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Scientific Contribution in Oil and Gas Industry Vol 35, Number 1 April 2012

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CoverTools Name : ASTM 1266 iChief Editor:Dra. Yanni Kussuryani, M.Si. (Chemist)Managing Editor:Ir. Daru Siswanto (Chemical Engineering)Ass. Managing Editor:Drs. Heribertus J oko Kristadi, M.Si. (Geophysic)Senior Editors:1.Prof,Dr. Maizar Rahman (Chemical Engineering) 2.Ir. E. J asj, M.Sc., APU. (Chemical Engineering) 3.Prof. Dr. Suprajitno Munadi (Geophysics) 4.Prof. M. Udiharto (Biology)5.Prof. Dr. E. Suhardono (Industrial Chemistry) 6.Ir. Bambang Wicaksono T.M., M.Sc. (Petroleum Geology)Editors:1.Dr. Ir. Usman, M.Eng. (Petroleum Engineering)2.Ir. Sugeng Riyono, M.Phil. (Chemical Engineering)3.Dr. Ir. Eko Budi Lelono (Palynologist)4.Abdul Haris, S.Si., M.Si. (Chemistry and Environment)Peer Group:1.Prof. Dr. Ir. Septoratno Siregar (Petroleum Engineering)2.Prof. Dr. R.P. Koesoemadinata (Geological Engineering)3.Prof. Dr. Wahjudi Wisaksono (Energy and Environment) 4.Dr. Ir. M. Kholil, M.Kom. (Management of Environment)5.Dr. Ir. Bambang Widarsono, M.Sc. (Petroleum Engineering) 6.Ferry Imanuddin Sadikin, S.T., M.E. (Electrical Engineering) Secretariat:Publications Affairs Publisher:LEMIGASResearch and Development Centre for Oil and Gas Techno logy Alliation and Publication DivisionPrinted by:Graka LEMIGASVolume 35, No. 1, April 2012SCIENTIFIC CONTRIBUTIONS OIL & GAS is a printing media to promote research and developmentactivities which have been done byLEMIGASResearch and Development Centre for Oil and Gas Technology.AddressLEMIGAS Research and Development Division for Alliation and Publication, J l. Ciledug Raya, Kav. 109, Cipulir, Kebayoran Lama, P.O. Box 1089/J KT, J akarta Selatan 12230INDONESIA, STT: No. 348/SK/DITJ EN PPG/STT/1987/May 12, 1977, Phone: 7394422 - Ext. 1222, 1223, Fax : 62 - 21 - 7246150, e-mail: [email protected] Contributions Oil & Gas has been published since 1977 it had been named LEMIGAS Scientic Contributions (LSC),3timesayear. Theeditorreceivesscienticarticlesaboutresearchresults,relatedtotheoilandgas research.Scientic Contributions Oil & Gasis published by LEMIGAS Research and Development Centre for Oil and Gas Techno logy. Chief Editor : Dra. Yanni Kussuryani, M.Si. Managing Editor:Ir. Daru SiswantoISSN : 2089-3361iiVolume 35, Number 1, April 2012PageCONTENTSiiINTRODUCTION iiiABSTRACTSivCHARACTERIZATION OF THERMAL PRECIPITATOR IN SMOKECOLLECTOR BY USING PARTICLE COUNTERImansyah Ibnu Hakim, Bambang Suryawan, I Made Kartika D., Nandy Putra,and Cahyo Setyo Wibowo1 - 10INHIBITION OF MILD STEEL IN 1M HCLBY CATECHIN MONOMERS FROM COMMERCIALGREEN TEA EXTRACTS Nofrizal11 - 24THE IMPROVEMENT OF MERCURY REMOVAL IN NATURAL GASBY ACTIVATED CARBON IMPREGNATED WITH ZINC CHLORIDELisna Rosmayati25 - 29COMPARISION DEPOSIT FORMATION ON THE VALVE DIESELENGINE CAUSED BY BIODIESEL AND PETROLEUM DIESEL FUELSMaymuchar, and Ismoyo Suro Waskito31 - 37DILUTE ACID PRETREATMENT AND ENZYMATIC HYDROLYSISOF LIGNOCELLULOSICBIOMASS FOR BUTANOLPRODUCTION AS BIOFUELDevitra Saka Rani and Cut Nanda Sari 39 - 48ISSN : 2089-3361 iiiINTRODUCTIONDear Readers,Scientic Contributions Oil & Gas has a very signicant role in Indonesia science community and oil and gas industry for information dissemination in oil and gas research and studies. Scientic Contributions Oil & Gas April2012, Volume 35, Number 1 presents some se-lected results of studies and research in LEMIGAS:1. Characterization of Thermal Precipitator In Smoke Collector by Using Particle Counte;2. Corrosion Inhibition of Mild Steel in 1M HCL by Catechin Monomers From Commercial Green Tea Extracts; 3. The Improvement of Mercury Removal in Natural Gas by Activated CarbonImpregnated With Zinc Chloride; 4. Comparision Deposit Formation on The Valve Diesel Engine Caused by Biodiesel and Petroleum Diesel Fuels; 5. Dilute Acid Pretreatment and Enzymatic Hydrolysis of Lignocellulosic Biomass for Butanol Production As Biofuel.April 2012 edition Scientic Contributions Oil & Gas Editorial Team hope that Scientic Contributions Oil & Gas can be a reference for the authors/researchers. Reader feedbacks and inputs for development are strongly suggested and will be highly appreciated to improve next edition of Scientic Contributions Oil & Gas.Editorial board, Publisher and Manajemen extend highly gratitude for authors, reviewers and editors who have worked very hard to making this edition of Scientic Contributions Oil & Gas is possible to succesfull published. J akarta, April 2012RedactionivImansyah Ibnu Hakim1), Bambang Suryawan1), I MadeK arti kaD.1),NandyPutra1),and Cahyo Setyo Wibowo2)1)Department of Mechanical Engineering, Faculty of Engineering Universitas IndonesiaKampus UI Depok 16424 J awa Barat. Phone: 62-21-7270032, Fax: +62-21-7270033, E-mail: [email protected])Researcher at LEMIGAS R & D Centre for Oil and Gas Technology J l. Ciledug Raya, Kav. 109, Cipulir, Kebayoran Lama, P.O. Box 1089/J KT, J akarta Selatan 12230INDONESIA. Tromol Pos:6022/KBY B-J akarta12120,Telephone: 62-21-7394422,Faxsi mi le:62-21-7246150CHARACTERI ZATI ONOFTHERMAL PRECIPITATOR IN SMOKE COLLECTOR BY USING PARTICLE COUNTERScientic Contributions Oil & Gas, April 2012, Volume 35, Number 1, p. 1 - 10ABSTRACTAir pollution in major cities in many countries hasreachingaveryconcerninglevel.Oneofthe cause of air pollution is pollution caused by smoke aerosol. Smoke aerosols that has an average particle diameter of 0.1 m 1 m can be found in cigarette smoke, diesel vehicle fume, industrial fume and many else. This condition willbe worsen by the increase in the number of smokers, motor vehicles and industry. Therefore we need to pursue the control method for that kind of air pollution. In the literature study, its found that the cleaning method of air ltration for ne particle with dimension of 0.01 5 m are by using thermal precipitator. Thermal precipitator is one method of air ltration based on thermophoretic force,whichisifthereisatemperaturedifference between two plates, it will cause the force that will pushtheparticlesbetweenthetwoplatestoward theplatethathaslowertemperature.Intheeffort to help control and reduce the air pollution, for this study we made a thermal precipitator test equipment todeposittheparticlesintheairwiththeuseof thermophoretic force. That force is the force applied to the particles that suspended in the uid ow. The temperaturedifferencebetweentwoplatesisset atT=5,10,15,and20oC.Thisstudyutilizedgas sensorstoobservethecharacterizationofthermal precipitator.Fromtheexperimentandanalysiscan be concluded that thermal precipitator can be applied as a smoke collector.(Author)Keywords: thermal precipitator, smoke collector, gas sensorNofrizal (Researcher at LEMIGAS R & D Centre for Oil and Gas Technology)J l. Ciledug Raya, Kav. 109, Cipulir, Kebayoran Lama, P.O. Box 1089/J KT, J akarta Selatan 12230 I NDONESI A. Tromol Pos: 6022/KBYB-J akarta 12120, Telephone: 62-21-7394422, Faxsimile: 62-21-7246150 CORROSION INHIBITION OF MILD STEEL IN 1M HCL BY CATECHIN MONOMERS FROM COMMERCIAL GREEN TEA EXTRACTS Scientific Contributions Oil & Gas, April 2012, Volume 35, Number 1, p. 11 - 24ABSTRACTTheinhibitoryeffectoftwoIndonesiangreen teaextracts(containingvariouscatechins)were investigated on the corrosion of mild steel (MS) in 1M HCl medium. The anticorrosion effect was evaluated by conventional weight loss method, potentiodynamic polarisation, electrochemical impedance spectroscopy (EIS) studies and scanning electron microscopy (SEM) technique.Theresultsevidencedthatboththetea extractsactasagoodcorrosioninhibitorandthe inhibition efciencies (% IE) were in good agreement forallthestudies.Adsorptionofgreenteaextract constituent was found to follow Langmuir adsorption isotherm and the calculated Gibbs free energy values indicated the physisorption of inhibitor over the mild steel surface. SEM - EDX studies show the adsorption of catechin monomers which forms a protective layer The descriptions given are free terms. This abstract sheetmay be reproduced without permission or chargeABSTRACTS voverthemilssteelsurface.Highperformance liquidchromatography(HPLC)analysiswas carriedouttoquantifythecatechinfractionsin the tea extract and it was found that eight catechin monomers were present in both tea extracts. From all of monomers, it was found that four monomers were identied as components responsible for controlling the dissolution of mild steel in 1 M HCl medium. (Author)Keywords:mildsteel,corrosioninhibition,green tea, HPLC, potentiodynamic, EISLisnaRosmayati(TechnologicalAssessorat LEMIGASR&DCentreforOilandGas Technology)J l. Ciledug Raya, Kav. 109, Cipulir, Kebayoran Lama, P.O. Box 1089/J KT, Jakarta Selatan 12230 I NDONESIA. Tromol Pos: 6022/KBYB-J akarta 12120, Telephone: 62-21-7394422, Faxsimile: 62-21-7246150 THE IMPROVEMENT OF MERCURY REMOVALIN NATURAL GAS BY ACTIVATED CARBONIMPREGNATED WITH ZINC CHLORIDEScientic Contributions Oil & Gas, April 2012, Volume 35, Number 1, p. 25 - 29ABSTRACTNaturalgasbeingproducedfromgasfields around Indonesia areas, along with a large number ofotherharmfulsubstances(CO2,H2S,RSH,COS etc) often contains mercury. Even in small amounts, mercuryanditscompoundshaveanextremely harmful effect on human health. Mercury content in the natural gas should be removed to avoid equipment damage in the gas processing plant or the pipeline transmission system from mercury amalgamation and embrittlement of aluminium. Mercury can be removed byusingadsorptionprocessessuchasactivated carbonthatisimpregnatedwithchlor,iodineor sulfur.Thisresearchisdealingwiththeprocess ofmercuryremovalfromgasbasedonprinciple ofadsorptionandofchemisorptionofmercuryby means of activated carbon impregnated with ZnCl2. Time of impregnation is a signicant variable that can effect adsorption capacity. The experiment results showedthatZnCl2impregnationtimeof12hours signicantlyenhancedtheadsorptivecapacityfor mercury vapour. (Author)Keywords:mercuryremoval,activatedcarbon, impregnated zinc chlorideMaymuchar1), and Ismoyo Suro Waskito2)1)Researcher, 2)Litkayasa, at LEMIGAS R & D Centre for Oil and Gas Technology J l. Ciledug Raya, Kav. 109, Cipulir, Kebayoran Lama, P.O. Box 1089/J KT, Jakarta Selatan 12230 I NDONESIA. Tromol Pos: 6022/KBYB-J akarta 12120, Telephone: 62-21-7394422, Faxsimile: 62-21-7246150 COMPARI SI ONDEPOSI TFORMATI ON ONTHEVA LV EDI ESEL ENGI NE C A U SE DB Y B I ODI E SE L A N DPETROLEUM DIESEL FUELSScientific Contributions Oil & Gas, April 2012, Volume 35, Number 1, p. 31 - 37ABSTRACTThe research on the inuence of the biodiesel to the formation of deposits on the intake and exhaust valves diesel engine has been carried out by means analysis of merit rating. The fuels used on this study are FAME (B-100), a mixture of 50% (v)ofFAME in diesel fuel 48 (B-50), and diesel fuel 48 (B-0). The objective of thisresearchistoobtaindatawhichrepresentthe inuence of the biodiesel to the formation of deposits on the intake and exhaust valve diesel engine. The test used a diesel engine driving 5 KVA generator which is operated for 100 hours with 1.000 Watt electrical load. The results of the studyshow that the use of either FAME or biodiesel as alternative fuel in the diesel engine generator 5 KVA has a positive effect onreducingthedepositontheintakeandexhaust valves.(Author)Keywords:Biodiesel,intakevalve,exhaustvalve, diesel engineover the mils steel surface. High performance liquid chromatography(HPLC)analysiswascarriedout to quantify the catechin fractions in the tea extract and it was found that eight catechin monomers were present in both tea extracts. From all of monomers, itwasfoundthatfourmonomerswereidentied ascomponentsresponsibleforcontrollingthe dissolution of mild steel in 1 M HCl medium. (Author)Keywords: mild steel, corrosion inhibition, green tea, HPLC, potentiodynamic, EISLisnaRosmayati(TechnologicalAssessorat LEMIGASR&DCentreforOilandGas Technology)J l. Ciledug Raya, Kav. 109, Cipulir, Kebayoran Lama, P.O. Box 1089/J KT, Jakarta Selatan 12230 I NDONESIA. Tromol Pos: 6022/KBYB-J akarta 12120, Telephone: 62-21-7394422, Faxsimile: 62-21-7246150 THE IMPROVEMENT OF MERCURY REMOVALIN NATURAL GAS BY ACTIVATED CARBONIMPREGNATED WITH ZINC CHLORIDEScientific Contributions Oil & Gas, April 2012, Volume 35, Number 1, p. 25 - 29ABSTRACTNaturalgasbeingproducedfromgasfields around Indonesia areas, along with a large number ofotherharmfulsubstances(CO2,H2S,RSH,COS etc) often contains mercury. Even in small amounts, mercuryanditscompoundshaveanextremely harmful effect on human health. Mercury content in the natural gas should be removed to avoid equipment damage in the gas processing plant or the pipeline transmission system from mercury amalgamation and embrittlement of aluminium. Mercury can be removed byusingadsorptionprocessessuchasactivated carbonthatisimpregnatedwithchlor,iodineor sulfur.Thisresearchisdealingwiththeprocess ofmercuryremovalfromgasbasedonprinciple ofadsorptionandofchemisorptionofmercuryby means of activated carbon impregnated with ZnCl2. Timeofimpregnationisasignicantvariablethat can effect adsorption capacity. The experiment results showedthatZnCl2impregnationtimeof12hours signicantlyenhancedtheadsorptivecapacityfor mercury vapour. (Author)Keywords:mercuryremoval,activatedcarbon, impregnated zinc chlorideMaymuchar1), and Ismoyo Suro Waskito2)1)Researcher, 2)Litkayasa, at LEMIGAS R & D Centre for Oil and Gas Technology J l. Ciledug Raya, Kav. 109, Cipulir, Kebayoran Lama, P.O. Box 1089/J KT, Jakarta Selatan 12230 I NDONESIA. Tromol Pos: 6022/KBYB-J akarta 12120, Telephone: 62-21-7394422, Faxsimile: 62-21-7246150 COMPARISION DEPOSIT FORMATION ON THE VALVE DIESEL ENGINE CAUSED BY BIODIESEL AND PETROLEUM DIESEL FUELSScientific Contributions Oil & Gas, April 2012, Volume 35, Number 1, p. 31 - 37ABSTRACTThe research on the inuence of the biodiesel to the formation of deposits on the intake and exhaust valves diesel engine has been carried out by means analysis of merit rating. The fuels used on this study are FAME (B-100), a mixture of 50% (v)ofFAME in diesel fuel 48 (B-50), and diesel fuel 48 (B-0). The objective of thisresearchistoobtaindatawhichrepresentthe inuence of the biodiesel to the formation of deposits on the intake and exhaust valve diesel engine. The test used a diesel engine driving 5 KVA generator which is operated for 100 hours with 1.000 Watt electrical load. The results of the studyshow that the use of either FAME or biodiesel as alternative fuel in the diesel engine generator 5 KVA has a positive effect onreducingthedepositontheintakeandexhaust valves.(Author)Keywords:Biodiesel,intakevalve,exhaustvalve, diesel engineviDevitra Saka Rani 1) and Cut Nanda Sari1)1) Researcher at LEMIGAS R & D Centre for Oil and Gas TechnologyDI L U T E A CI DP RE T RE AT M E NT ANDENZY MATI CHY DROLY SI SOF LIGNOCELLULOSICBIOMASS FOR BUTANOL PRODUCTION AS BIOFUELScientific Contributions Oil & Gas, April 2012, Volume 35, Number 1, p. 39 - 48ABSTRACTBiobutanol is one of the promising biofuel for sub-stituting gasoline. Biobutanol produced from biomass fermentation using solventogenic clostridia which are able to convert a wide range of carbon sources to fuels suchasbutanol.Therefore,lignocellosicbiomass hasgreatpotentialasfermentationsubstratefor biobutanol production. Lignocellosic biomass should be hydrolized before fermentation by a pretreatment processandenzymatichydrolysis.Thevarious lignocellulosic biomass pretreatment will inuence inbutanolproductiondependingonfermentable sugars content. The objective of this research is to getpotentiallignocellulosicbiomassusingdilute acid pretreatment and enzymatic hydrolysis process forbiobutanolproduction.Eighttypesofbiomass from sugarcane bagasse, rice straw, rice husk, empty fruit bunch (EFB) of palm oil, corn cob, pulp waste, traditionalmarketorganicwaste,andmicroalgae wereusedinthisexperiment.Afterhydrolysis, thehighresultoftotalfermentablesugarsincorn cobs,bagasse,ricestraw,andricehusk,shows goodopportunityofthesebiomasstobeusedas fermentation feedstocks for biobutanol production. In addition, pulp waste, organic waste, and microalgae areprospectiveasrawmaterialbutrequiremore appropriate treatment either for to break down the cellulose/hemicellulose or to enhance reducing sugar content.Finemillinganddelignicationhaveno signicanteffectoncellulosicbiomassconversion intofermentablesugars.Therefore,theproduction cost can be reduced. In order to enhance the sugar content and reduce the formation of inhibitor product, it is necessary to examine dilute acid pretreatment variations and appropriate operating conditions of enzymatic hydrolysis process.(Author)Keywords: biofuel,biobutanol,lignocellulosic biomass,diluteacidpretreatment,enzymatichy-drolysis

1CHARACTERIZATION OF THERMAL PRECIPITATORIN SMOKE COLLECTORBY USING PARTICLE COUNTERImansyah Ibnu Hakim1), Bambang Suryawan1), I Made Kartika D.1), Nandy Putra1),and Cahyo Setyo Wibowo2)1)Department of Mechanical Engineering, Faculty of Engineering Universitas IndonesiaKampus UI Depok 16424 Jawa BaratPhone : 62-21-7270032, Fax: +62-21-7270033, E-mail : [email protected])Researcher at LEMIGAS R & D Centre for Oil and Gas Technology Jl. Ciledug Raya, Kav. 109, Cipulir, Kebayoran Lama, P.O. Box 1089/JKT, Jakarta Selatan 12230INDONESIATromol Pos: 6022/KBYB-Jakarta 12120,Telephone: 62-21-7394422, Faxsimile: 62-21-7246150First Registered on November 30th 2012; Received after Corection on April 18th 2012Publication Approval on :April 30th 2012ABSTRACTAir pollution in major cities in many countries has reaching a very concerning level. One of the cause of air pollution is pollution caused by smoke aerosol. Smoke aerosols that has an average particle diameter of 0.1 m 1 m can be found in cigarette smoke, diesel vehicle fume, industrial fume and many else. This condition willbe worsen by the increase in the number of smokers, motor vehicles and industry. Therefore we need to pursue the control method for that kind of air pollution. Intheliteraturestudy,itsfoundthatthecleaningmethodofairltrationforneparticlewith dimension of 0.01 5 m are by using thermal precipitator. Thermal precipitator is one method of air ltration based on thermophoretic force, which is if there is a temperature difference between two plates, it will cause the force that will push the particles between the two plates toward the plate that has lower temperature. In the effort to help control and reduce the air pollution, for this study we made a thermal precipitator test equipment to deposit the particles in the air with the use of thermophoretic force. That force is the force applied to the particles that suspended in the uid ow. The temperature difference between two plates is set at T=5, 10, 15, and 20oC. This study utilized gas sensors to observe the characterization of thermal precipitator. From the experiment and analysis can be concluded that thermal precipitator can be applied as a smoke collector.Keywords: thermal precipitator, smoke collector, gas sensorI. INTRODUCTION Air pollution in major cities in many countries has reaching a very concerning level. This condition isalsohappenedinIndonesia,particularlyinthe capital city of Jakarta, which became a barometer for other cities in Indonesia, has reached a concerning levelsoitcausedthedropinairqualityand environmentalsupportcapacity.Smokeaerosol isoneoftheairpollution.Smokeaerosolwith submicron-micron sized particle (0.01 5 m) are often found in cigarette smoke, diesel vehicle fumes, industrial fumes and many others. Efforts to control airpollutionarelimitedintheformofpamphlets, banners,etc.Eveniftherearerulesthatprovide sanction to air pollution, but the implementation in the eld is not optimum. Thermophoresisplaysanimportantrolein themechanismofmovementofsubmicron-sized particle in the aerosol technology. Thermophoresis phenomenondescribesthemovementofparticle caused by temperature difference around the particle. Ifthereisanytemperaturedifferencearoundthe particle between two regions (e.g plate), it will cause theforceandtheparticlebetweentwoplateswill movetowardtheplatethathaslowertemperature. Thisthermophoresiseffectwasfirststudiedby 2CHARACTERIZATION OF THERMAL PRECIPITATOR SCIENTIFIC CONTRIBUTIONS OIL & GASIMANSYAH IBNU HAKIM, ET AL.VOL. 35,NO. 1,APRIL2012 : 1 - 10Tyndalin1870andlaterby Aitkenin1884.They claried, that particles must be driven away from hot surface. This occurs due to a net force, acting in the opposite direction to the gradient temperature, toward the low-temperature region and is a direct result of thedifferentialbombardmentofthegasmolecules that comes from the relatively hot and relatively cold regions in the vicinity of the particles. A phenomenon referrednowtoasthermophoresis.Depositthat accumulated in heat exchanger equipments is caused bythermophoresis,studiedbyNishioetal.Byres et al. and Romay et al.StandfordResearchInstitute(Figure1)in 1961statedthatthecleaningmethodforparticle withdimensionof0.015marebyusing thermal precipitation particle separation by using heat.Thermophoresisinalaminartubeowhas beenstudiedthoroughly.Stratmannetal.(1989) experimentallystudiedthermophoreticdeposition using0.0050.1mmonodisperseaerosolina laminar tube ow. Montassier et al. (1990) carried out experiment with an experimental set-up that was similar to that employed by Stratmann et al. except forthedirectionoftheflowandthemeasuring technique.A.Messerer,etal.in2003using thermophoresistodepositsootaerosolparticlesin the exhaust system of diesel engine. Byung Uk Lee, et al. in 2006 conducted a similar study to A Messerer and stated that thermophoresis is a dominant factor to deposit the particle with 0.02 0.05 m of size inthevehicleexhaustsystem.Laterin2008Zhou Tao et al. conduct an experiment to visually prove that thermophoresis has a great inuence to make a 1 30 m particle deposit, but a little for the particle larger than 30 m. Earlier in 2004, Gallis M.A., et al. thermophoresisforcecanbeusedasthermal precipitator that can be applied more broadly in life, especially for pollution control. The same thing was observed by Gonzales D. et al. in 2005. K.K. Dinesh et al. studied the thermophoretic deposition in natural convectionowthroughaparallelplatechannel with heat sources. Effect of thermophoresis particle deposition from a horizontal at plate embedded in a porous medium was studied by Adrian Postelnicu (2007).Notonlyexperimentally,thermophoresis in annular ow theoretically studied by D.P. Healy et al. in 2010.Figure 1Particle size and character

3Figure 2Gas sensor garo 2600CHARACTERIZATION OF THERMAL PRECIPITATOR SCIENTIFIC CONTRIBUTIONS OIL & GASIMANSYAH IBNU HAKIM, ET AL.VOL. 35,NO. 1,APRIL2012 : 1 - 10Fx =6n. p. p2Cs. (K + Ct. Kn)p(1 +SCm. Kn)(1 +2K +2Ct. Kn)1IoIox Depositofneparticleisnotonlyinuenced bythermophoresis.Chi-ChangWangstudieda combined effects of inertia and thermophoresis on particle deposition onto a wafer with wavy surface. OtherresearcherslikeImanZahmatkeshclaried that, deposition particle ~ 100 m mainly occurs by inertial impaction. Thermophoresis is the dominant depositionmechanismforparticles~10m. Brownian diffusion contribute on the deposition of 10 nm. On the another hand, Changfu You studied the effect of electrostatic eld and thermophoresis on inhalable particulate matter. Effect of thermophoresis andelectrophoresisonparticledepositionontoa vertical at plate was studied by R. Tsai et al.Manyresearchaboutthermophoresishasbeen conducted and it is said that thermophoresis is the driving force for the deposit accumulation. But, research regarding thermal precipitator is rare. Therefore the smoke collector device has been conducted. That is the reason why we are conducting this research by conducting ex-perimental study of thermal precipitator test equipment to deposit the particles in the air by utilizing thermophoretic force. Therefore, rst thing to do is by investigating and characterizing the thermal precipitator itself.II. THEORY Thermophoresis force was studied by M. Eipstein in 2005 by assuming spherical particle and the uid is ideal gas, stated that thermophoretic force:.. (1)Where Fx is Thermophoresis force, Kn is Knudsen number=2/Dp,isparticledistance,K=k/kp, where k is uid thermal conductivity, k = (15/4) R, kp = particle thermal conductivity, Cs = 1,17; Ct = 2,18;Cm=1,14,T=localuidtemperature,= uid viscosity.Inthispaper,anexperimentalstudywas conducted.theparticleconcentrationorsmoke depositedontheplatewasmeasuredbyusinggas sensorandparticlecounter.Thetypeofthegas sensor is Figaro TGS 2600 (Figure 2). It is designed to measure concentration of pollution that prevalent in the room such as cigarette smoke. This sensor is commonly used to detect the presence of gas. This gas sensor can be applied as an alarm and also to measure gasconcentrationdependsonthemicrocontroller circuitthatisused.Thisgassensorconsistofa resistance value (Rs) that will respond when exposed to gas and has a heater that is used to clean sensor in internal chamber from air contamination from the outside.Output voltage signed at the resistor RL (Vout) is used as aninput to microprocessor. The material ofgassensorismetaloxide,particularlySnO2 Stainlesssteel gauzeMetalcapLead pinGASSENSOR( - )RLVoutGASVHRSRHVC12434Figure 3Illustration of oxygen absorbtion by the sensorFigure 5Gas sensor and microcontrollerFigure 6Graph showing the relationshipbetween Rgas/Rair vs consentrationCHARACTERIZATION OF THERMAL PRECIPITATOR SCIENTIFIC CONTRIBUTIONS OIL & GASIMANSYAH IBNU HAKIM, ET AL.VOL. 35,NO. 1,APRIL2012 : 1 - 10compound. In Figure 3 and Figure 4 are shown the illustration of Oxygen absorbtion by the gas sensor, when crystal metal oxide (SnO2) is warmed at given temperature, oxygen will be absorbed in the crystal surface and oxygen will be negatively charged. The absorbed oxygen by the sensor can be seen from the following chemical equation:O2O2SnO2-xSnO2-xeVsi nAi rE ) ( ) ( 2 / 12*2 2SnO ad O SnO O +This will occur because the crystal surface donate electronstotheoxygencontainedinouterlayer, sothattheoxygenwillbenegativelychargedand positive charge will be formed on the outer surface of the crystal. Formed surface tension will inhibit the rate of electron ow.In the sensor, current ows through the junction area (grain boundary) of SnO2 crystal. At the junction, oxygenabsorptionpreventsthechargetomove freely. If the gas concentration decreases, deoxidation processwilloccur,surfacedensityofnegatively Figure 4Illustration when Gas is Detected

5Figure 7Particle calibration to pt/ccCHARACTERIZATION OF THERMAL PRECIPITATOR SCIENTIFIC CONTRIBUTIONS OIL & GASIMANSYAH IBNU HAKIM, ET AL.VOL. 35,NO. 1,APRIL2012 : 1 - 10charged oxygen will be reduced, and resulting in the decreasing of the barriers height in the junction area. If there is presence of CO gas that is detected, then chemical equation as follow. *2 2 2) ( ) (x XSnO CO SnO ad O CO + +Obtainedvaluefromthegassensorarestillin the form of voltage ratio (Rgas/Rair),then to get the number of particle, Rgas/Rair value must be converted to ppm (part per million) by using graph as shown in Figure 6.The signal data from the sensor will be sent to themicrocontrollerwhichisthendisplayedtothe LCD screen in digital form. The picture of the gas sensor system and the microcontrollercan be seen in Figure 5.CleanroomstandardissuedbyUSFEDSTD 209EandISO14644-1FEDSTD209Eareusing particle/m3orparticle/ft3 astheunit. Thereforethe data to particle/m3 or particle/ft3 were converted using particlecounterP-TRACK8525.P-TRACK8525 that have the following specication: concentration range:0-5x105particles/cm3,particlesizerange: 0.02 2.5 m, operation temperature range : 0 38 oC, and level of accuracy: 0.01%. Calibration process from the gas sensor to the particle counter were done in same condition at the time of experimentation. The graph in Figure 7 shows the result of the calibration. acrylic, and at this position one gas sensor is placed to measure the smoke density in the air. Through the inlet section, smoke ows to the test section consists of 2 stainless steel plate. One of the plate is attached to a heater in order to maintain the temperature on the hot side. To have the variation of the temperature onthehotside,voltageregulatorisapplied.The test plate section dimension is 15 cm x 50 cm and distancebetweentwoplatesis5mm.Tomeasure the air velocity, we use a hot wire anemometer. The averageairvelocityinthetestsectionis5cm/s. To maintain the temperature of the cold side of the plate stable, cooling water is owed into the plate. Temperature is maintained at 26.850C. Then smoke will be deposited in the cold side of the plate so the level of the smoke that coming out from test section 50000045000040000035000030000025000020000015000010000050000000,60 0,65 0,70 0,75 0,80 0,85 0,90 0,95 1,001.05Pt/ccRgas/RairNo Parameter Value Unit1Aerosol type2Aerosol name3Particle diameter 0.01 ~1 m4Density 1.1 g/cm35Molecular mass 162.23 g/mol6Boiling point 247oCRef.: British American Tobacco (www.batscience.com)Smoke Table 1Test particle specicationFromthecalibrationweobtainthe following equation:y = - (3e+7)x3 + (7e+7)x2 (6e+7)x + (2e+7) ... (2)with a deviation R2 = 0.994. III. EXPERIMENTAL SETUPParticle used in this study is cigarette smoketypewiththespecicationsas shown in Table 1.In general, as shown in Figure 8, the experimental apparatus consist of a inlet andoutletsmokecontainerbox,test section is equipped by a heater in order to keep the hot side of the plate and cooling water to keep the cold side of the plate, gassensorTGS2600,microcontroller, andLCDdisplay.Cigarettesmokeis storedinthecontainerboxmadeof 6Figure 8Testing schemeCHARACTERIZATION OF THERMAL PRECIPITATOR SCIENTIFIC CONTRIBUTIONS OIL & GASIMANSYAH IBNU HAKIM, ET AL.VOL. 35,NO. 1,APRIL2012 : 1 - 10throughgassensorthatplacedinthe outlet section can easily be known. Data received by the gas sensor was sent to the microcontrollerthendisplayedtinthe LCD screen in digital form. 7 pieces of gas sensor (G1 G7) is mountedin the test section as shown in Figure 9. Thevariationoftemperature difference(T)betweenhotplate andcoldplatearesetasfollow:0o, 5o,10o,15o,and20oC.Buttoavoid themisinterpretationoftemperature difference(T)inthermophoresisfor exampleifhotplatetemperature(T2) = 50oC and cold plate temperature (T1) =27oC,thenTwillbeT=T2T1 =23oC.ThisT=23oCcanalsobe Figure 9Test section

7 TThotTcoldT*IN (pt/cc)OUT (pt/cc)IN (pt/cc)OUT (pt/cc)IN (pt/cc)OUT (pt/cc)IN (pt/cc)OUT (pt/cc)IN (pt/cc)OUT (pt/cc)14.160,99 13.328,08 15.536,47 6.524,99 15.954,46 6.974,51 16.092,46 6.795,21 16.922,06 13.084,78Deposited Particle0,17832 9011 8979 9297 383740250,38025250,00530252045250,441035250,2915Table 2The number of deposited particleFigure 11Deposited particles at T*=0CHARACTERIZATION OF THERMAL PRECIPITATOR SCIENTIFIC CONTRIBUTIONS OIL & GASIMANSYAH IBNU HAKIM, ET AL.VOL. 35,NO. 1,APRIL2012 : 1 - 10interpretedT2=100oCandT1=77oC,where bothofthemhaveadifferentradiationand convectioneffect.Thereforewecreatenew non-dimensionalparameterfortemperature, namely T*. Where T* = (Thot Tcold)/Thot or T*= (T2T1)/T2.Temperatureismeasuredusing Type-K thermocouple and data collection was carriedoutusingadataacquisitionsystem (NI cDAQ-9174). In this research 5 (T1 T5) thermocouples type-K were used and mounted on the surface of the plate as shown in Figure 9.Photo of the experiment equipment can be seen in Figure 10.Toclarifytheeffectofgravityonthis research, the position of hot plate are arranged so that may be positioned above and below. Other factors affecting the particle movement will be discussed inthe result and discussion. IV. RESULT AND DISCUSSIONDatafromtestingresultscanbeseenin Table2.,whilethetestgraphcanbeseenin Figure 11- 15.Figure 11 shows the graph of the test result for T = 0oC or T* = 0 when the heater is not operatedsothetestequipmentworksinthe ambienttemperature.Theaveragenumber ofparticleintheinletsectionis14,160pt/cc and in the outlet section is 13,328 pt/cc, so the average difference is 833 pt/cc. It means that the deposited particles are very small, so it can be said that the thermophoretic force did not occur, Figure 10Thermal precipitator test equipment8Figure 14Deposited Particles at T*=0.38CHARACTERIZATION OF THERMAL PRECIPITATOR SCIENTIFIC CONTRIBUTIONS OIL & GASIMANSYAH IBNU HAKIM, ET AL.VOL. 35,NO. 1,APRIL2012 : 1 - 10its mean no deposited particles.The graph in Figure 12 shows the number ofparticlewhenenteringandexitingthetest section for the temperature difference between hot plate and cold plate at 5oC or T* = 0.17. In the rst 5 seconds, the effect of thermophoresis is cannot be observed yet but in the next second and so on, there is a very signicance difference in the particle number. The average number of particles in the inlet is 15,536 pt/cc (particles per cubic centimeter) and in the outlet is 6,524 pt/cc, so the average difference is 9,011 pt/cc. This amount is the particle that deposited on the cold side of the test section. The similar result was obtained if the cold side of the test section in placed on the top. This means there is no gravity that inuences the particle. So, how about the inuenceofbuoyancyforce,Shafmannlift force, Brownion motion and electrostatic force, will be described below.Bouyancyforcearisesbecauseofthe viscositydifferenceinauid.Inagaseous uid, viscosity will decreases with increasing temperature. The inuence of buoyancy force in a uid can be known from the heat transfer mechanism experienced by the uid. Bouyancy force only appears on the convection that occurs naturally. To determine the type of convection that occurs, we can compare its Grasshoff value and Reynolds square value (Gr/Re2) of the uid. Inthisexperiment,thecomparisonbetween GrasshoffvalueandRayleighsquareisso small, so the Bouyancy force can be ignored.Saffmann lift force is a lift force on a particle caused by the friction between particle and uid ow. Due to extremely ne particle diameter, theparticlewillbeliftedagainsttheforceof gravity. In this experiment, the air velocity is very low at 5 cm/s, therefore the Shafmann lift force can be ignored and if Shafmann lift force does exist, it would be very little.AccordingtoBrownionmotion,this motionoccursinsubmicron-sizedparticle (dEGC>C>caffeine>EGCG>EC> GCG> ECG > and > CG (Figure 5).In order to determine the anticorrosion ingredients ofteaextractsquantitatively,HPLCanalysisof testsolutionswascarriedoutbeforeandafterthe corrosion processes. The concentrations of catechin consumedaftertheinhibitionprocessfromthe weight loss measurements are given in Table 6. In all previous reports (Rahim et al., 2007), it was assumed that all monomers would act as inhibitors for steel corrosion and their inhibitive performance depended on their concentrations. However, a key ndings of this study was that only certain catechin monomers gavesignificantcontributionstothecorrosion inhibition. Amongt heei ght cat echi nmonomer s presentintheteaextract,onlyepicatechin(EC), epigallocatechin (EGC), epicatechin gallate (ECG) dan epigallocatechin gallate (EGCG) were found to be consumed in the inhibition process as witnessed fromthereductionofpeakareasintheHPLC chromatogram. The order of increasing consumption and thus adsorption is as follows EC < EGC < ECG < EGCG. The peak areas for the other components were virtually unchanged.Interestingly, none of the chiral counterparts[(C),(GC),(GCG)and(CG)]were found to participate in the inhibition process although some of these monomers have shown inhibitive effect whenusedindividually(Rahimetal.,2007).This suggests that the inhibition is stereospesic and the (R, R) conformation. (Figure 6)mayhavefacilitatedthe absorption of these molecules. Thehighercatechincontent oftheGT2extractshowed hi gher consumpt i onof themonomers, whichis consistentwiththehigher inhibitionefficiencyofthe GT 2 extract as compared to the GT 1 extract. The amount of monomers consumed also showed a positive correlation withthetimeofimmersion whenhigherconsumption ofmonomerswasrecorded fortheweightlossmethod. Surprisingly,althoughboth greenteaextractshadthe highestcaffeinecontent,theHPLCresultsdidnot showtheconsumptionofcaffeinealkaloid.This contradicts to the earlier studies thatreported caffeine as an effective metal corrosion inhibitor (Anthony et al., 2004). This disparity could be due to the fact that the presence of the catechin monomers (EC, EGC, ECG and EGCG) may have blocked the adsorption ofcaffeinemoleculeovertheMSsurfaceordue tothedifferentelectrolyteused.Thestructuresof thevariouscatechinsandcaffeineareshownin Figure 6. F. FT IR studiesThegreenteaextractswerestudiedbyFTIR spectroscopyinordertoidentifythefunctional groups. Figure 7 shows the IR absorption spectrum ofthegreenteaextractsandthetypicalfunctional groups of catechin namely O-H, C=C (for aromatic rings)andC-Othatwereevidencedat3400-3100, 1600 and 1150 1010 cm-1, respectively (Maoela et al., 2009). These are the functional groups that were already identied as potent anticorrosion groups in organiccorrosioninhibitorsasreportedbymany researchers (Blustein et al., 2006).Itwasassumedthatacatechinmonomer whichhasmorenumbersofheterofunctionality andelectroniccloudscouldserveasabetter corrosion inhibitor. According to this consideration, Epigallocathecingallate(EGCG)monomerwas assumedtocontributemoreduringthecorrosion Figure 7IR spectra of (a) GT 1, and (b) GT 2 extracts.CORROSION INHIBITION OF MILD STEEL IN SCIENTIFIC CONTRIBUTIONS OIL & GASNOFRIZALVOL. 35,NO. 1,APRIL2012 : 11 - 24

21inhibitionprocesssinceithasthree aromaticringsalongwitheightOH groupswhileECGcontainsseven OHgroupsandEC,EGChavingless numbersofaromaticringsandOH groups.Indeed,asmentionedearlier, HPLCresultsshowedthatEGCG monomerwasconsumedthemost during the inhibition process, suggesting thatthepresenceofheterofunctional groups(OH)and-electronson thebenzeneringcontributedtothe corrosion inhibition by EGCG. G. Scanning Electron Microscopy-Energy Dispersive X-Ray Spectroscopy (SEM-EDX) studiesTomonitorthemorphological changes on the MS surface during the corrosion process, SEM EDX studies werecarriedout.MSspecimenswere screened after the potentiodynamic po-larisationstudiesandthemicrographs are given in Figures 8a, b and c. From Figure 8a. It is clearly seen that the surface is very rough and severely damaged in the absenceofinhibitorswhileinFigures 8b and 8c the surfaces are transformed intosmoother,moreuniformdeposits upon addition of the green tea extract. The distribution of rough surfaces were signicantly reduced. The composition ofthesamplefromtheEDXanalysis showedtheincreaseofcarbonand reductionofoxygenatomsduetothe reduction of corrosion products (Table 7), probably due to the adsorption of the monomers of the green tea extract.IV. CONCLUSIONSThetwocommercialIndonesian greenteaextractsshowedcomparable inhibitionpropertiesforthecorrosion of mild steel in 1 M HCl medium. The %IEobtainedviapolarisationmea-surementisingoodagreementwith Fe O C97.57 0.88 1.5474.23 23.54 1.4189.21 7.45 4.8190.68 5.79 4.07GT green tea Mild steel with GT 2 extractSampleElement (%) Fresh mild steel Mild steel without inhibitor Mild steel with GT 1 extractTable 7The composition of samples from the EDX analysisthat obtained by using the weight loss and impedance methods. The polarisation results also revealed that both inhibitors control the cor-rosion through mixed mode of inhibition. SEM - EDX studies show the adsorption of catechin monomers which forms a protective layer over the MS surface. Both the tea extracts were found to obey the Langmuir adsorption isotherm and the thermodynamic parameters prove the physical adsorption of the phytoconstituents. The HPLC Figure 8SEM images of mild steel in 1M HCl medium(a) absence of inhibitor (b) GT 1, and (c) GT 2 extractsCORROSION INHIBITION OF MILD STEEL IN SCIENTIFIC CONTRIBUTIONS OIL & GASNOFRIZALVOL. 35,NO. 1,APRIL2012 : 11 - 24aMag:1.5 KX 10umbcMag:1.5 KX 10umMag:1.5 KX 10um22technique proved to be an indispensable tool for the simultaneous determination of the active components of the green tea extracts that are responsible for the inhibition of MS corrosion.V. RECOMMENDATIONTheHPLCtechniquehasproventobean essentialtoolforsimultaneousdeterminationof catechinmonomersthatareresponsibleforthe corrosioninhibitionofmildsteel.Thistechnique can be used to explore different corrosion inhibition mechanismforvariouscorrosivemediaviz., H2SO4,basicelectrolytes(e.g,NaOH)andneutral electrolytes(e.g,NaCl)aswellasforvarious metals viz., Zn, Cu dan Al. The active constituents fromothernaturalproductscontainingalkaloids, avonoids and polyphenols for corrosion inhibition of metals can be similarly determined. In addition, through the same technique, the antioxidant studies of these plant extracts can be correlated to the corrosion inhibition properties.REFERENCES1.Anthony,N.,Malarvizhi,E.,Maheshwari, P., Rajendran, S., & Palaniswamy, N. (2004). Corrosion inhibition by caffeine: Mn2+ system. Indianjournalofchemicaltechnology,11(3), 346-350.2.Ashassi-Sorkhabi,H.,Shaabani,B.,& Seifzadeh, D. (2005). Effect of some pyrimidinic Shciffbasesonthecorrosionofmildsteelin hydrochloric acid solution. Electrochimica acta, 50(16-17), 3446-3452.3.Benabdellah,M.,Touzani,R.,Aouniti,A., Dafali,A.,ElKadiri,S.,Hammouti,B.,& Benkaddour,M.(2007).Inhibitiveactionof some bipyrazolic compounds on the corrosion of steel in 1 M HCl:: Part I: Electrochemical study. Materials Chemistry and Physics, 105(2-3), 373-379.4.Bentiss,F.,Lebrini,M.,Lagrene,M., Traisnel, M., Elfarouk, A., & Vezin, H. (2007). The inuence of some new 2, 5-disubstituted 1, 3, 4-thiadiazoles on the corrosion behaviour of mild steel in 1 M HCl solution: AC impedance study and theoretical approach. Electrochimica acta, 52(24), 6865-6872.5.Bentiss, F., Traisnel, M., Chaibi, N., Mernari, B., Vezin, H., & Lagrene, M. 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Bothi,R.P.,Abdul,R.A.,Hasnah,O.,& Khalijah, A. (2010). Inhibitory Effect of Kopsia Singapurensis Extract on the Corrosion Behavior of Mild Steel in Acid Media. Acta Phys. Chim. Sin, 26(8), 2171-2176.11.Duke,S.O.,Romagni,J.G.,&Dayan,F. E.(2000).Naturalproductsassourcesfor newmechanismsofherbicidalaction.Crop Protection, 19(8-10), 583-589.12. El-Etre,A.(2003).Inhibitionofaluminum corrosionusingOpuntiaextract.Corrosion Science, 45(11), 2485-2495.13. El-Etre, A., Abdallah,M.,&El-Tantawy,Z. (2005). Corrosion inhibition of some metals using lawsonia extract. Corrosion Science, 47(2), 385-395.14. Fallavena, T., Antonow, M., & Gonalves, R. S. (2006). Caffeine as non-toxic corrosion inhibitor for copper in aqueous solutions of potassium ni-trate. Applied surface science, 253(2), 566-571.CORROSION INHIBITION OF MILD STEEL IN SCIENTIFIC CONTRIBUTIONS OIL & GASNOFRIZALVOL. 35,NO. 1,APRIL2012 : 11 - 24

2315. Fan, H. B., Fu, C. Y., Wang, H. L., Guo, X. P., & Zheng, J. S. (2002). Inhibition of corrosion of mild steel by sodium n, n-diethyl dithiocarbamate in hydrochloric acid solution. British Corrosion Journal, 37(2), 122-125.16. Fernandez,P.,Martin,M.,Gonzalez,A., &Pablos,F.(2000).HPLCdeterminationof catechins and caffeine in tea. Differentiation of green,blackandinstantteas. Analyst,125(3), 421-425.17. Hamilton-Miller,J.(1995).Antimicrobial propertiesoftea(CamelliasinensisL.). Antimicrobial agents and chemotherapy, 39(11), 2375.18. Hara, Y. (2006). 3 Prophylactic Functions of Tea Catechins.Protectiveeffectsofteaonhuman health, 16.19. Hosseini, M., Ehteshamzadeh, M., & Shahrabi, T.(2007).Protectionofmildsteelcorrosion withSchiffbasesin0.5MH2SO4solution. Electrochimica acta, 52(11), 3680-3685.20. Hosseini,M.,Mertens,S.F.L.,&Ar-shadi , M. R. ( 2003) . 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Technol, 97(5), 790793.27. Maoela,M.S., Arotiba,O. A.,Baker,P.G. L.,Mabusela,W.T.,Jahed,N.,Songa,E. A.,&Iwuoha,E.I.(2009).Electroanalytical determinationofcatechinflavonoidinethyl acetateextractsofMedicinalPlants.Int.J. Electrochem. Sci, 4, 1497-1510.28. Morad,M.,&El-Dean,A.(2006).2,2-Dithiobis(3-cyano-4,6-dimethylpyridine):A newclassofacidcorrosioninhibitorsformild steel. Corrosion Science, 48(11), 3398-3412.29. Nishitani,E.,&Sagesaka,Y.M.(2004). Simultaneous determination of catechins, caffeine and other phenolic compounds in tea using new HPLC method. Journal of Food Composition and Analysis, 17(5), 675-685.30. Nmai,C.K.(2004).Multi-functionalorganic corrosioninhibitor.CementandConcrete Composites, 26(3), 199-207.31. Rahim,A.A.,&Kassim,J.(2008).Recent DevelopmentofVegetalTanninsinCorrosion Protection of Iron and Steel. Recent Patents on Materials Science, 1(3), 223-231.32. Rahim, A. A., Rocca, E., Steinmetz, J., & Jain Kassim, M. (2008). 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G., Vadivel, P., & Kumar, K. P. V. (2001). Tea wastes as corrosion inhibitor for mild steel in acid medium. J. Electrochem. Soc. India, 50, 143-146.38. Setiawan, V. W., Zhang, Z. F., Yu, G. P., Lu, Q. Y., Li, Y. L., Lu, M. L., Wang, M. R., Guo, C. H., Yu, S. Z., & Kurtz, R. C. (2001). Protective effect of green tea on the risks of chronic gastritis andstomachcancer.Internationaljournalof cancer, 92(4), 600-604.39. Shahrabi,T.,Tavakholi,H.,&Hosseini, M.(2007).Corrosioninhibitionofcopperin sulphuricacidbysomenitrogenheterocyclic compounds.Anti-CorrosionMethodsand Materials, 54(5), 308-313.40. Taniguchi, S., Kuroda, K., Doi, K. I., Inada, K., Yoshikado, N., Yoneda, Y., Tanabe, M., Shibata, T., Yoshida, T., & Hatono, T. (2007). Evaluation of gambir quality based on quantitative analysis ofpolyphenolicconstituents. Yakugakuzasshi, 127(8), 1291-1300.41. Wang,H.,Helliwell,K.,&You,X.(2000). Isocratic elution system for the determination of catechins,caffeineandgallicacidingreentea using HPLC. Food chemistry, 68(1), 115-121.42. Zhong, L., Goldberg, M. S., Gao, Y. T., Han-ley,J. A.,Parent,M..,&Jin,F.(2001). A population-basedcase-controlstudyoflung cancer and green tea consumption among women living in Shanghai, China. Epidemiology, 12(6), 695-700.CORROSION INHIBITION OF MILD STEEL IN SCIENTIFIC CONTRIBUTIONS OIL & GASNOFRIZALVOL. 35,NO. 1,APRIL2012 : 11 - 24

25 THE IMPROVEMENT OF MERCURY REMOVAL IN NATURAL GAS BY ACTIVATED CARBONIMPREGNATED WITH ZINC CHLORIDELisna RosmayatiTechnological Assessor at LEMIGAS R & D Centre for Oil and Gas Technology Jl. Ciledug Raya, Kav. 109, Cipulir, Kebayoran Lama, P.O. Box 1089/JKT, Jakarta Selatan 12230INDONESIATromol Pos: 6022/KBYB-Jakarta 12120,Telephone: 62-21-7394422, Faxsimile: 62-21-7246150 First Registered on January 30th 2012; Received after Corection on March 14th 2012Publication Approval on : April 30th 2012ABSTRACTNatural gas being produced from gas elds around Indonesia areas, along with a large number of other harmful substances (CO2,H2S, RSH,COS etc) often contains mercury. Even in small amounts, mercury and its compounds have an extremely harmful effect on human health. Mercury content in the natural gas should be removed to avoid equipment damage in the gas processing plant or the pipeline transmission system from mercury amalgamation and embrittlement of aluminium. Mercury can be removed by using adsorption processes such as activated carbon that is impregnated with chlor, iodine or sulfur.This research is dealing with the process of mercury removal from gas based on principle of adsorption and of chemisorption of mercury by means of activated carbon impregnated with ZnCl2. Time of impregnation is a signicant variable that can effect adsorption capacity. The experiment results showed that ZnCl2 impregnation time of 12 hours signicantly enhanced the adsorptive capacity for mercury vapour. Keywords: mercury removal, activated carbon, impregnated zinc chlorideI. INTRODUCTIONMercury is a trace element in the natural gas with relatively low contents. Mercury is vaporized from the natural gas and exists as elemental mercury (Hg0). Mercury is emitted to the atmosphere as a hazard air pollutant if without effective gas purication systems. Generally, mercury can be removed from the natural gasthroughactivatedcarbons.Inthenaturalgas processingindustry,activatedcarbonisfrequently employedfortheremovalofmercurytoprotect aluminum heat exchangers as well as providing a safe working environment at the plant. Mercury content in the natural gas should be removed to avoid damaging equipment in the gas processing plant or the pipeline transmissionsystemfrommercuryamalgamation andembrittlementofaluminium.Mercuryisthen removedbyusingadsorptionprocessessuchas activatedcarbonthatisimpregnatedwithzinc chloride (ZnCl2).Elementalmercury(Hgo)isoxidisedtoform mercuric oxide (HgO), mercuric chloride (HgCl2) and mercurous chloride (Hg2Cl2). Only a small amount ofvapor-phasemercuryisremovedbyparticulate controldevices,e.g.electrostaticprecipitatorsor bag house and the rest are emitted to the atmosphere asahazardairpollutantifwithouteffectivegas purication systems. Mercury may accumulate and concentratewithinlivingorganismbyfoodchain, causingvariousdiseasesanddisorderstoanimals andhumans.Generally,oxidizedmercurycanbe removed from the natural gas or ue gas through wet scrubbing or dry sorbent injection. Adsorptionbyactivatedcarbons,particularly those impregnated with sulfur (S), chloride (Cl) or Iodine (I), is a technology that offers great potential for the removal of Hgo from the natural gas.The main scope of this paper is to investigate the removal of Hgo fromthenaturalgasbygranularactivatedcarbons treated with zinc chloride (ZnCl2) impregnation. The effects of ZnCl2 time impregnation at an adsorption temperatureandZnCl2solutionconcentrationon themercuryremovalperformancewerestudied.26The treatment with ZnCl2 impregnation on activated carbon have been effectively reducing the mercury content in natural gas. Hypothesis of this research is increasing time of ZnCl2 impregnation will improve the mercury adsorption by activated carbons. II. EXPERIMENTALA. Sample PreparationThe test material in this research used was carbon blackoractivatedcharcoalandthechemicalused were Zinc Chloride (ZnCl2) 5%, Chloride Acid (HCl) 0,5 N dan 5%, Iodium ( I2) 0,1 N, Sodium thiosulphat (Na2S2O7)0,1N,Kaliumdichromat(K2Cr2O7)0,1 N, Indicator, Whatman paper No.40 and distillation water.Commercialgranularactivatedcarbonswas sieved to have 70 mesh size, prepared from coconut shellscharcoalbyactivationat700oCinatubular stainles steel reactor. The obtained Activated carbons werethenbyimpregnatedwith5%(w/v)ZnCl2 solution for 6, 12 and 24 hours. Impregnated activated carbons were dried in an oven at 90oC, cooled down to the room temperature and then stored in a desiccators for future use. B. Sample CharacterizationThecharacteristicsofadsorbentsamplewere determinedbyIodinenumber,BET(Brunauer-Emmett-Teller) and Scanning Electron Microscope (SEM).TheIodineNumberisdeterminedby iodometricmethod.BET analysisisameasurement ofsurfaceareaandpore distributionbyadsorption anddesorptionofN2gas. SEM-EDXisascanning El ect ronMi croscopyt o determine the micro structure of a material including texture, morphology,composition andchristallographyparticle surface.Themorphologyis monitoredbySEManalysis were shape, size and particle formation.EDX(Energy Dispersive X-ray), is a material characterization method using x-rayemission.TheResult dataofEDXanalysiswill showtheconstituentofCl-impregnatedactivated carbons (see Table 1). The EDX analysis used ZAF method quantitative analysis.C. Adsorption of Mercury Removal from Natural GasThe working principal of this mercury removal equipmentistofollowthenaturalgascontaining mercuryvaporatknownconcentrationthroughan adsorbent. An amount of mercury will be adsorbed and the remaining mercury in the natural gas will be adsorbed by KMnO4 solution.After that the solution is analyzed by Lumex mercury analyzer. The volume of the owing gas is measuredby a wet test meter equipment. A schematic diagram of the experimental setup usedinmercuryadsorptiontestsisshownin Figure 1.Figure 1An experimental setup of mercury adsorption testElement Mass %C K 81.99O K 5.87Al K 1.32Si K 0.23Cl K 4.94Zn K 5.65Total 100.00Table 1Adsorbent composition analyzedby ZAF methodTHE IMPROVEMENT OF MERCURY REMOVAL SCIENTIFIC CONTRIBUTIONS OIL & GASLISNA ROSMAYATIVOL. 35,NO. 1,APRIL2012 : 25 - 29

27Measurement of standard mercury and mercury sample in Outlet Adsorber-The natural gas is own through mercury cylinder placed in a water bath at a temperature of 37oC. -The gas from the outlet of the mercury cylinder is put into a mercury solution ( KMnO4 + H2SO4) .-Themercuryconcentrationisinthesolution analyzedbyMercuryAnalyzer(Lumex91), measured in g/m3.III. RESULTS AND DISCUSSIONA. Experimental ResultSEM and EDX CharacterizationB. DiscussionAdsorption results of Hg0 onto the untreated as wellasimpregnatedZnCl2activatedcarbonsfor 6,8,12and24-htestingtimeareshownin Figure4and5.ItcanbeseenthatHgcon-centration at the outlet of adsorber having no adsorbent is 27.633 g/m3 (Table 3). For the untreated activated carbon, the amount of Hgo adsorbed decreased progressively, indicating a typical physisorption mechanism due to van der Waalsforcesbetweentheadsorbateand the adsorbent. For the activated carbon with impregnatedofZnCl2solution,theamount ofHgoadsorbedincreasedprogressively, becauseZnCl2propertiescanbehavioras chemical activator, increasing the adsorption capacityoftheactivatedcarbonandZnCl2 solutioncancreatenewporesandcanform C-Cl bonding whenever Cl group can attach the mercury (Hg) by chemical bonding to be HgCl or HgCl2Optimum adsorption occurs for adsorbent of12 hours impregnation time and in vertical positionadsorber.Amountofmercury adsorbedintheadsorbentwas96%. ImpregnationwithZnCl2,particularlywith thesolutionconcentrationof5%,increased theHg0adsorptionamountsignificantly. Thisoptimumadsorptionprobablydueto the occurrence of chemisorption by forming chemicalbondsbetweentheadsorbateand thechloridespresentontheadsorbent.Itis worth to note that the impregnation of ZnCl2 longer than 12 hours decreased the mercury adsorptionoftheactivatedcarbonsamples. This probably due to the blockage of internal pores by incorporated ZnCl2 molecules. Figure 2SEM foto of the sample at T = 700OC,12 h impregnationafter activationFigure 3EDX result of the sample at T = 700OC,12 h impregnation after activation700 219,26 463,17Temperature (oC)Pore diametre (nm)Surface Area (m2/g)Table 2 BET (Brunauer-Emmett-Teller) resultBET CharacterizationTHE IMPROVEMENT OF MERCURY REMOVAL SCIENTIFIC CONTRIBUTIONS OIL & GASLISNA ROSMAYATIVOL. 35,NO. 1,APRIL2012 : 25 - 2928While generally, for pure physisorption process,theadsorptivecapacityofthe activated carbon increases with increasing the specic surface area, in this research is suggested the occurrence of chemisorption ofelementalmercuryontotheCl-impregnated samples. Hg0 adsorbed onto the Cl-impregnated samples attributed to a combined physisorption and chemisorption. A typical physisorption mechanism due to van de Waals forces between the adsorbate andtheadsorbent.Themechanismof chemisorptions of elemental mercury onto the Cl-impregnated activated carbons was proposed as follows. During impregnation, ZnCl2 was reduced by the carbon content in activated carbons and some Cl-contained complexes were formed:ZnCl2 + CnHxOy Zn+[ Cl2-CnHxOy ]TheseCl-containedfunctionalgroups accountedforthechemisorptionofHgo through the following reactions below :Hg0 + [Cl]-[HgCl]+ + 2e andHg0 + 2[Cl]-[HgCl2] + 2eInthepresenceofextraClspecies,the mercuryatomevenistendedtoadopt four-coordination numbers as:[HgCl2] + 2[Cl]-[HgCl4] 2- ThecharacterizationtestbySEM-EDX instrument has detected Cl-contained functional group on the activated carbon adsorbent. IV. CONCLUSIONS1. ZnCl2aschemicalactivatorisvery important for increasing the adsorption capacityactivatedcarbonbecauseit can create new pores and can form C-Cl bonding the Cl group can then catch the mercurybychemicalbondingtobe HgCl or HgCl22. Hg0 adsorbed onto the Cl-impregnated adsorbentattributedtoacombined physisorption and chemisorption3. Mercuryadsorptionbyactivated carbons that impregnated ZnCl2 for 12 hours shows the best result. 1Without adsorbent 27.6332Adsorbent without ZnCl22.653 Horizontal Adsorber 3Adsorbent without ZnCl22.564 Vertical Adsorber PositionExperiment numberType of SampleMeasurementHg in KMnO4 solution (g/m3)Adsorption Result and Mercury AnalysisTable3Hg concentration measurement without adsorbent,and adsorbent without ZnCl2Figure 4Mercury concentration at adsorber outlet horizontal position Figure 5Mercury concentration at adsorber outlet vertical positionTHE IMPROVEMENT OF MERCURY REMOVAL SCIENTIFIC CONTRIBUTIONS OIL & GASLISNA ROSMAYATIVOL. 35,NO. 1,APRIL2012 : 25 - 29

294.AschemisorptionofmercurybyCl-contained functionalgroups,createdbyZnCl2impregna-tion, were probably due to the formation of vari-ous complexes.5.Theexperimenttestshowedthatindicating theimpregnatedadsorbentwasabletoadsorp mercury (Hg) as much as27.629,94 g/m3.6.The mechanism of chemisorptions of elemental mercuryontotheCl-impregnatedactivated carbons.REFERENCES1. AWWA.1974.StandardforGranularCarbon. AWWA B604-74. Colorado.2. ASTMD4607-94.StandardTestMethodfor DeterminationofIodineNumberofActivated Carbon.3. ASTMD1510-03.StandardTestMethod forDeterminationofCarbonBlack-Iodine Adsorption Number 4.Radisav D.Vidic, Control of Mercury Emissions inFluegasesbyActivatedCarbonAdsorption, University of Pittsburgh, PA 15261.5.RongYan;YuenLingNg,Bench-Scale ExperimentalStudyonTheEffectofFluegas Composition on Mercury Removal by Activated carbonAdsorption.Energy&Fuels2003,17, 1528 1535.6.HESSLER, J.W. 1951. Active Carbon, Chemical Publishing Co Inc. Brooklyn.7.HancaiZeng,FengJin,Removalofelemental mercuryfromcoalcombustionfluegasby chloride-impregnated activated carbon. Science Direct, Revised 13 May 2003.8.Kaut ubhaMohant y, Preparat i onand Characterizationofactivatedcarbonsfrom Sterculiaalatanutshellbychemicalactivation withzincchloridetoremovephenolfrom wastewater. Springer Science, Revised : July 5, 2006.9.GiacomoCorvini,JulieStiltner,Mercury RemovalfromNaturalGasandLiquidStream. UOP LLC, 2002.THE IMPROVEMENT OF MERCURY REMOVAL SCIENTIFIC CONTRIBUTIONS OIL & GASLISNA ROSMAYATIVOL. 35,NO. 1,APRIL2012 : 25 - 2930

31COMPARISION DEPOSIT FORMATION ON THE VALVE DIESEL ENGINE CAUSED BY BIODIESEL ANDPETROLEUM DIESEL FUELSMaymuchar1), and Ismoyo Suro Waskito2)1)Researcher, 2)Litkayasa, at LEMIGAS R & D Centre for Oil and Gas Technology Jl. Ciledug Raya, Kav. 109, Cipulir, Kebayoran Lama, P.O. Box 1089/JKT, Jakarta Selatan 12230 INDONESIATromol Pos: 6022/KBYB-Jakarta 12120,Telephone: 62-21-7394422, Faxsimile: 62-21-7246150 First Registered on December 13rd 2011; Received after Corection on April 17th 2012Publication Approval on : April 30th 2012ABSTRACTThe research on the inuence of the biodiesel to the formation of deposits on the intake and exhaust valves diesel engine has been carried out by means analysis of merit rating. The fuels used on this study are FAME (B-100), a mixture of 50% (v)ofFAME in diesel fuel 48 (B-50), and diesel fuel 48 (B-0). The objective of this research is to obtain data which represent the inuence of the biodiesel to the formation of deposits on the intake and exhaust valve diesel engine. The test used a diesel engine driving 5 KVA generator which is operated for 100 hours with 1.000 Watt electrical load. The results of the studyshow that the use of either FAME or biodiesel as alternative fuel in the diesel engine generator 5 KVA has a positive effect on reducing the deposit on the intake and exhaust valves.Keywords: biodiesel, intake valve, exhaust valve, diesel engineI. INTRODUCTIONTheuseofbiodieselasanalternativefuelfor diesel engines is a government policy which aim to developtheapplicationofbiofuels.Thisprogram has already stated in Presidential Decree No. 1 2006. Thisprogrambecomesaprioritytodecreasethe dependence on fossil fuels in the future. ThespecificationofDieselFuel48or51 statedintheDirectorateGeneralofOilandGas No.SK.3675K/24/DJM/2006datedMarch17, additionofFAMEintodieselfuelupto10%of volumeisallowed.This10%additionofFAME isstilldebatable,especiallybythemanufacturers ofvehiclesandmachinery.AccordingtoWorld Association of the vehicle and engine manufacturers (ACEA, Alliance, EMA, JAMA) in the World-Wide Fuel Charter (WWFC) September 2006 still restricts thecontentofFAMEindieselfueltoamaximum of 5% by volume of Categories 1, 2 and 3, whereas Category4ismentionednon-detectable.The limitationofbiodieselisduetothenegativeside athighconcentration,i.e:unstabletooxidation, theproblemofviscosityatlowtemperatures, hygroscopicproperties,thecompatibilityofthe components of natural rubber seals and the formation of deposits on parts of the engine including the intake and exhaust valve.Intake and exhaust valve are parts of the engine mechanismthatarelocatedoncylinderhead.The functionofthesevalvearetoregulateuidorgas inandoutthecombustionchamber.Intakevalve regulates the fresh air needed for combustion coming into the cylinder. This air intake process occurs due to the piston movement from top to bottom dead center. Whereas the exhaust valve is to let the combusted gas ows from the combustion chamber. The mechanism of exhaust gases of the combustion occurs in exhaust stroke where the piston moves from the bottom dead center to the top dead center. The more uid can move in and out of the engine the more efcient and power the engine is. Therefore, the intake and exhaust valve plays a signicant role in an engines performance.Theobjectiveofthisresearchistoobtaindata which represent the inuence of the biodiesel to the formation of deposits on the intake and exhaust valve diesel engine. 32 Type:4 stroke, 1 cylinder, Horizontal Type Injection :Direct Injection Displacement :583 cc Power (Cont.) :9,2 HP / 2400 rpm Power (Max) :10,5 HP / 2400 rpmTable 1Test engine specicationFigure2Parts of valve observedCOMPARISION DEPOSIT FORMATION ON THE VALVESCIENTIFIC CONTRIBUTIONS OIL & GASMAYMUCHAR AND ISMOYO SURO WASKITOVOL. 35,NO. 1,APRIL2012 : 31 - 37II. RESEARCH PREPARATION AND METHODA. Test FuelThereare3kindsoffuelusedinthisresearch that is diesel fuel with cetane number 48, Fatty Acid MethylEster(FAME)orbiodiesel,anddieselfuel and biodiesel blend.1.DieselFuel 48 gradeOne of the fuels used is diesel fuel 48 which has a minimum cetane number 48. This fuel is used as a reference fuel for comparison to other fuels. The fuel is later referred to as B-0.2. FamePalm-based biodiesel is often called FAME has a chemical formula: OIIR C O CH3FAME is the result of trigliseride process of palm oilwithmethanol(CH3OH)viatransesterication processusingacatalystofsodiumhydroxide (NaOH). The fuel is later referred to as B-100.3. BiodieselBiodiesel is a mixture of petroleum diesel fuel 48 with biodiesel FAME. The blending concentrations are respectively 50% and then called as B-50.B. Test EngineDiesel engine generator with a 5 KVA capacity asatestenginethatiswidelyusedincommunity asapowersupplyforsmallhouses.Themain specication of the diesel engine used are listed in Table 1.The test engine shows on Figure 1.Figure1Diesel engine generator 5 KVA The research was conducted in two phases of test; fuel characteristics test and applied test. The fuel used bythetestparameterstestedcharacteristicscetane number, distillation, viscosity, density and lubricity in accordance with the specications and standard test methods. The applied test is carried out by using a diesel engine driving generator. The 5KVA generator dieselengineisrunbyfuelB-0,B-50andB-100. Each of the fuel was used to operate the engine test for 100 hours with 1.000 Watt electric load. After 100

33Table 2Characteristic B-0 andB-50 test result10 Calorific value Mj/Kg 38.3 - D2409 Lubricity, scare diameter micron 196 - D60798 Sulphur content % m/m 0,01 Max 0,01 D12667 Acid number mg-KOH/g 0,32 max 0,8 D6646 Carbon residu % massa 0,028 max 0,05 D45305 Cooper corrosion No.ASTM No.1 max No. 3 D1304 Flash point C 134 min 100 D933 Cetane number CN 51,4 min 51 D6132 Density @40C, kg/m3884 850 - 890 D12981 Kinematic viscosity @40C mm2/s 6,0 2,3-6,0 D445No Characteristic Unit B-100Biodiesel specificationTest methodCOMPARISION DEPOSIT FORMATION ON THE VALVESCIENTIFIC CONTRIBUTIONS OIL & GASMAYMUCHAR AND ISMOYO SURO WASKITOVOL. 35,NO. 1,APRIL2012 : 31 - 37hours of operation, the engine was overhauled and the deposits on valve was assessed and weighed.Intake and exhaust valve for each test of each fuel must be in new condition. Replacing parts were also done to the parts which affect the performance of the engine such as fuel lters, oil lters, etc. The Evaluation is done by comparing the results ofassessmentofintakeandexhaustvalveengine withfuelB-100,B-50withB-0.Valvecondition assessmentwasdoneintwowaysthatismerit analysis by using standard CEC (The Coordinating EuropeanCouncil)andweighingthedeposit.The observed parts of the valve arehead/topside valve and tulips/ underside valve (Figure 2).III. RESULT AND DISCUSSIONA. Characteristic FuelThelaboratorytestresultsshowthemain characteristics of the sample B-0 used as reference fuel and B-50 whichmeets the requirements of test specicationssetbythegovernmentaccordingto Director General of Oil and Gas Decree No.3675.K/24/4 9 2 0 5 0 D445B501 Ki i i i @ 40C24 4No Characteristic UnitResultDiesel fuel 48 specificationTest methodB-0D664 7 Acid number mg KOH/g 0 09 0 2 Max 0 6D1306 Carbon residu % massa 0,01 0.09 Max 0,1 D45305 Cooper corrosion No.ASTM No.1 No.1 Max No 1D6134 Flash point C 67 96,5 Min60 D933 Cetane number CN 48,6 50,2 Min484,9 2,0-5,0 D4452 Density @ 40C, kg/m3849 867 815-870 D12981 Kinematic viscosity @ 40C mm2/s 4,4D607910 Calorific value Mj/Kg 4377 39.9 - D2409 Lubricity, scare diameter micron 286 205 -D6648 Sulphur content % m/m 0,15 0.09 Max 0,35 D12667 Acid number mg-KOH/g 0,09 0.2 Max 0,6Table 3Characteristic B-100 test result34Figure 4Deposit on tulip intake valve B-0, B-50 and B-100After 100 hour operationFigure 3Deposit on top head intake valve for B-0, B-50 and B-100 After 100 hour OperationB-0 B-50 B-100Merit Rating8,643 8,643 8,643B50:B0 B-100:B00,00% 0,00%EffectTable 5Merit rating and effect deposittop head intake valveCOMPARISION DEPOSIT FORMATION ON THE VALVESCIENTIFIC CONTRIBUTIONS OIL & GASMAYMUCHAR AND ISMOYO SURO WASKITOVOL. 35,NO. 1,APRIL2012 : 31 - 37DJM/2006 decree dated March 17, 2006 for diesel fuel 48. The result is showed in Table 2.Fromtheresultsoflaboratoryteststhemain characteristicsofthesampleB-100,whichisused asbiodieselfuelmeetstherequirementsoftest specications set by the government according to the Indonesian National Standard as outlined in the SNI 04-7182-2006. The result is shown in Table 3.B. Rating Top Head and Tulip Intake ValveRating deposit at the top ofintake valve has been donefor fuel B-0, B-50, and B-100. The results of depositratingtopheadintakevalveforB-0,B-50 and B-100 is shown in Table 5. From the results of merit rating deposits at the top head intake valve,the value of merit rating for B-0, B-50 and B-100 is the same,8.643 respectively.

35Therearenodifferencesshownintheformation ofdepositsonintakevalvetopheadinbiodiesel addition.Physicallythedepositonthetophead intake valve for fuel B-0, B-50 and B-100 is shown in Figure 3.Theresultsoftheintakevalvetulipsdeposit ratingtoB-0,B-50andB-100isshowninTable 6. From the results merit rating tulips intake valve deposits, the value of merit rating to B-0, B-50 and B-100are8.643,9.643and9.708,respectively. Value shows the addition of biodiesel tends to reduce depositformationintheintakevalvetulips.The value of merit rating tulips intake valve B-50 to B-0 is 10,37% and B-100 to B-0rises 12.32%.Physically deposits on the tulips intake valve to fuel B-0, B-50 and B-100 after 100 hours of operation is shown in Figure 4.Weightmeasurementsshowedthattheintake valve deposits on the B-0 is heavier than the B-50 and B100 (see Table 7). Although the results of the rating on the top head have the same value but the tulip rating results B-0 are relatively poor. C. Rating Top Head and Tulip Exhaust ValveThe results merit rating top head exhaust valve deposits the value of merit rating to B-0, B-50 and B-100 respectively 8.342, 8.643, and 8.643 (see Table 8).Thevalueshowsthattheadditionofbiodiesel tendstoreducedepositformationinthetophead exhaustvalve. Theeffectvalueofmeritratingtop headexhaustvalveB-50toB-0rose3.60%,and B-100 to B-0 rose 3.60%.Physically deposit on top head exhaust valve to fuel B-0, B-50 and B-100 after 100 hours of operation is shown in Figure 5.B-0 B-50 B-100Merit Rating8,643 9,643 9,708B50:B0 B-100:B010,37% 12,32%EffectTable 6Merit rating and effect deposit Tulip intake valve 0 hour 100 hoursB 0 470 005 471 655 0 1650Inlet Valve Weight (gr)Effect Fuel B-0 470.005 471.655 0.1650 B-50 470.400 470.944 0.0544 B-100 475.976 476.568 0.0592Table 7Weight Measurement of Intake ValveB-0 B-50 B-1008 342 8 643 8 643Merit Rating8,342 8,643 8,643B50:B0 B-100:B03,60% 3,60%EffectTable 8Merit rating and effect deposit Top head exhaust valve Figure 5 Deposit on top head exhaust valve B-0, B-50 and B-100After 100 hour operationCOMPARISION DEPOSIT FORMATION ON THE VALVESCIENTIFIC CONTRIBUTIONS OIL & GASMAYMUCHAR AND ISMOYO SURO WASKITOVOL. 35,NO. 1,APRIL2012 : 31 - 3736Rating deposits in the exhaust valve tulip has been donefor the fuel B-0, B-50, B-100 and the resultis shown in Table 9. From the results merit rating tulips exhaust valve deposits, the value of merit rating to B-0, B-50 and B-100 are respectively 4.812, 5.237, and6.827.Thevalueshowsthattheadditionof biodieseltendstoreducedepositformationinthe exhaust valve tulips. The value of merit rating tulips exhaustvalvefortheB-50:B-0rose8.84%,and B-100: B-0 rose 41.87%. Physically the deposits on the tulips exhaust valve to fuel B-0, B-50 and B-100 after 100 hours of operation is shown in Figure 6.The results of weighing the deposit that occurs at the outlet valve is shown in Table 10.IV. CONCLUSIONSAfterassessingpartsoftheintakeandexhaust valve in 100-hour-engine operation to see the impact ofusingbiodieselontheformationofdepositson enginevalves5 KVADieselgenerator,itcanbe summed up as follows:-Theratingofthevalvesaboveshowsthatthe use of biodiesel as a fuel substitution fordiesel fuel on the generator 5 KVA diesel engine has a positive effect on reduction of deposit formation on valves, especially the tulips.-Biodieseldoesnotmakeadifferenceinthe formation of deposits on the top head intake valve, the value of merit rating to B-0, B-50 and B-100 is the same that is 8.643.-The addition of biodiesel tends to reduce the formationofdepositsontheintakevalve tulips,theeffectoftulipsratingB-50:B-0 andB-100:B-0are10,37%and12.32% respectively.B-0 B-50 B-1004,812 5,237 6,827B50:B0 B-100:B08,84% 41,87%Merit RatingEffectTable 9Merit rating and effect deposit Tulip exhaust valve 0 hour 100 hours B-0 409.651 418.251 0.8600 B-50 403.401 406.325 0.2924 B-100 403.098 405.389 0.2291Exhaust Valve Weight (gr)Fuel EffectTable 10Weight Measurement of Exhaust ValveFigure 6Deposit on tulip exhaust valve B-0, B-50 and B-100 After 100 hour operationCOMPARISION DEPOSIT FORMATION ON THE VALVESCIENTIFIC CONTRIBUTIONS OIL & GASMAYMUCHAR AND ISMOYO SURO WASKITOVOL. 35,NO. 1,APRIL2012 : 31 - 37

37-Theadditionofbiodieseltendstoreducethe formationofdepositsonthetopheadexhaust valve,theeffectoftulipsratingB-50:B-0and B-100: B-0 are 3.60%.-The effect of addition of biodiesel 50% to diesel fuel tends to reduce the formation of deposits in the tulip exhaust valves 8.84%, but using 100% biofuel will reduce deposit on the exhaust valve 41.87%.REFERENCES1.ACEA, Alliance,EMA,JAMA,2002,World-Wide Fuel Charter, December 20022.Ayhan D, Biodiesel; A Realistic Fuel Alternative forDieselEngines,SpringerVerlagLondon Limited, 20083.BadanStandardisasiNasional,2006,Standar Nasional Indonesia Biodiesel, SNI 04-7182-2006, Jakarta4.Chevron Oronite, 1998, Diesel Fuels Technical Review, Chevron Product Company, USA5.DirjenMigas,1999,SpesikasiBahanBakar Jenis Minyak Solar, SK No. 3675.K/24/DJM/2006 tanggal 17 Maret 2006, Jakarta6.Knothe, G, Krahl J, Gerpen JV, The Biodiesel Handbook,AOCSPress,Champaign,Illinois, USA 2005 7.Keith Owen, Trevor Coley, 1995,Automotive FuelsReferenceBook,SocietyofAutomotive Engineers,Inc., USA8.UOP,1998,DieselFuelSpecificationsand Demandforthe21stCentury,UOPLLC,Des Plaines, Illinois, USA.COMPARISION DEPOSIT FORMATION ON THE VALVESCIENTIFIC CONTRIBUTIONS OIL & GASMAYMUCHAR AND ISMOYO SURO WASKITOVOL. 35,NO. 1,APRIL2012 : 31 - 3738

39DILUTE ACID PRETREATMENT AND ENZYMATICHYDROLYSIS OF LIGNOCELLULOSIC BIOMASSFOR BUTANOL PRODUCTION AS BIOFUELDevitra Saka Rani 1) and Cut Nanda Sari1)1) Researcher at LEMIGAS R & D Centre for Oil and Gas TechnologyJl. Ciledug Raya, Kav. 109, Cipulir, Kebayoran Lama, P.O. Box 1089/JKT, Jakarta Selatan 12230 INDONESIATromol Pos: 6022/KBYB-Jakarta 12120,Telephone: 62-21-7394422, Faxsimile: 62-21-7246150 First Registered onMarch 19th 2012; Received after Corection on April 19th 2012Publication Approval on : April 30th 2012ABSTRACTBiobutanolisoneofthepromisingbiofuelforsubstitutinggasoline.Biobutanolproduced from biomass fermentation using solventogenic clostridia which are able to convert a wide range of carbon sources to fuels such as butanol. Therefore, lignocellosic biomass has great potential as fermentation substrate for biobutanol production. Lignocellosic biomass should be hydrolized before fermentation by a pretreatment process and enzymatic hydrolysis. The various lignocellulosic biomasspretreatmentwillinuenceinbutanolproductiondependingonfermentablesugars content. The objective of this research is to get potential lignocellulosic biomass using dilute acid pretreatment and enzymatic hydrolysis process for biobutanol production. Eight types of biomass from sugarcane bagasse, rice straw, rice husk, empty fruit bunch (EFB) of palm oil, corn cob, pulp waste, traditional market organic waste, and microalgae were used in this experiment. After hydrolysis, the high result of total fermentable sugars in corn cobs, bagasse, rice straw, and rice husk, shows good opportunity of these biomass to be used as fermentation feedstocks for biobutanol production. In addition, pulp waste, organic waste, and microalgae are prospective as raw material but require more appropriate treatment either for to break down the cellulose/hemicellulose or toenhancereducingsugarcontent.Finemillinganddelignicationhavenosignicanteffect on cellulosic biomass conversion into fermentable sugars. Therefore, the production cost can be reduced. In order to enhance the sugar content and reduce the formation of inhibitor product, it is necessary to examine dilute acid pretreatment variations and appropriate operating conditions of enzymatic hydrolysis process.Keywords:biofuel,biobutanol,lignocellulosicbiomass,diluteacidpretreatment,enzymatic hydrolysisI. INTRODUCTION Biofuels development for fossil fuels replacement has increased in recent years. One of the promising biofuel for substituting gasoline is biobutanol, a four carbonalcoholproducedbybiomassfermentation usinganaerobicbacteria.Comparedtoethanol, butanol has many superior properties as an alternative fuel. Butanol contains more energy, less hygroscopic, andeasilymixwithgasolineinanyproportion. Furthermoretheair-fuelratioofbutanolinengine combustionchamberisclosetogasoline.Butanol can be used directly or blended with gasoline without any vehicle retrot. In addition, butanol is also can be supplied through the existing gasoline pipes without any problems1. Themostabundantsourcesofrenewable biomassislignocellulosicbiomassobtainedfrom energy crops, wood and agricultural residues2. Using biomasstoproduceenergycanpossiblysolvethe problems that world faces because of excessive use of fossil fuels, and may signicantly reduce greenhouse gasemissions,pollutionandwastemanagement problems1. Indonesia has great natural resources and biomass to produce biofuels. Agricultural residues, 40domestikorganicwasteandothernon-edibleare easily found in a large amount. According to Ministry ofEnergyandMineralResourcesRepublicof Indonesia,thepotencyofIndonesianbiomassfor energy is 49.81 GW, while installed capacity is only about1618MW.Itmightbecausedbyalackof biotechnology research for industrial-scale biofuels production. Anaerobicbacteriasuchassolventogenic clostridiaareabletoconvertawiderangeof carbohydratestobiofuelsandchemicalssuchas biobutanol.Therefore,theuseoflignocellosic biomassasasubstrateisgoodapproachfor biobutanolfermentation3.Butanolfermentationby different strains using various biomass substrates has been reported in recent years. These inovations may help reduce fermentation substrate costs4. Biobutanol fermentationtechnologyhaschangedrapidlyin thelastfewyearsandacommercialscaleprocess based on biomass materials is nearly achieved. The useoflignocellulosicsubstratesincombination with developed technology is expected to make the production of biobutanol economically viable3. Sincemicroorganismsdonothaveenzymesto digest cellulose, it is essential to treat lignocellosic materialsbeforefermentationinordertobreak itdownintosimplesugar1.Theproductionof fermentablesugarsfromlignocellulosicbiomass after initial mechanical process is usually carried out in two steps: a pretreatment process, and enzymatic cellulosehydrolysis5.Pretreatmentisacrucial processstepandithasbeenrecognizedasoneof themostexpensiveprocessingstepsincellulosic biomasstofermentablesugarsconversion.The pretreatment process needed to liberate the cellulose from the lignin seal and its crystalline structure thus makes cellulose more accessible to the enzymes that convert the carbohydrate polymers into fermentable sugars6.Oneofthemosteffectivepretreatment methodsforlignocellulosicbiomassisdiluteacid pretreatment5.Diluteacidhydrolysishasbeen extensivelyreviewedandisconsideredtobeone of the treatment methods with greater potential for wide-scale application. For a given material, the best conditions for hemicelluloses removal and recovery inthehydrolysatedonotalwaystranslateintothe bestenzymaticdigestibility.Enzymatichydrolysis isreactionusingspeciccellulaseenzymesthat brakes cellulose into glucose molecules1. Obstacles in the pretreatment and hydrolysis processes include theinsufcientconversionofcellulosetoglucose, highlignincontentwhichisrecalcitrantfraction, highuseofchemicalsand/orenergy,considerable waste production, and formation of by-products that inhibit fermentation 5. This research examine most of all Indonesian potential biomass such as sugarcane bagasse, rice straw, rice husk, empty fruit bunch of palmoil,corncob,pulpwaste,traditionalmarket organic waste, and microalgae. The objective of this researchistogetpotentiallignocellulosicbiomass usingcombinationofdiluteacidpretreatment andenzymatichydrolysisprocessforbiobutanol production.II. MATERIALS AND METHODSA. Biomass PreparationEight prepared biomass from sugarcane bagasse, rice straw, rice husk, empty fruit bunch (EFB) of palm oil, corn cob, pulp waste, traditional market organic waste, and microalgae are used in this experiment. The sugarcane bagasse is obtained from sugar mill, whereas EFB and pulp waste are collected from palm oil mill and pulp industry respectively. Two types of pulp waste, i.e TR (rough) and TF (ne) are used in this experiment. The biomass used in this study are shown in Figure 1. All of the biomass used are based on%drysolidexceptfororganicwastewhichis based on its % wet solid, because the structure and compositionofcarbohydratesmaybedegradedin the drying process and consequently affect reducing sugar yield7.B. Dilute Acid Pretreatment and Enzymatic HydrolysisDiluteacidpretreatmentwasconductedusing 0.5 - 4% sulphuric acid with 1.5-12.5% w/v biomass. The process was carried out in an autoclave either at 121C for 60 min or at 130C for 30 min. The mixture was then cooled to room temperature and followed by neutralization with NaOH 10 M. The hydrolysate wasnallyseparatedfromthesolidfraction.The hydrolisatewasthenexaminedforreducingsugar content,whilethesolidfractionwassubjectedto hydrolysisprocess.Thediluteacidpretreatment condition for each biomass is described in Table 1.In order to recognize the effect of lignin removal on reducing sugar enhancement, the delignication DILUTE ACID PRETREATMENT AND ENZYMATIC SCIENTIFIC CONTRIBUTIONS OIL & GASDEVITRA SAKA RANI AND CUT NANDA SARIVOL. 35,NO. 1,APRIL2012 : 39 - 48DILUTE ACID PRETREATMENT AND ENZYMATIC SCIENTIFIC CONTRIBUTIONS OIL & GASDEVITRA SAKA RANI AND CUT NANDA SARIVOL. 35,NO. 1,APRIL2012 : 39 - 48

41DILUTE ACID PRETREATMENT AND ENZYMATIC SCIENTIFIC CONTRIBUTIONS OIL & GASDEVITRA SAKA RANI AND CUT NANDA SARIVOL. 35,NO. 1,APRIL2012 : 39 - 48test was performed using pretreatment solid fraction from 3 biomass, i.e bagasse, rice husk, and rice straw. Thedelignicationprocesswasconductedbefore enzymatic hydrolysis, using 1.5% NaOH at 100C for60minutes8,thenneutralizedwithH2SO4and washed with destillate water. Figure 1Eight cellulosic biomass after mechanical preparation H2SO4 Temp.Time (%)(C) (min)1. Bagasse 8 10 0.5 130 302. Rice straw 98.6 1 121 603. Microalage 101.5 1 130 304. Rice husk 1115 1 121 605.Organic waste 30* 1 130 306.Corn cob10 1 121 607. EFB palm oil 1212.5 4 121 608.Pulp waste 10 1 130 30No. BiomassDilute acid pretreatment conditionDry Solid (%)*Wet solidTable 1Dilute acid pretreatment condition for each biomassDILUTE ACID PRETREATMENT AND ENZYMATIC SCIENTIFIC CONTRIBUTIONS OIL & GASDEVITRA SAKA RANI AND CUT NANDA SARIVOL. 35,NO. 1,APRIL2012 : 39 - 4842Thesolidfractionobtainedfromtheprevious process was then hydrolyzed using an enzyme mixture of Cellulase (Sigma, Cat. No. C1184) and Xylanase (Sigma, Cat. No. X2753). Each enzyme powder was dissolved 1 g/L in citrate buffer solution. Hydrolysis process was carried out in 500 ml Erlenmeyer ask containing250mlofenzymesolutionincitrate buffer, incubated in a shaker incubator at 50C and pH 4.8, with 120 rpm, for 72 hours. Finally, the ask wassterilizedtodenaturedenzymes.Hydrolysate from the enzymatic hydrolysis process was sampled for reducing sugar analysis. exhibits that the highest cellulose content found in pulp waste TF, followed by pulp waste TR, bagasse, and rice husk, respectively. The highest hemicellulose contentfoundinorganicwaste,followedbycorn cobs,andmicroalgae,respectively.Thehighest lignin content found in the EFB palm oil, followed bybagasseandorganicwasterespectively.EFB Palmoilwhichhashighestlignincontentisnot appropriateforconventionalbutanolfermentation becauseofhighenergyconsumeforpretreatment andhydrolysis.AccordingtoHarmsenetal.5 biomasswithhighligninissuitableforheatand Cellulose Hemicelullose Lignin1.Rice straw 29.94 23.93 9.212.Rice husk 33.85 24.06 8.563.Bagasse 43.49 23.5 16.154.Corn cob 23.29 37.64 9.645.Microalgae 21.72 30.79 9.236.Pulp waste TF 74.78 9.8 3.877.Pulp waste TR 58.21 1.06 8.128.EFB palm oil 25.24 7.45 27.929. Organic waste 22.08 58.91 15.23No. BiomassCarbohydrate composition (%)Figure 2Comparison of carbohydrate composition from each biomassC. AnalysisThecarbohydrateandreducing sugarweredeterminedquantitatively using gravimetric method and Nelson-Somogyi met hod, respect i vel y. Carbohydrateanalysiswasconducted in Centro Agro-Based Industry, Bogor andCenterforFoodandNutrition Studies,GadjahMadaUniversity, Yogyakarta.III. RESULTS AND DISCUSSIONA. Carbohydrate compositionTheaveragecontentofcellulose, hemicelluloses,andligninfromeach biomassarepresentedinTable2. Analysisofbiomasscomposition Table 2Composition of various cellulosic biomassDILUTE ACID PRETREATMENT AND ENZYMATIC SCIENTIFIC CONTRIBUTIONS OIL & GASDEVITRA SAKA RANI AND CUT NANDA SARIVOL. 35,NO. 1,APRIL2012 : 39 - 48

43electricity production. Carbohydrate composition of lignocellulosic biomass vary greatly, depending on the type of plant, cultivation condition and the age of plant12. Carvalho showed that there was different cellulose content between two types of bagasse which used in his research13. Baseonthecomparisonofcarbohydrate compositions(Figure2),thehighestfermentable carbohydrate from the total amount of cellulose and hemicellulose, is found in pulp waste TF, followed by organic waste and bagasse. The highest of cellulose and hemicellulose content in the biomass is expected to be superior in terms of highest butanol production yield.B. Dilute Acid PretreatmentThe conversion process of carbohydrate into sugar hasbeencommencedondiluteacidpretreatment, asindicatedbythecolorchangesofthesolution (Figure 3).Thehighestsugarcontentafterpretreatment process is found in corn cob, followed by rice husk, bagasse,andorganicwaste,respectively.When comparedbetweenthepercentagesofreducing sugarperdryweightbiomass,theorganicwaste givethehighestresultwith39.79%followedby corncobandbagasse.Reducingsugarcontentof each biomass after pretreatment withdilute acid is shown in Table 3.A comparison between the percentages of reducing sugar per weight biomass with hemicellulose content of each biomass is shown in Figure 4. It exhibit that the greater the hemicelluloses, the greater the sugar content obtained from the pretreatment process. The high difference between hemicelluloses and reducing sugar content on microalgae, pulp waste TF, and rice strawshowsthatoptimalconditionofdiluteacid pretreatment process for these biomass has not been achieved. The cellulose and hemicellulose are more easy tobreakdowninsmallparticles.Howeverthe examination of particle size effect on sugar content No. Biomass % Dry Solid % Reducing sugar% weight Biomasssugar Reducing1. Organic waste4.8 1.91 39.792. Corn cob 10 2.93 29.303. Bagasse 10 1.93 19.304. Rice straw 8.6 1.54 17.915. Rice husk 15 2.02 13.476. Microalgae1.5 0.18 12.007 EFB palmoil 12 5 1 19 9 52weight Biomasssugar Reducing7. EFB palm oil 12.5 1.19 9.528. Pulp waste TR 10 0.59 5.909. Pulp waste TF 10 0.42 4.20weight Biomasssugar ReducingTable 3Reducing sugar content after dilute acid pretreatmentFigure 3Rice husk pre- (left) and post- (right)dilute acid pretreatmentDILUTE ACID PRETREATMENT AND ENZYMATIC SCIENTIFIC CONTRIBUTIONS OIL & GASDEVITRA SAKA RANI AND CUT NANDA SARIVOL. 35,NO. 1,APRIL2012 : 39 - 4844afterhydrolysisprocessindicate thatreducingthesizeofbiomass is not followed by increasing sugar content.Theincreaseofsugar content after milled only found in corncobs(Figure5). Thismeans that only certain biomass undergoes increasing in sugar content when its particlesizereduced. Asaresult, theeliminationoffinemilling processcanreduceproduction costs.AccordingtoCarvalho 13,severaltypesofhighenergy consuming grinding against some typesofbiomass,butitworks muchbetterwithotherbiomass. However,grindingisanenergy intensiveprocesswhichisoneof themostimportantlimitationsin theapplicationofindustry-wide scale. Figure 4Comparison of hemic


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