High-temperature pH measuring during hot-water extraction of hemicelluloses from wood

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Industrial Crops and Products 61(2014)9–15Contents lists available at ScienceDirectIndustrial Crops andProductsj o u r n a l h o m e p a g e :w w w.e l s e v i e r.c o m /l o c a t e /i n d c r opHigh-temperature pH measuring during hot-water extraction of hemicelluloses from woodJens Krogell a ,∗,Kari Eränen b ,Kim Granholm c ,Andrey Pranovich a ,Stefan Willför aaÅbo Akademi Process Chemistry Center,c/o Laboratory of Wood and Paper Chemistry,Porthansgatan 3,FI-20500Åbo Turku,FinlandbÅbo Akademi Process Chemistry Center,c/o Laboratory of Industrial Chemistry and Reaction Engineering,Biskopsgatan 8,FI-20500Åbo Turku,Finland cÅbo Akademi Process Chemistry Center,c/o Laboratory of Analytical Chemistry,Biskopsgatan 8,FI-20500Åbo Turku,Finlanda r t i c l ei n f oArticle history:Received 25February 2014Received in revised form 4June 2014Accepted 23June 2014Available online 12July 2014Keywords:Hot-water extraction HemicellulosesHigh-temperature pH pH calibration Spruce wooda b s t r a c tA high-temperature pH measuring system was developed,calibrated,and validated for measuring pH during hot-water extraction of hemicelluloses from wood.The aim was to measure in-line pH during extraction in order to control the extraction pH.An yttria-stabilized Zr/ZrO 2electrode was used for measuring the potential.Phthalate and phosphate buffers were used to calibrate the system at 160,170,and 180◦C.Also,different buffer concentrations were tested for stability.Tap water and different salt solutions were tested to investigate the system response to pure water and water solutions.Calibration curves were acquired from the calibration results and Nernst equation was used to calculate the in-line pH during wood extractions.The setup showed stable and reliable potential readings during both calibration tests and wood extractions.The in-line pH was found to be 0.35pH units higher than when measured at room temperature with a conventional pH meter.©2014Elsevier B.V.All rights reserved.1.IntroductionHigh-temperature pH measurements are vastly desirable and important in several scientific and industrial fields such as geother-mal studies,water coolant circuits in nuclear reactors,plumbing,food industries,and high-temperature thermodynamic studies of aqueous solutions (Lvov et al.,1998;Manna et al.,2004;Huang et al.,2009;Jung and Yeon,2010).Biorefinery of renewable plant materials is a new emerging field where high-temperature pH mea-suring will become important.Nowadays modern biorefineries aim to utilize as much as possi-ble of a wide range of different renewable raw materials.Paper mills today use the cellulose in wood for paper production and the other wood components,mainly hemicelluloses and lignin,are often burned for energy production.Although the energy produced is vital for the process,utilizing more or even all the components in the tree for more value-added products the industry might improve the financial revenue significantly.A common method for obtaining various hemicelluloses from wood is with pressurized hot-water extraction (Song et al.,2008;Leppänen et al.,2011;Krogell et al.,2013).In recent years,studies on hot-water extraction of hemi-celluloses from wood presents an interesting additional step in∗Corresponding author.Tel.:+358400690029;fax:+35822154868.E-mail addresses:jekrogel@abo.fi,krogellj@ (J.Krogell).a biorefinery process (Yoon and van Heiningen,2008,2010;Liu,2010),where pH plays an important role.The extracted hemicel-luloses could be used as feedstock for bioethanol,biopolymers,emulsion stabilizers,and in possible health applications (Hartman et al.,2006;Ragauskas et al.,2006;Willför et al.,2008;Mikkonen et al.,2009;Xu et al.,2011).Many water properties change at higher temperature;the dielectric constant decrease,viscosity decreases,lower surface ten-sion (Yang et al.,1998),and also pH decrease.These property changes could be a reason why hot-water extraction is such a good method for hemicellulose extraction.The drop in pH during a hot-water extraction of wood is a result of a combination of the enhanced auto-ionization of water at higher temperatures,which increases the H 3O +ion concentration (Zumdahl and Zumdahl,2007)and an induced formation of acetic acid from cleaved acetyl groups from the hemicellulose chains (Liu,2010).It is a well-known fact that in acidic media,acid hydrolysis cleaves the glycosidic bonds between the sugar units in the hemicellulose chain with chain degradation and loss of molar mass as results (Lai,2001).The pH may also affect the dissolution of the hemicelluloses from the wood matrix through breaking of glycosidic bonds;however this is not yet fully proven.These examples show the importance of pH and correct in-line pH measuring and eventually in-line pH-control during extraction of hemicelluloses from wood.The conventional glass pH electrodes are not suitable for mea-surements of pH at elevated temperatures because the hydrogen/10.1016/j.indcrop.2014.06.0460926-6690/©2014Elsevier B.V.All rights reserved.10J.Krogell et al./Industrial Crops and Products61(2014)9–15ion sensitive glass membrane will degrade and loose its ion sensi-tivity(Galster,1991;Morf,1995).The upper working temperature for commercial laboratory pH electrodes are about80–100◦C, depending on if the inner reference electrolyte is in gel or liq-uid form(SI Analytics,2012).Further on,calibration of pH meters is also difficult at higher temperatures.The pH measurement is highly temperature dependent,especially at elevated temperatures (>100◦C),very little information on measured pH values for buffers at these temperatures are to be found.Some literature mention measured pH values above100◦C but they are few and originate from1960s(Le Peintre,1960;Krykov et al.,1966).Over the last decades,beginning in the early1980s,high-temperature and high-pressure compatible pH electrodes have been developed.These electrodes are mainly ceramic solid metal/metal oxide electrodes and the yttria-stabilized zirconium oxide(YS Zr/ZrO2)electrode is probably the most common (Niedrach,1980a;Niedrach and Stoddard,1985;Lvov et al.,2000, 2003).The YS Zr/ZrO2ceramic membrane is in fact an oxygen-ion conducting membrane,but because of the close relation between oxygen and hydrogen ions in the potential determining reaction O2+4H++4e−=2H2Othe electrode also functions well as a hydrogen sensitive(pH)elec-trode(Niedrach,1980a,b).Since the Zr/ZrO2electrode also is very stable regarding corrosion and redox potential at high tempera-tures it has been used as an excellent reference electrode when measuring corrosion and redox potentials in high temperature aqueous solutions(Niedrach,1982;Niedrach and Stoddard,1985).The aims of this work were to construct,calibrate,and validate the setup for a high-temperature and high-pressure pH measur-ing system,as well as evaluate the measurements for hot-water extraction of hemicelluloses from spruce wood.2.Material and methods2.1.Reactor setupThe experiments were carried out in a1000mL stainless steel 316batch reactor system(Autoclave Engineers,PA,USA)(Fig.1). The system was equipped with a Dispersimax TM turbine stirrer, heating mantle,and a sampling valve.The temperature was con-trolled by a Eurotherm2416temperature controller(Eurotherm, VA,USA)and logged to a computer with PicoLog TC datalogger and PicoLog software.Furthermore the system was equipped with a solid ZrO2-based high-temperature and high-pressure pH elec-trode(Corr Instruments,TX,USA)and a high-temperature and high-pressure Ag/AgCl reference electrode(Corr Instruments,TX, USA).The pH electrode was an yttria-stabilized Zr/ZrO2membrane electrode with a Queon TM seal and a pressure range of0–136bars and temperature range of90–305◦C.The reference electrode was a0.1N KClfilled internal pressure-balanced Ag/AgCl electrode witha ceramic frit as a junction partly based on ZrO2,Queon TM seal and a pressure range of0–136bars and temperature range of0–305◦C. The potential was recorded with a MeterLab®PHM220lab pH meter(Radiometer Analytical,Lyon,France)high-input impedance voltmeter and logged to a computer.2.2.MaterialsThree different sets of water samples were used for testing the system response for only water.Normal tap water from the labora-tory tap,ultrapure water with0.05M NaCl(Merck KGaA,Damstadt, Germany,Analysis grade),and ultrapure water with0.05M KCl (J.T.Baker®,Deventer,The Netherlands,Analysis grade).The ultra-pure water was taken from a Milli-Q Advantage A10Ultrapure Fig.1.Batch extractor setup.ADC,analog digital converter;PI,pressure indicator; TIC,temperature indicator and controller.Water purification system(Millipore Corporation,Billerica,MA, USA).Potassium hydrogen phthalate,C8H5KO4(Merck KGaA, Damstadt,Germany),Potassium dihydrogen phosphate,Na2HPO4 (VWR,Leuven,Belgium),and sodium monohydrogen phosphate, H2KPO4(J.T.Baker,Deventer,Holland)were used for the calibration solutions.All salts for calibration solution preparation were of analysis grade.The wood used in the extractions was knot-free sapwood from a healthy Norway spruce tree,felled in southern Finland.2.3.Methods2.3.1.TheoryNormally when measuring pH,a conventional laboratory pH meter,the glass electrode,is used.The pH meter measures the difference in potential caused by hydrogen ion activity in a solu-tion between a hydrogen ion sensitive electrode and a reference electrode(usually an Ag/AgCl electrode).Normally both electrodes are embedded in the pH probe along with a thermometer.In fact, the measured potential consists of several intermediate potentials within the pH meter.Such are the potential difference between the sample solution and the gel layers on the glass membrane(inside, as well as outside),the potential difference between the reference electrode and the reference electrolyte solution and the potential difference between the reference electrolyte and the sample solu-tion through a junction.These form a potential chain where all but the potential between the sample solution and the glass membrane are constant.With the measured potential and the temperature the pH meter uses Nernst equation(1)(Christian,1994).Although the high-temperature pH electrode used in this study is not glass-basedJ.Krogell et al./Industrial Crops and Products61(2014)9–1511 it has been shown that it follows Nernstian behavior and thereforeEqs.(1)and(2)can be used(Lvov et al.,2003).E=E0−2.303RTF×(−lg(˛H))(1)or rearranged Eq.(2)to calculate pH from the potentialpH=E0−ES(2)where E is the measured potential,E0is the standard electrode potential,R is the gas constant,T is the temperature in Kelvin,Fis Faradays constant,a is the activity of the measured specie,in this case the hydrogen ion and S is2.303×RT/F.S is also known as the calibration slope.The standard electrode potential,E0,is a constant that includes the different internal potentials e.g.diffusion poten-tial,different phase boundaries potential,as well as an asymmetry potential.The asymmetry potential exists across the glass mem-brane and is a result from physical defects of the membrane such as non-uniform composition,mechanical and chemical attacks,and the degree of hydration.This will slowly change with time and it is therefore very important to calibrate the pH meter from time to time(Christian,1994).2.3.2.CalibrationBecause the working range of the commercial high-temperature pH electrode used in this work is from90◦C to200◦C,it is not possible to calibrate the system with buffers at room temperature, as it is normally done with conventional laboratory pH meters. And because the potential response is very temperature depend-ent,calibration at room temperature would not be valid at higher temperatures anyway.Nernst equation(Eq.(2))is used for calculating pH values from the measured potential.To be able to do so,E0and S should be known and to determine E0and S for the system one should have solutions with known and stable pH at the used tempera-tures.Data on pH values for diluted sulfuric acid(0.0005M)and diluted sodium hydroxide(0.001M)at elevated temperatures was provided by the manufacturer and these solutions were tested at 170◦C.Unfortunately the potential responses from the electrodes were not very stable(especially for the NaOH)and,because of drifting,no good readings could be achieved.Hence buffers with different pH were tested at160◦C,170◦C,and180◦C.The different buffer solutions were0.05mol/kg potassium hydrogen phthalate with a pH of4.005at25◦C,0.025mol/kg disodium hydrogen phos-phate+0.025mol/kg potassium dihydrogen phosphate with a pH of 6.857at25◦C.These buffers gave stable mV readings at the studied temperatures.The pH values for these buffers at the high tempera-tures were taken from Galster(1991)in accordance to the electrode manufacturer.Galster reported pH values for the phthalate buffer up to150◦C so an extrapolation was made with goodfit to provide the pH values for160,170,and180◦C.The pH values for the phos-phate buffer was reported for100,125,150,175,200,225,and 250◦C so a model wasfitted to the plotted curve to get the pH val-ues at160,170,and180◦C for the phosphate buffer as well.With these acquired values,it was possible to plot the known pH val-ues against the measured potential of the phthalate and phosphate buffers at different temperatures to acquire the calibration curves.Inserting the y-axis intercept(E0)and the slope(S)from the calibration curve with the potential(E)measured during a wood extraction into Eq.(2)gives the in-line pH value during the extrac-tion.2.3.3.Wood extractionWood extractions were carried out with wood particles (1.25–2mm)of spruce sapwood with a liquid to wood ratio of33at 170◦C to test the system response.A removable protection net was20406080100120140160180200 2503003504004504321Time (h)Potentia l (m V)Temperature (°C)Temperatur ePotentialTapwater20406080100120140160180200 3253503754004321KClNaClTemperatur ePotentialTime (h)Potentia l (m V)Temperature (°C)water with saltsUltrapureFig.2.Potential response from different water tests at160,170and180◦C Tap water (top)and ultrapure water with0.05M NaCl and0.05M KCl salt addition(bottom).constructed and installed in the reactor between the electrodes and the wood material and stirrer.This was used during wood extrac-tions to prevent wood particles from damaging the electrodes and prevent particles to get stuck inside the protective tube of the elec-trodes.Samples of the extract were taken from the reactor when the temperature reached170◦C,after2.5min,5min,10min,20min, 60min,and120min.The samples were then cooled down to room temperature and pH was measured with a conventional glass elec-trode pH meter.The heating time for the system to reach170◦C was about40min.3.Results and discussion3.1.Water testsTap water,0.25M NaCl and0.25M KCl solutions of ultrapure water were tested to investigate how the electrodes respond to pure water and water solutions.Parallel experiments were made at160,170,and180◦C for each sample.The salt solutions showed by far the best stability for electrochemical potential readings with very little signal noise compared to the tap water(Fig.2).The tap water tests showed more signal noise than the salt solutions, which corroborates that ions in general,not necessarily hydrogen ions,present in the solution stabilize the system due to increased conductivity(Galster,1991).The conductivity for tap water was 218␮S/cm,and much higher for the0.25M NaCl and the0.25M KCl solutions,2.9mS/cm and3.4mS/cm,respectively.A slight shift in potential between the parallel experiments,nor-mally between0and5mV could be observed for all the different water tests.Recalculated to pH a difference of5mV corresponds to about0.08pH units at room temperature.The difference in poten-tial was also slightly increasing with a couple of mV during the experiment time for the tap water.Overall the repeatability can be considered good since the difference in mV between the experi-ments only corresponds to a difference in pH of about0.08.TheJ.Krogell et al./Industrial Crops and Products 61(2014)9–1513y = 0.00002x 2+ 0.00119x +3.96800R² = 0.999003.544.5520015010050Phthalate bufferTemperature (°C)pHy = 0.00002x 20.00194x + 6.88378-R² = 0.9963067830025020015010050Phosphate bufferTemperature (°C)pHFig.4.pH values at different temperatures for 0.05mol/kg potassium hydrogen phthalate buffer and 0.025mol/kg disodium hydrogen phosphate +0.025mol/kg potassiumdihydrogen phosphate buffer.The thick lines are values from literature (Galster,1991)while the dotted line is an extrapolation of the literature values.y = -76.01x + 950.27y = -87.89x + 986.21y = -90.09x + 992.39y = -92.29x + 1,001.4625030035040045050055060065070012108642100 °C 160 °C 170 °C 180 °CPot ent ial (mV)Estimated pHFig.5.Calibration curves for 100◦C,160◦C,170◦C,and 180◦C with the slope factor and intercept described in the line equations for the different temperatures.With the measured potential for the different buffers at the dif-ferent temperatures and the estimated pH it was possible to plot the potential versus the estimated pH (Fig.5).The plot describes lines with a slope and an intercept,which are used in Eq.(2)for calculating the in-line pH value during wood extractions at the different temperatures.Table 2presents the slopes and intercepts,as well as the potentials and estimated pH values at the different temperatures.To check how close the measured slope was to the theoretical values,a comparison between these two was made.The theoretical slope for the high temperatures was calculated as mentioned in Section 2.3.1and the results are presented in Table 3.The theoretical calibration slope is naturally a straight line,but the measured slope starts to differ from the theoretical after 100◦C.As stated earlier,not even laboratory pH meters show the theo-retical pH even at room temperature;normally a deviation of a couple of percent is acceptable (SCHOTT Instruments handylab pH 12Operation manual 2011).Therefore,the deviation of the slope for the high-temperature pH electrodes at the high temperatures is to be expected.Furthermore,as the electrodes undergo aging the potential response also changes with time.The high-temperature electrodes have also showed this behavior,approximately a dif-ference of 5mV over a 6months period.Therefore it is important to calibrate the electrodes before using them on a weekly basis as it is for conventional glass pH meters.The change in poten-tial varies depending on usage,application conditions,and storage conditions.A buffer concentration study was made to investigate what effect the buffer concentration has on the potential response.Phthalate buffer (pH 4)and phosphate buffer (pH 7)was selectedfor300350400450500550600650mol/L(mV)Potential Fig.6.Potential response for phthalate buffer and phosphate buffer solutions with different concentration at 160◦C,170◦C and 180◦C.this study with three different concentrations respectively,0.01M,0.05M and 0.1M.Fig.6shows the result from the concentration study.The results in Fig.6suggest that the potential responses are slightly lower with increased temperature for both buffers.This phenomenon can be explained from the nature of Nernst equa-tion (1);when the temperature increases on the right-hand side of the equality sign it decreases the potential on the left-hand side.The same was seen in the buffer solution experiments (Fig.3).The slight incline of the lines in Fig.6shows that the potential response is slightly lower for more diluted buffers.In terms of pH,this means that pH actually increases when a buffer is diluted.This is due to a decrease in ionic strength,which will increase the activity coef-ficient of the buffer salt leading to a slight increase in pH (Perrin and Dempsey,1974;Christian,1994).This phenomenon was also observed when the same buffers with the same concentrations were tested at room temperature with a conventional pH meter.The relative standard deviation for the buffer concentration tests were between 0.25and 3.2mV for the phthalate buffer and below 1mV for the phosphate buffer.A general trend was that the RSD decreased with increasing concentration,especially for the phos-phate buffer.The stable results from the buffer concentration study also confirm that the high-temperature electrodes were working properly and can be used in practice,i.e.for wood extractions.3.3.Wood extractionWith stable and reliable potential readings from the different buffers,it was possible to recalculate the measured potential read-ings from the wood extractions using Eq.(2)and slope and intercept14J.Krogell et al./Industrial Crops and Products 61(2014)9–153.03.54.04.55.03:303:002:302:001:301:000:300:00Time (h)Fig.7.In-line pH measurements during two 170◦C hot-water extractions of spruce wood.Solid lines represent in-line measurements and dotted lines pH measured with a conventional glass electrode at room temperature.from Table 2to actual in-line pH during wood extraction.Two par-allel wood extractions were made at 170◦C and the in-line pH of those extractions is presented in Fig.7,as well as the measured pH after sample cool down.The pH value measured in-line was about 0.35pH units higher than that measured at room temperature.A reason for this dif-ference could be that the dissociation of acetic acid,the main contributor to the pH drop during the extraction,is slightly exother-mic and p K a increases at higher temperatures (Fisher and Barnes,1972).The equilibrium is therefore shifted toward the protonated form of the acid,with less free hydrogen ions in the solution.When the samples cool down to ambient temperatures,the pH thus decreases.Previous studies of hot-water extraction of hemicellu-loses from spruce show the same pH profile and also a significant depolymerization of the hemicelluloses when the pH decreases (Song et al.,2008,2011;Krogell et al.,2013).At pH 4and below,the average molar mass decreased substantially already after 10min of extraction.These new findings in our study suggest that the hydrol-ysis of hemicellulose chains takes place already at significantly higher pH at these elevated temperatures.With a potential RSD 0.5mV that corresponds to a pH RSD of 0.01units between the parallel wood extractions show yet again good repeatability and stability and more important,the pH measured in-line follows in parallel with the pH measured with a laboratory pH meter after the samples cooled down.This gives an indication that the in-line pH system is working and the calculation theory is correct.This will have a positive impact on the possibility to measure and adjust the pH in hot-water extractions of a particular plant biomass and thus to control the extraction and subsequent degradation of polymeric substances.4.ConclusionsRepeatable and reliable high-temperature pH measurements can be made during hot-water extraction of hemicelluloses from wood with an yttria stabilized Zr/ZrO 2pH electrode after calibra-tion with phthalate and phosphate buffers.The in-line pH at 170◦C was shown to be about 0.35units higher than when samples had been cooled down to room temperature and measured with at con-ventional pH meter.The in-line pH measurement possible it opens up for the possibility of continuous in-line pH control during extrac-tion process and with that a better opportunity to tailor the end products.AcknowledgementsThe authors would like to thank Lietai Yang,Ph.D.at Corr Instruments for the help with the many questions about the elec-trodes and Jimmy Dahlqvist at the 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