Phosphoric Acid Activation of Nutshells for Metals and Organic Remediation: Process Optimization Chris jopher A. Toles,* Wayne =. Marshall & Mitchell M. Johns USDA-ARS-SRRC 1100 RE. Lee Blvd, New Orleans, LA 70124, USA (Received 28 August 1997; revised version received 19 November 1997; accepted 19 January 1998) Abstract: Almosd, pecan, English walrat, black walnut and macadamia nut Shalls were chosen ay hard Hgnocellulose: precursors fr the preducton of sfa- dular activated carbons (GACs). They were activated with HyPO, under a ‘arsty of condivons. Following activation, a portion of each GACs was oxidized inairat 3b) for hin order to creat a athon surace presumably with more ‘oxjgen functional groups fr the adsoopsion of metal cations. Aso investigated ‘wats stfeamiang of the production tichnigues used, Several of the samples ‘were subjected toa “Continuous” processin which the carbon was activated and ‘upon cooling 10 300°C wae oxidized wi ait. Beyond this activation, methods ‘were developed chercin the activation process took place under sir and without 2 discret, separate oxidation step. Those processes were signed to determin i Any ofthe carbons capabilities would belestor enhanced in comparison to the ‘ore standard activate-cool-nash oxidize method. The carbons produced rom ‘these various asvation oxidation mtheds consistently. and without repard to [rccursorcompsition, soquestered over 90% of avalable copper from a 3 mat onper chloride ext solution and often aorbod organic contaminants asec: {ively as some commercial carbons. © 1998 SCT Key words: granular activated carbons: adsorbents; romadiation; agricultural INTRODUCTION Activated carbons are high porosity, high surface area ‘materials used in industry for environmental remed tion, purification and chemical recovery operations, Activated carbons can be produced from number of ‘precursor materials including coal, peat, wood und wgri- cultural wastes. These precursors are normally exposed lo « numberof dierent activation methods in an effort toachieve a carbon with the best qualities for a particu- lar application. While most activated carbons are wsed for adsorption of organic compounds, previous studies have shown that many activated carbons can sequester metal ons {rom solution? Metals uptake is assumed to be a func- tion of polar or acidic surlace groups on the carbon. * To whom correspondence shouldbe address. ass ‘The goal of our research is to develop commercially viable adsorbents from agricultural waste We selected. pecan, almond, black walnut, English wainul and mac~ ‘adamia nut shells cause oftheir availablity and desir able physical characteristics as activated carbon precursors. These nulshells have a variety of uses such as mulch, poultry bedding, and as a component of drill- ing mud, all with relatively low value. In the ease of macadamia nuls these are almost exclusively produced im Hawai and an opportunity to develop an environ mentally useful material from them would lessen the reed for such remediation materials to be shipped 10 this slate. All of these materials are renewable on a yearly basis unlike coal, peat and wood. ‘Walnut, macadamia nut and pecan shells are all hard, high density, low ash materials, thus eliminating. the eed for @ binder, which would ease the cost of pro duction, Due to their unique makeup they ure a very © 1998 SCL J.Chem. Teel. Borel 0268.257598)317 50. Printed in Groat Britaincosteflective allemative to more polluting precursors suet as coal in the production of activated cartons. Since these ar largely waste materials they are a much ‘cheaper commodity thar coal which requires mining Tr thi ody, a cores of casboms was produced Erm pect, almond, Bich walnet, Fnaish sen and mac adamia nu stells using various phosphoric acid activa tion methods in an effort to develop granular activated carvons with superior melas adsorpion capaly and io substantial abibty to adsorb organic eomposns Sompared silk select conemercial carbone) For this study, we chose to monitor copper uplake, since copper is 4 ubiquitous metal in pliting and jewelry mamefuc- luring wastewaters. Organic compounds chosen for ‘udsorpion asiessmeat included methanol acetone, ace lone, Ttdiowine, hersene and toluene These organic compounds were chosen because they are low molecular weight priority pollulnis and express anely of polantis. These inorganic and onganic ralyts should land as teat cx for potntial applic Saitione of these carbons. We have also inched an analysis of reactant recycling and eleciveress in this study. 2. EXPERIMENTAL 2A Procersr materiahe Table | shows the most recent available igure for US production of the ruls whose shells are used in this Sludy as well as gn estimate ofthe weigh! of shalspro- duced inthe US US Veuly Produsion of Nuts and Shots? matic tons) whichare Used in thi Stuy Pecan shells were obtained from SunDiamond of New Mexico, Las Cruces, NM and almosd shell fom Caliorsia Almord Hluls, Turlock, CA. The black walnut shels Were provided by the Hammons Products Co. of Stoskton, MO; the English walnut shells wore presided by Sanilippo and Sone of Gung. CA: and the macadamia nut shells were provided by Hawaiian Macadamia Company, Ine. of Keaau, Hawaii. All of these materia are relatnely low-value agrcullsral waste producs, Pecan, walnut and macadamia sul Shells ate hard, dense matersls « properiy that makes them an atlructive precusor for granular activated carbons since loss due 1 particle attrition i undesir- ble The shells vere ground in a Glenn Mls micro- farmer cutter sieved to 4 10-< 29 mesh (2 rim AI jm) particle size proe Uo activation except for the black walnut shells which were recived as pres round, preseined 12% 20 mesh (168 men x 841 um) particles. Proximale analyses of the sells were cared ‘at by Weodbon-Teact Labs (Mempis, TN) and are (Sher in Table 2 Hull densiy was etimated by placing 2 known weight of shell in a graduated eylinder and lapping unil + minimum volume was oocupsed by the shells 22 Activationjoxidaton methods Tarlier sities have shown that chemical sctivaion sine phosphoric acid a moderate temperatures pro- duces, in certain lignocelilesic materials snd coul mac- ‘aly @ high surface area and a high degree of jeroporosty +! The wutshells were mised in faw SO. HPO, and allowed to soak for 0-24 at room temperature, The samples were placed in a pyrolysis furnace and Tushed with nitrozen (S;Mlowrate = 01 mh). The samples were heated 10 = Frio taper” MSC HOG) whee hey were eld for 08-1 HATH) uns’ Ae slow lpr eatment (LTT the tome Nas See ae entre was ceed lo aah ee eae em simtS4— Feraure ITT ee CSC) whe hey wee eld Ted mp re aor EEA cept vet load ost Fee aay ITS SR ear lactation the sample were rin ina Mink RERY RRP PRIM sont exter with died water ut he pH ofthe Se water wes or marae, & sal sample Proximate Analysis Daa fr the Prcusors Uc in ths Study Prciror Moisire ash Cage re) ‘Almond sb 9026 ae ‘Black walna ss 38 0G 24 Engish waleut shel 89168 ‘Macadamia shell woo 02 ate. ‘elas Heniclase Bulk dowry on eo) won) x69 9 oa 519 B66 52 os BS besActivation of nutshell: for remediation the wash water, as well as the washed) carbon (in approximately S0 em of distiled water, were boiled seperately and lor cooling amayed wih an O08 M PhYNO,}, solution to determine the presence of any residual free or loosely bound. phosphate. This ree phosphate could coscenably bind with some of the ‘nelals in solution and precipitate them out a ivoluble phosphates during we. Thi isan undesirable property for metals applications. IF lead phosphate prespiiate appeared in the test sample, then the carbon ws ‘washed for a longer perod of time until no prespiate ‘vas obseried. For these samples, approximately 30 z of carbon washed for 21-36 bin thin mareer van wally ‘lean enogh for use: Previa sides ave found tha this cleaning effectively removes most of the phos- pheeus, leaving enly about 3 wits P in the carbon by [XRF analysis** Afler washing, dhe samples were dried jn a vacuum oven at 110°C for at last 3 hy after which synthesis yield were calelated. ‘Aller washing, the phosphoric acid was reclaimed by evaporating of the wash Water until the aex! solution ‘vas ator aear a density of 1-68 gem’ *, the density of the original 87% HPO, sued in the proses. To asset the purity of the Teclimed phosphoric acid it was analyzad by P NMR using a GE NMR spectrometer ‘quipped vitha S00 MEH) magne ‘Aismallscale study was made of the rewsatility of tho acids which prompted the exploration of soveral alterations of the reeyeing methods. Alternately recy ‘led and raw aid were mixed and ased for activation as ‘vas acd that was only recycled once and then nly boiled down to approximately 40 wi wc water, 221 ‘Standard’ actcaion/oxidation method ‘ble 3 isan ouline of al of the melhods we in this dy. H describes the activation temperatures as wel the oxidation mtheds and amoxpheres ued in the pyrolysis oven during the activation. In the ‘Standard’ ‘method, the washed and dried acvated carbons were subjected to oxidation by at (loweng at 1 m? 8?) at 27 300°C for 4h inthe pyrolysis fumace und then allowed {o cool to room temperate 222 Comimwus acttaon/oxidation method ‘Some of the musells wore activated at 450°C under nitrogen as previously described. However, instead of removal and. ashing followed by exidaton of the ‘arbons, these carbons are oxidized under breathing (wade a a1 300°C for 4 without first removing and Swashing the sample. Thow are relerol (ous "Contin ‘aos sesvation eialion run i he text and tables. 22.4 “Airactisaton’ method Some of the nuthels were adivated al an TT (70C and HIT 450 for Fh as in the earlier, Standard’ method, but under flow of brealh- fing grade air at 0-1 m! he! Nowrate Aller thie the oxen ‘was shot of an allowed to cool to near room tem= perature undera flow of ai. ‘There was no discrete oxidation step separate from the activation step. Ths was done lo test the Hypothesis that an air atmosphere would mot acgatvey alec the production of surace area and may even obviate the reed for a separate ait-oxiation step, thus greally reducing the ume and material needed for the pro duction of high surfice area tivated carbons wih ‘lal adsorption capabibien 224 Quen activation method ‘This set of samples was run im order to determine the role of the activating atmosphere and healing rezimes. Ts the ‘Quench’ method the samples were acivaed as bore in the ‘Airactivation’ russ, uti this axe the temples were wo cooled to roora empocae ley i fhe oven, bul were remaved ane quenched either in oom temperature disilled water ori air. Ths method will determine if additional sir-oxidation occurs aller the activation during cool down inthe oven. Dsscrgtion of Actvation Methods usd t» Produce GACS fom Nussels Gas Temperctun Tine Sandard NX, HOGOS 1a ew 450 C1h ‘continuous N, mOCOSIA Mew 45001 Airastvation Ae 110-005-108, thn svc h Qusrch Ae 0CDSIR then 45001 h Modticd Quench Ar 480 CT Sep (temperate) —fomee ep CHR —-s0CHR Ye None None Ys enth None None No ve ah28 225 “Modified Quench aeseatio method Select sarpes were mun sing a modification of the “Quench? method, In thiscate the semples were rot held ALLTT for any length of tine. stead the saraples were ‘ramped up to HTT onder ir nl eld therefor 1, Aller whith they were removed [eam the oven and Allowed te cool rapil. 25 BET wrfacoaroa and pore size distribution ‘The DET she area romaremamia wore oblainad Irom witrogen adscephion ethers at 77K sing Micromeritis Gemini 2375 Surfuce Area Analyzzr.Spe- cic surface areas (Spe) Were taker, asi other studs, {rom adscepion Soherms using the WET equation =" TThe mesc- and macreperosites were calculated using the BUH model, and poresize distributions were caleue lated using eplots!= 24. Meta adhorption A3 mu solution of CuCl, was made up in a 6-07 modal solium aceate-O08 moll acetic acid bufer (pH 48) ‘One gram of carbon was sired for 24 Bin 1Dem? of the metal olution. The pl of the lary wa ecerded at the start and a the end ofthe experiment. An abiguot of any carbon particles The sump was diluted 1:10 by ‘olume with 4 vol% HNO, (Ultrapure, ICP grade) and aralyzal by ICP spectroscopy using & Leeman Labs ‘Plasms-Spec sequential ICP. Teale mmeul alsorption studies indicated that, ‘without a bulfer in the sistem, the carbons were able 10 ‘lier the pH of the slory (9 wales ant ofthe range optimum meta adorplion, Previous stad of meta ladkorption by carbons from agricultural waster fund thit optimum metals asorption occured above plT 4 A protons ately at ts Ltboratry compared, metal Uuplake in bulfeed and unbuffered solutions with almond sell crtors. The bufered solutions rested in the absence of visite metal precipitates aller the Souk timeand 2 higher metal adsorption overall. Th light of almost tolal removal of Cull) fora the 13 mu solutcns by some ofthe acd-activated carbons in ihis study, series of metals uptake experiments were dome om elected acl-activaed carbome xing bufered WOrar aC), ssluon under the same conditions ax shove 25. Determination of total table negative wrface charge: A method bused on that of Boch! way moti to ascent tou Urable charge en the surtace of these CA. Toles, WB. Marshall. MM. Jakns ‘carbons ia an ellot to relale surface charge the ‘copper uptake behavior of the carbons, The method invobes suspending O5 of the carbon jn 0-100 © NaOW solation and stirrng in = dosed esl for approximately 20-24 Mle this fiese an bguot of the lury Glered and 10cm? are ade to 1S em? of OFS NICL The HCI neutralizes the uncom sumed base ard keeps farther reaction beswaoe atmo spheric CO; und NuOH from covering. This solution ‘sen back-titaied with O4 NaOH sn! the amount of ‘rable negative suri charge per gram of carbon can be calculated ae mol Hg" earton. 26 Organic adsarpion The six compounds chosen for adsorption by the ‘carbons in ths study; beszene, toluene, 1,tdioune, ‘acctoniri acetone apd methanol were chosen because ‘ofthe range of plarites these compounds show. as well, OF g carbon in contact with 4 soluton watain 80 ppm cach of the it alps Ind above. The ‘carbon was lll comlact withthe analytes for 24 at oom lemperalurs, aller which an alguot of the solu- ‘ion was drawn off and un internal sandard of topro= penal was added. The headspace was sampled using pelydinethyisioxane-divinlbenzene SPME. fiver for analysis by a Hewlet-Puckardl GC equipped with 30m » O53 mm id VOCOL column and Mame ion ination detector The inkl aed detector lerapeaties were sel (9 220°C. The sample was thermally desorbed he fier for 5 mai a te ine eraperatr. 3, RESULTS AND DISCUSSION AL Activation and ox For the carbons produced in this study the yields ore batween 3) ane A184 (Tabled) Asin previous work it appears that thee & yery litle difleence beeen the Ccurbons produced ftom difeing precursor materials. Almost al ef the carbons develope surface areas near orimexcess of 10) m= 2 ‘One of the goals of this research was to allem to streamline the process of acid-uctvatien/odation 10 produce carbors with high metals und organics uptake “To thie end. there were several livation oxidation schemes explored, namely: Stindard” ‘Continuo’, “Aer soivation: “Quench and Modiied Quench aetna Lions al of which were decribed earir ‘The ‘Slandant" activation onidation enthod was con Sider time consuming and inefiient in its approachTWBLE Product Ves and Surface areas (5) OF Nats GACs Made by Diferen Methods oy a wea lo aching an oxidized surfs, The Continacus ‘method was investigated te save preventing ine and te determiae if Ue sample could be succesfully exilized while We phosphoric acid and phnphates were sill in the carbon, und to determine if oxtalion adverse lected th eeyclabily ard rewabiity of tread The *Contimuous’ method proved quite succes in producing an activated carton with almest the same Dpropertis as thos produced from the Sundard Inethod in which the acid was washed out of tre carbon Prior to oxidation. Black walnut shell carbons and mac. adamant shell carbons had very smlar BET surface frets (Table 4) Surince areas and ys values were nO reilly diminished i= carbons From almond shells pects shall or English walnut shelly either Ths ind (Sites that osidation wih the aid stl prowrt did not ‘Shc itherlathor signiicantmrlace ar developer fr mrfaze area less Vicks are ail abut the same for the wo piowesies, thu indicating ne sigaifeant change jn earbon mass eas. ‘Mais uptake By the ‘Continuous carbons were as good as those carbons synthesized by the ‘Sundard ‘method (Table 5), Both the ‘Standard and "Continuous fashons.ouiperformel. the commercial carbons in copper uplake by about 200% (Table 6, “The nest sien in sieumbning the proces was to explore th effect of ar exidizing atmosphere during the nou nat alec roses A numberof eardons were pyrayeed,acvate (Sh and ovidizad ia ait and are sdelied ae “Air~ ‘ctivalion carbons. The resuls of ths experiment agree With the observation by Molinz-Sabio etal! thatthe cexidiang atmosphere does not seem (0 affect surfoce fare development, bul in the case cf most nutshell ‘irons stad here i! appears that no separate oxida tor sep & necessry (0 develop high metals uptake (Table 5. IC was orsially thought that perhaps during the cooling sep the midationlakex place, thus prodae jag a good melal-uplate carbon These carbone ako Iie some of the highest matals uptake valucs of ay of the other carbons meuured in tht stdy (Tables Saad ry Ta un effort to determine the effect ofthe cooling stp under air, sect nutshell amples were moved fiom the ‘oven immediaely aller the 480°C HTT step (1) and ‘quenched im water The samples were washed and then analyzed lor metals, and organics uplake as well as ‘urlice area. The Spey for the sarapes was not dimin- ‘shed by the lack of a cool-down step unde ar, with 3 sarlace areas in excess of (200mg The metus uptake & also very high, indicating thatthe oxidation Copper Uptake (mmoles Cut! adsorbed g' carbon) fmt nw and 10m Cu! Solutions for Nusbcl GAC# Made by araction Demi aliied Quoc Sma aM aM lm San mat ‘Ainone os 0” 0@ — 056 ‘ac walnut = os bots engi walnut oo 0 Oem Macdama 0% om 0M 08