocess. Epoxystearic acid is believed tosubstantial amount of RFA is dissolvedarise from hypochlorination of oleic acidEXPERIMENTALas sodium salt in kraft cooking processin the chlorination stage and subsequentand removed with the black liquor, somedehydrochlorination during causticResin acids and chloro fatty acids wereamount of RFA passes along with theextraction. Another toxic component, obtained from Helix, Canada and fttypulp even after brown stock washing.dichlorostearic acid, may be formed bythe acids from Sigma, USA. StandardSubsequent bleaching of the pulp withreaction of chlorine with oleic acid.solution of resin acids and fatty acids wereTwo methods developed by NCASI,prepared in 10% methanol ether solution.chlorine, extraneous components mayget transformed into organically boundUSA国I and British Colombia Research'Other reagents used for identificationchlorine compounds which are more toxicinvolve the isolation of resin and fattystudies were of analytical reagent grade.acids by extraction with diethyl etherUnbleached washed mixed pulp was takenthan its parent components.Extensive research, particularly byor sorption on XAD-2. In both methods from nearby paper mill. The kappa numberBritish Columbia Research in Canada, hasthere is a formation of emulsion, whichof pulps (Table 1) was determined byestablished that resin acids and to a lessergives poor rcovery of the some of RFA_ standard method, the kappa numbers ofextent, unsaturated fatty acids are majorIcomponentsIBs. The method中国煤化工- are given in Table 1. The: was calculated from thecontributors to the toxicity of softwoodVoss overcomes the problenYCNMHGle.pulp and paper mill efuents to fshhh as formation; this mehod has!resin & fatty acid determination'Chlorine demand (%) = 0.25 x kappa numberdetermined from acute lethal bioassays.In the present study, we report thePulp bleaching is carried out in moreReceived date:2006-10-24results on estimation of resin and fattythan one bleaching stage. 70% of chlorine《中舅勞数糖07年第26卷第5期●29.研究论文demand has been applied as elemental total dissolved solids, BOD3 (biochemical was derivatized with dropwise additionchlorine during the chlorination stage. All oxygen demand)and COD (chemicalof ethereal solution of diazomethane till achemicals are applied as % od pulp (oven oxygen demand)Io. Color measurementpale yellow color persisted for sometime.dried; heated to constant weight in an oven was performed spectrophotometrically on The excess diazomethane was removed byat 105C for 12h). .a Shimadzu spectrophotometer model UVdropwise addition of glacial acetic acid.Unbleached pulp (equivalent to 35g 2100/S.The solution was made up to 0.5mL withod pulp) was bleached9in the laboratory50mL of E stage or 100mL of C stage10% methanol-ether and 0.5μL of theto generate effluents. The bleaching effuent adjusted to pH value 9 was solution was injected into the column forconditions are shown in Table 2. The extracted with equal volume of methylthe analysis of resin and faty acids (Fig.I).volumes of effluent generated in the tertiary butyl ether for 1 hour. The etherC stage and E stage were 1.81L and layer was separated and evaporated almost RESULTS AND DISCUSSION2.02L, respectively. The effluents were to dryness. It was then dissolved in 0.1mLThe various resin and fatty acids havecharacterized by determining the pH value, of methanol and the resulting solutionbeen identified by matching the retentiontime with the retention time of pureTable 1 Kappa number of various pulpssaturated compounds. The separation of33 resin and fatty acids has been achievedRaw materialKappa No.Eucalyptus17on OV-101 column (Table 3). HoweverKahi grass23certain groups of acids like oleic/inolenic/Bagasse24elaidic; isopimaric, 0-mecthylpodocarpicWheat straw26.3and levopimaric/palustric are notMixed pulpseparated on OV-101 column. In these31.5(Pine:Euca. :Bamboo=(40~ 50):(40~ 50):10cases, the quantities have been determinedBamboo37.5by taking as if only one is present andthen calculating the average value. TheTable 2 Bleaching conditionsconcentrations of various resin and fattyacids in C and E stage effluents fromParameterC stageE stagemixed pulp are given in the Table 4. TheCl2 applied (% demand)7values of some agro-residues and strawNaOH applied (% od pulp)pulp are also included for comparison.Consistency (%)3.5An examination of data in Table 4pt1.8-~2.011~12indicates that various categories of acidsTemperature(C)260have been identified. These are saturatedTime (min)6(75fatty acids (SFA), unsaturated fatty acidsNote Consistency (%)= g od pulp1 100 g pulp suspension(UFA), resin acids (RA) and chlorinatedresin acids (Ch. RA). The quantitiesEffluent Sampleof individual member of the variouscategories of acids are in general higher inAdjusted to pH vahue 9 using 0.5 mo/L NaOHE stage efuent than in C stage efluent forEfluent Sample(pH9)all the raw materials studied. Comparisonof the total estimated quantities of SFA,Extracted with Methyl Tertiary Butyl EtherUFA, RA, Ch. RFA and RFA in bleachplant efluent of various pulps have beenEther layerAqucous layershown in the Fig.2- -Fig.6.Among the SFA, palmitic, stearicand tricosanoic in general contribute aEvaporated to drynessmajor share to the total saturated fattyDry Residueacid content in the effluent. Palmitic acidis among the bighest contributor in allDissoved in 2 drops of methanol and diluted to 0.5 mLwith 10% methanol ether,methylated with diazomethanepulps studied. The quantity is higher for中国煤化ralypbus and bambo inMethylated derivatives of acids-agasse, wheat straw andYHC N M H Gquantity of stearic acidnas Deen lound to be much higher inQualitative and Quantitative analysis by GCkahi grass than in other non-wood pulps.Behenic acid has been detected only inFig.1 Separation of resin and ftty acids from efluentChina Pulp & Paper Vol.26, No.5, 2007"方数据研究论文Table3 GC Conditionspulps is as follows:ParameterColumn 0V-101Mixed pulp> Bamboo> Bagasse> Kahi>DetectorFIDWheat straw > EucalyptusDetector range0°Chart speed (cm/min)Oleic/ linolenic 1 elaidic fraction is theSample sie (4)0.5~1major contributor to the total unsaturatedInjection splitless (min)2fatty acid content. Eucalyptus has theColumn dimensions30m x 0.32 mmFilm thickness(μm)0.25maximum value of this fraction. Agro-Carrier gas (N2 ) flow rate (mUmin)20residues have a lower value of thisMake up N2 flow rate (mL /min)10fraction, the values being comparableInjection and detector temperature ( C)00in the case of bagasse, wheat straw and190 for 4 minkahi grass but the values are lowest190~ 210 at 1C /minfor bamboo. Erucic acid is anotherColumn temperature ( C)210~ 230 at 2 Cminunsaturated fatty acid detected in mixed230~250 at 3 C/min250 for 15 minpulp, eucalyptus, wheat straw and bagasse.The quantity is the highest in the case ofmixed pulp, wheat straw and bagasse. general in the various pulps. Howevermixed pulp and lowest in the case of wheatLignoceric, heptadecanoic, arachidic and theses quantities are much smaller thanstraw. Palmitoleic acid in mixed pulp &docosahexaenoic 1 heneicosanoic are the other saturated fatty acids. The totaleucalyptus and linolenic acid in eucalyptusother saturated fatty acids identified in identified SFA concentration from various& wheat straw have been detected in veryTable 4 Concentration of resin and fatty acids (g/lodt) present in the C stage & E stage efuent from various pulpsMixed PulpEucalyptusBambooKahi grassWheat strawBagasseName of acidCstageEstage Cstage Estage Cstage Estage C stage E stage C stage E stage C stage E stagePalmitoleicPalmitic30.50 117.13 17.06 125.00 49.11 154.0. 12.40 98.09 36.19 92.32 36.19 67.51Heptadecanoic2.072.311.554.04 0.36 3.05 1.03 4.04 0.520.80 5.17 9.81LinolenicOleicd/ Linolenic/ Elaidic10.30 43.27 6.7277.89 5.1716.15 4.49 32.89 4.80 32.88 11.37 32.31Stearic7.2048.46 4.6516.151.0317.30 1.5542.69 5.6816.7310.58 22.50Pimaric0.311.730.160.29 0.460.41Nonadecanoic-0.524.03Sandracopimaric5.77O-Methylpodocarpic90.6 2.7435.19 2.5816.15 4.6535.19 1.291.81Levopimaric/Palustric0.38 27.69 0.5210.96Dinydroisopimaric1.03960.2612.46 0.25Arachidic1.039.23 1.55.1.730.413.46 1.0310.380.412.07 0.8312.11Abietic.037.50一Neoabietic2.88 0.101.1524.810.773.365.77 0.7712.690.256.63HeneicosanoicCholorodehydroabietic I4.65 26.54 1.039.818.07 3.108.07 1.038.070.25Erucic29.47 79.62 11.37一一- 0.72-3.6213.27Chlorodehydroabietic II17.07 44.4313.85 3.623.46 0.98Behenic19.13 21.9--5.177.503.62Tricosanoic4.65 18.46 0.524.04 3.10中国煤化工2.30 0.41 21.92 .12,14-Dichloro Dehydroabietic6.920.100.29 1.03CNMHG2.88 0.4610.38Lignoceric4.13 8.651.21.44 5.1714.4C 1.U35.77 0.0529,10,12,13-Tetrachloro stearic1.864.610.922.062.88 0.52Note +very small amownt is detected; - not detected.《中国浩纸》3907年第26卷第5期●31●[ 研究论文口C StageOC StageOc StageBESlage 14026QEStageoE Stuge250-20017100-60马150-是60三100乐100si血Euca Kahi Baga Wh.St. Mixed BambooEuca Kahi Baga WhSt. Mixl. Mixed BambooMixed BambeBarmbooPuipRaw MaterialFig.2 Quantity of saturated fatty acids fromFig.3 Quantity of unsaturated fatty acids Fig.4 Quantity of resin acids from dfferentdifterent pulpsfrom diferent pulpspulpsocsuge unsaturated fatty acids. The saturated fttyDCStageDESuge53JE Stageacids are relatively non-toxic in nature.60t. 500-The data given in Table 4 indicate that the400311 298total resin acid content and unsaturated之30045 23030252 200fatty acid content in the mixed pulp and监eucalyptus pulp are higher than non-woodEuca Kahi Baga whsMixed BambooEuca Kahi Baga Wh.st. Mixed Bamboopulps and hence the waste water fromPurpdBanbooPulmixed pulps would contain comparativelymore toxic components than from non-Fig.5 Quantity of chlorinated resin and fttyFig.6 Quantity of resin and fatty acids fromwood pulps. Kahi grass is an exception,acids from dfferent pulpsdiferent pulpsin which the total resin acid content issmall amounts. Total identified UFA in resin acid content for both C and E stageslightly higher than that in eucalyptus.various raw materials is the highest in effuents for all raw material pulps studied.Thus the contribution to effluent toxicityfrom resin and fatty acids of kahi grassmixed pulp but much lower in the case ofi)The quantity of total SFA is muchwould be higher than other non-woodagricultural residues as shown in Fig.3. higher than total UFA, in all the pulpspulps. Likewise toxic content of resin andThe total identified UFA from various studied.pulps is as fllows:ii)The quantity of chlorinated resinfatty acids would be higher in E stage thanacids contributes a major share to the totalC stage efuent.The concentration of various resin acidsMixed pulp > Euca. >Bagasse > Wheat identified chlorinated resin and fatty acidsand unsaturated fatty acids determined arestraw > Kahi >Bamboofor all the pulps studied.in general below the respective LC5o valuesfor all the pulps studied. The exceptionsAn examination of results in Table 4The LCo values!"" reported for variousare isopmaric/o-methlpododarpic acidshows that the total resin acids and fatty resin acids and fatty acids are given inconcentration from mixed pulp and kahiacids are comparable in non-wood pulps. Table 5. The LC5o values are in generalgrass and chlorodehydro abietic acidThe highest value is for mixed pulp and lower for resin acids in comparison toconcentration from E stage of mixed pulp,the value is slightly higher than non-wood pulps in the case of eucalyptusTable5 LCso Values of various resin and fatty acids(Fig.6). The approximate composition ofAcidsLCso (mg/L)eucalyptus,pine and bamboo in the mixedpulp is(40-0):(40- 50):10. It is a knownPalmitic>20HeptadecanoicNAfact that the resin content in pine is muchStearic .higher in comparison to hardwoods andOleic3.2 ~8.0 .other sofwoods. Thus the mixed pulp isLinoleic2.0~ 4.5 .expected to contain higher proportion ofLinolenic3.0~6.0total resin acid and ftty acid . The resultsPimaric7.0 ~1.2also reveal that this content is higher in ESandracopimaric0.4stage than in C stage efuents. This is duelsopimaric0.4~ 1.0to higher solubility of resin and fatty acidsPalusric0.5~ 0.6in alkaline media than in acidic media.Abietic中国煤化工0.7 - 1.5The following conclusions have beenDehydro-abietic-0.8~ 1.7drawn from study:Neo- abieticMHCNMH G0.6-0.7Chlorodehydrobietic0.6- 0.9i)The total identfied fatty acid content12,14-dichlorodehydroabietic0.6~1.2is much higher in comparison to total9.10-dichloro stearic0.6 ~1.2"方方数据China Pulp & Paper Vol.26, No.5, 2007研究论文]where the values exceed LC30 values. Indehydroabietic acid as one of the major346 : 205the case of wheat straw, concentrationpollutants particularly from debarking,[7] Sharma C, S Mohanty, S Kumar, etof levopimaric/palustric acids is slightlyboth mechanical and chemical pulping andal. Gas Chromatographic analysis oflower than the lower limit of LCso valuc.whole mill effluent. Monochloroabieticchlorophenolics, resin and fatty acidsIdentified fatty acids(in the caseand dichloroabietic acids have beenin efluents from bleaching process ofof wheat straw) are comparable with detected, but dehydrobietic andagricultural residues. Intern. J. Environ.those reported by Folke and Pl2l.dichloroabietic acids have not beenAnal Chem, 1996, 64 : 289Tricosanoic, heneicosanoic, heptadecanoic,detected from both C and E stage effluents[8] Sharma C, S Mohanty, S Kumar, etlinolenic, oleic, elaidic, 9, 10, 12, 13-tetrafrom all the pulps studied. Howeverchlorostearic acid are in gencral identifiedtetrachlorostearic acid has been detected.chlorophenolics, resin and ftty acids inin all the pulps studied, but these are not The detection of epoxystearic acid was notchlorination and caustic extraction stagereported by Folke and Pallel20. Palmitic,attempted.effluents from Kahi-grass. The Analyst,stearic, behenic, oleic, lignoceric and1996, 121(12): 1963arachidic acids are identified in wheatREFERNCESstraw and also reported by Folke and9] Singh R P. The bleaching of pulp. ThirdPallel20. The concentration of palmitic[1] Rogers I H, Mahood H, Servizi J, et al.Ed. Revised. Atlanta : Standard Press andacid is higher than other ftty acids.TAPPI Pess, 1979Identifying extractives toxic to aquatic life.The quantities of identified resin acids[10] Greenberg A K. Standard Methods.Pulp & Paper Canada, 1979, 80 (9):94from different pulps are generally lower[2] Walden C C, Howard T E. Toxicity of pulpSixteenth Ed. American Public Healththan the results reported by Voss andAssociations, 1985and paper mill efluents : a review. Pulp &Rapsomatiotis" but higher than those[1] Lee H, Peart T, Carron J M. GasPaper Canada, 1981, 82 (4):115reported by Lee et al". In the case ofchromatographic and mass spectrometricmixed pulp (contains softwood pulp),[3] Claeys R R. National Council of Paperdetermination of some resin and fttypimaric isopimaric/o methylpodocarpic,Industry Air stream Improvement, Streamacids in pulp mill effluents as theirdihydroisopimaric, abietic, neoabietic,Improvement. Tech. Bull. No. 281(1975)pentafuorobenzyl ester derivatives. Joumalchlorodehydroabietic (two isomers) and[4] Leach J M, Thakor A N. Isolation ofof Chromatography, 1990, 498 :36712, 14- dichlorodehydroabietic acid arethe toxic constituents of kraft pulp mill[12] Folke J, Palle Jorgensen L. Organicsidentifed. Quantities of these resin acidseffluents. Environmental Protectionin wheat and rye straw pulp bleachingare in general lower but in the case ofService. Canada, Ottawa, CPAR projectand combined mill efluents, chemicalchlorodehydroabietic acid (two isomersreport No.1-5(19741)characterization and biodegradation& isopimaric acid) concentration is[5] Richardson D E, Bloom H. Analysis ofstudies. Toxicological and Environmentalhigher than that reported by Voss andresin acids in untreated and biologicallyChemistry, 1985, 10:1Rapsomatiotis'.Leach and Thakorel'3l have reportedtreated thermomechanical pulp efluent.[13] Leach J M, Thakore A N. Compounds toxicAPPITA, 1982, 35(6) :477the presence of four resin and fatty acids[6] Voss R H, Rapsomatiotis A. An Improvedto fish in pulp mill waste streams. Prog.viz., monochloroabietic, dichloroabietic,Wat. Tech, 1977,9:787 CPPSolvent Extraction based Procedure for thedichlorostearic and epoxystearic as theGC Analysis of Resin and Fatty Acids inmain toxicant from extraction stage. Many(责任编辑:关颖)Pulp Mill ffluents. J. Chromatogr, 1985,workers have reported the presence of。消息。2007年(第七届)中国造纸化学品开发应用国际技术交流会在杭州召开2007年(第七届)中国造纸化学品开发应用国际技较好地反映了我国造纸化学品研究与应用的最新成果。术交流会于2007年4月24- -26 日在杭州成功召开，会美国亚什兰集团、日本播磨化成株式会社、丹麦丹议由中国造纸化学品工业协会主办。会议采取专题报告尼斯克有限公司的代表就纸机上沉积物的控制和施胶和论文集相结合的形式，就造纸化学品新产品、新技术增强剂的干发与中田笔作了专晒道。国内的科研单位的开发及应用开展交流，旨在增进造纸化学品行业与纸和企MH中国煤化工纸化学品研究与生产厂的沟通与合作。来自国内外从事造纸化学品研究、开应用CN MH G与会企业用户代表与发、生产、应用的企事业单位和高等院校的教授、专家化学品公司就各自感兴趣的问题进行了沟通，各方面的近200人出席了本次国际交流会，收集到论文50余篇，代表对此次国际交流会取得的成绩表示满意。《中国華秀新理?7年第26卷第5期●33.