Freeman, R.R.

Kim, Y.M

Soll, M.

Teramae, N.

Wang, K.

Watanabe, Chu

Watanabe, Ichi

English

Engineering Conferences International

Engineering Conferences InternationalECI Digital ArchivesBiorefinery I: Chemicals and Materials FromThermo-Chemical Biomass Conversion and RelatedProcessesProceedings2015On-line analysis of catalytic biomass products usinga high pressure Tandem mirco-Reactor GC/MSM. SollFrontier LaboratoriesR.R. FreemanFrontier LaboratoriesChu WatanabeFrontier LaboratoriesIchi WatanabeFrontier LaboratoriesY.M KimFrontier LaboratoriesSee next page for additional authorsFollow this and additional works at: http://dc.engconfintl.org/biorefinery_IPart of the Chemical Engineering CommonsThis Conference Proceeding is brought to you for free and open access by the Proceedings at ECI Digital Archives. It has been accepted for inclusion inBiorefinery I: Chemicals and Materials From Thermo-Chemical Biomass Conversion and Related Processes by an authorized administrator of ECIDigital Archives. For more information, please contact franco@bepress.com.Recommended CitationM. Soll, R.R. Freeman, Chu Watanabe, Ichi Watanabe, Y.M Kim, N. Teramae, and K. Wang, "On-line analysis of catalytic biomassproducts using a high pressure Tandem mirco-Reactor GC/MS" in "Biorefinery I: Chemicals and Materials From Thermo-ChemicalBiomass Conversion and Related Processes", Nicolas Abatzoglou, Université de Sherbrooke, Canada Sascha Kersten, University ofTwente, The Netherlands Dietrich Meier, Thünen Institute of Wood Research, Germany Eds, ECI Symposium Series, (2015).http://dc.engconfintl.org/biorefinery_I/22AuthorsM. Soll, R.R. Freeman, Chu Watanabe, Ichi Watanabe, Y.M Kim, N. Teramae, and K. WangThis conference proceeding is available at ECI Digital Archives: http://dc.engconfintl.org/biorefinery_I/22On-line analysis of catalytic biomass products using a high pressure Tandem mirco-Reactor GC/MSM. Soll1) , R.R. Freeman1), Chu Watanabe1), Ichi Watanabe1), Y. M. Kim1), N. Teramae2) and K. Wang3)Frontier Laboratories(1) , Tohoku University(2) and Iowa State University(3)September 27-October 2, 2015Atlantica Caldera Crete Paradise HotelChania (Crete), GreeceBiorefinery I: Chemicals and Materials From Thermo-Chemical Biomass Conversion and Related Processes“Almost everything in your daily life depends on catalysts.” – Argonne National Laboratory ● Continuous search for new catalysts and “good” biomasses – one that works “better” than those being used for a given process● Test parametersTemperatureSurface area (contact time)AtmospherePressureEffective life timeActivity regeneration● Rapid screening of new catalysts (and biomasses) is essential if sustainable “green” products are going to exist in the future.Dimensions for “Rapid screening” Think smal !Think „smart“: fast, flexible, µ scale, online GC/MS analysis !Pyrolyzers and µ-ReactorsFast pyrolysis: Important features for GC/MSSample Conditioning Gases, liquids and solids                vapors Precise Temperature Control Low dead volume Inert surfaces No cold or hot spotsDesign of Single µ-ReactorGC OvenFurnaceInterfaceCatalystCatalyst reactiontube (quartz)Split ventSelective samplerMicroJet cryo-trapSeparation columnMSReaction Gas  Catalyst bedQuartz woolQuartz wool(6 mm o.d.; 5 mm i.d.) Quartz reaction tube(4 mm o.d.; 3 mm i.d.)Deactivated stainless steel tube78 mm40 mmCoil springO-ring (Viton)•Catalytic pyrolysisCatalytic crackingHydropyrolysisHigh pressure pyrolysisFrom Single to Tandem µ-ReactorTandem µ-ReactorRx-3050TRSingle µ-ReactorRx-3050SRGC Injector1st µ-Reactor(40 - 900ºC,Max. 200 ºC/min) 2nd µ-Reactor(40 - 900ºC, max: 200 ºC/min)Carrier gasReactantgasSS tubeIn-situ onlyIn-situ and ex-situµ-Reactor: 100ºC ( 2nd- ITF: 250ºC) µ-Reactor: 200 & 300ºC ( 2nd- ITF: 300ºC)µ-Reactor: 400-900ºC (2nd- ITF: 350ºC) 120mmCarrier or Reaction gasITF heaterµ-ReactorGC INJ.Catalytic bed temperature profiles [100 - 900⁰C]Catalytic bed temperature at various points020406080100120 mm100 300 500 700 900ºC100 200 300 400 500 600 700 800 900 1000ºCCatalytic bedtemperatureGC DET.(40mm)Pack a reaction tube with catalyst Introduce sampleHeating/Pyrolysis• Gas/liquid: preheating  or vaporization • Solid: pyrolysisCatalytic reactionThree temperature program modesMS or GC/MS analysisTo GCGC MSReaction tubeCatalystSolidGas/liquidSample cupMicro syringe,  Syringe pumpVaporization/Pyrolysis Reactor 1) Online monitoringm/z: xm/z: ym/z: z⇒ Temperature2) GC/MS analysis⇒ Time1st Reactor2nd Reactor1st Reactor1st Reactor2nd ReactorCatalystCatalystHandling and workflow3 Reactor heating profiles Temperature control and two analytical modes of Tandem µ-Reactor On-line EGA-MS analysistimeTempIsothermalEGA-Selective zone GC/MS analysisOven: Isothermal (300ºC)EGA tube(L=2.5 m, 0.15 Φ)HeAux Vent-freeadaptorGC column(L=30 m, 0.25mm)HeAuxSelective samplerReactor temp progr.Oven: temp program.Multi-linearStepwiseSeparation analysis“ Stepwise temp. mode ” Online – MS analysis“ Linear temp. mode ”TIC1st µ-Reactor: 100ºC, 2nd µ-Reactor: 100-400ºC (20 ºC/min)Catalyst: H-ZSM-5 Ethylene(m/z 28)Diethylether (m/z 74)Ethanol  (m/z 45)Water (m/z 18)100 200 300 400ºC2nd µ-Reactor temp.Peak Area2nd µ-Reactor temp.EthyleneEthanolDiethyl ether300 400ºC100 200H2OReaction temp. vs. Peak area1.0 2.0 3.0 4.0 min300100200400ºCEthyleneH2OEthanolDiethyl etherTime1st µ-Reactor: 100ºC, 2nd µ-Reactor: 100, 200, 300, 400ºC (1sec)Catalytic conversion of ethanol to ethylene (Std. config = low pressure)GC Cooling gas CarriergasAux Gas MFCMSLN2 trapSplit ventEGA orGC column MFC1st Reactor2nd ReactorInnovative pneumatics for HP Tandem µ-ReactorOPTIONHP flow moduleSampleSample cup/ALS (Solid)Micro syringe (Gas/Liquid)Micro feeder (Liquid)Open split interfaceRestrictor tube(deactivated) (0.05 mm i.d., 1 m) VentVentBP-1Max3.5 MPa VentBP-2Max0.4 MPa HP flow controllera) Ethylene (Peak Area: 99%)b) Propylenec) Acetaldehyded) iso-Butanee) trans-Butenef) cis-Buteneg) Ethanolh) Diethylether0.2 MPa1 2 3 4 5 6  min0200400600800x1000.4 MPa1 2 3 4 5 6  minx1000.6 MPa1 2 3 4 5 6  minx101 2 3 4 5 6  min0100200300400x100a)b) c) d) e) f) g) h)b)c)d)e)f)g) h)a)a)b)c) d) g) h)a) b)c)d)g) h)a)g) h)a)b)020040060080002004006008001 2 3 4 5 6 7 8 9  min01002003004001 2 3 4 5 6 7 8 9  min01002003004001 2 3 4 5 6 7 8 9  min01002003004001 2 3 4 5 6 7 8 9  min01002003004001.0 MPa2.0 MPa3.0 MPa0.5 MPaOld NewNo retention time shift due to BP regulators and open split interfaceCatalyst (ZSM-5) at 230ºC,：BP1: 0.5-3.0 MPa, BP2: 0.1 MPa, Restrictor: 40 cm , i.d. 50 μm, Column: UA1-30M-2.0F, Detector: FID120.07 MPa( 1.0 ml/min )( 3.8 ml/min )( 17.1 ml/min )( 11.6 ml/min )( 1.10 ml/min )( 1.12 ml/min )( 1.16 ml/min )( 1.14 ml/min )Sample is placed directly into the sample cup (Eco-Cup)High pressure sample injection of solidsRotating knobDrop to 1st ReactorHigh pressure solid samplerSpring 1SampleSpring 2Sample cupCup chuckStandard solid samplerDrop to 1st ReactorPush buttonTwo applications using the high pressure Tandem µ-Reactor1. Conversion of lignin (He/H2 and P)2. Conversion of Ethanol (T and P) Biomass (nature, amount) Catalysts (type, particle size, catalyst/biomass ratio) Temperature (1st and 2nd Reactor) Reaction-/Carrier-Gases (He/H2) (High)-Pressure GC/MS settingsApplying different parameters:EGA Thermogram of Kraft Lignin (second Reactor  = 320 0C)200 300 400 500 600 700 800First Furnace Temperature (℃)9001002.0 MPa1.5 MPa1.0 MPaTmax: 376±0.3℃5.00 10.00 15.00 20.00 25.00 30.00 35.0002000004000006000008000001000000Time-->Mass IntensityPyrogram obtained heart-cut EGA-GC/MS analysis from 300 to 500 under 2MPa of helium atmosphere CO2Methanol GuaiacolCreosolEthylguaiacolVinylguaiacolIsoeugenolNon-catalytic pyrolysis of kraft lignin under high pressure helium (carrier gas)Remained char after EGA-MS analysisNon-catalytic „hydropyrolysis“ of kraft lignin under high pressure hydrogenEGA Thermogram of Kraft Lignin under Different Hydrogen Pressure.200 300 400 500 600 700 800100 900First Furnace Temperature (℃)2.0 MPa1.5 MPa1.0 MPaTmax: 374±0.5℃Tmax: 640±1℃ABZone „A“Pressure(MPa) 1.0 1.5 2.0Char (wt.%) 35.2 26.3 21.4Remained char after EGA-MS analysisPyrogram obtained heart-cut EGA-GC/MS analysis from 100 to 800 0C under 2MPa of hydrogen atmosphere CreosolIsoeugenol5.00 10.00 15.00 20.00 25.00 30.000200000400000600000800000100000012000001400000Time-->AbundanceBenzeneToluenePhenol5.00 10.00 15.00 20.00 25.00 30.00020000040000060000080000010000001200000Time-->Abundance EthanePropaneBenzeneTolueneEthylbenzeneXylenePhenol NaphthaleneMethyl naphthaleneBiphenylMethyl biphenylPhenanthreneAnthraceneZone „B“Heart-Cut EGA-GC/MS at Different Hydrogen Pressures 200 300 400 500 600 700 8000100000200000Abundance100 900First Furnace Temperature (℃)5.00 10.00 15.00 20.00 25.00 30.00020000040000060000080000010000001200000Time-->Abundance5.00 10.00 15.00 20.00 25.00 30.00020000040000060000080000010000001200000Time-->Abundance5.00 10.00 15.00 20.00 25.00 30.00020000040000060000080000010000001200000Time-->Abundance123451 2 3 4 5Methanethiol propane waterethane1~51~51~5678 9 1011 12 13 14 15 16 17 18 19 212022 23 24 25678911 12 13 14 15 16 17 18 19 2022 23 24 251011 121314 15 17 18 22 23 24 256789 19 20 2111 13 1518 257 9,1020 216 8benzene toluene tolueneo,m,p-xylene12 16phenol creosol naphthalene14methylnaphthalene biphenyl16methylbiphenyl17phenanthreneanthracene19phenyl-naphthalene fluoranthene dihydropyrene22,23Beozofluorene?24benzoanthracene benzophenanthrenedimethylamineSamplingSecond EGA peak2.0 MPa1.5 MPa1.0 MPa17Results lignin conversion under high presssure hydrogen Heart-Cut EGA-GC/MS results showed that most of pyrolyzates offirst EGA peak were phenolic pyrolyzates of lignin, such asguaiacols, pyrocatechol, cresol, eugenol, and homovanillic acid. Second EGA peak shows quite large amount of valuable aromaticcompounds such as BTEXs, naphthalenes, biphenyls,phenanthrenes, and anthracenes and their peak intensities wereincreased under higher pressure. This can indicated that there is animportant interaction between char intermediates and hydrogen gasand this interaction can produce large amount of aromatic oil underhigh hydrogen pressure.1 2 3min1x10^71 2 3min1x10^71 2 3min1x10^7200400 5003MPa1MPa101010101011117133314544 8998551 2 3min1x10^730011 4 554 1123MPa1MPa3MPa1MPa3MPa1MPa771010111567111098 52711314 8952761: Ethylene, 2: Ethane, 3: Propene, 4: Water, 5: Acetaldehyde, 6,8,9: Butene, 7: Butadiene, 10: Ethanol, 11: Diethyl ether Ethanol over MgO-SiO2 Catalyst under hydrogen and high pressureplus different catalytic bed temperatures 1st furnace: 300℃ 2nd furnace: 200, 300, 400, and 500℃02040200 300 400 500Relative MS IntensityEthene1MPa3MPa0510200 300 400 500Relative MS IntensityEthane1MPa3MPa02550200 300 400 500Relative MS IntensityButadiene1MPa3MPaExperimental ConditionsSample: Ethanol, 2ulCatalyst: MgO-SiO2, 60mg1st furnace: 300℃2nd furnace: 200, 300, 400, and 500℃BP1: 1, 3 MPaBP2: 42 KPa (H2)System Split ratio: He 500:1Ethanol over MgO-SiO2 Catalyst under hydrogen and high pressure:Different catalytic bed temperatures Ethanol conversion and product distribution were quitedifferent at different catalyst bed temperature. Butadiene and ethene yield were maximized at 400 and500℃, respectively. By increasing reaction pressure from 1 to 3MPa,butadiene yield was decreased, however, ethene andethane yields were increased at all applied temperaturesSUMMARY Tandem µ-Reactor facilitates the rapid characterization of catalysts and biomasses Full spectrum of operating parameters can be investigated – SW controlled / online Easy and fast exchange of catalysts Real time analysis of gaseous or liquid samples automated analysis of solids (using “Autoshot” auto-sampler) species identification using MS High pressure option without loss of chrom. performanceThe development and use of “best”/proper catalysts means new products, lower costs, and a broader range of feedstocks 22Questions?

On-line analysis of catalytic biomass products using a high pressure Tandem mirco-Reactor GC/MS

https://dc.engconfintl.org/cgi/viewcontent.cgi?article=1022&amp;context=biorefinery_I

On-line analysis of catalytic biomass products using a high pressure Tandem mirco-Reactor GC/MS

Abstract

Similar works

Full text

Available Versions

Engineering Conferences International