TRACE ELEMENTS IN SOLUTIONS FROM ZEOLITE SYNTHESIS

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Grażyna Markowska
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1 CIVIL AND ENVIRONMENTAL ENGINEERING REPORTS No TRACE ELEMENTS IN SOLUTIONS FROM EOLITE SYNTHESIS dzisł ADAMCYK, E MAKOS, Ktrzyn NOWIŃSKA Silesin University of Technology, Gliice, ul. Konrskiego 22 The er resents the content of selected eleents in solutions fored fter the synthesis of zeolitic teril bsed on fly sh. Fly sh sles ere tken fro to ulverized fuel-fired boilers t the Rybnik Poer Plnt: one boiler fired solely ith col nd one co-fired ith col nd bioss. The tests conducted hve shon tht solutions reining fter zeolite synthesis fro fly sh generted in boilers co-fired ith col nd bioss hd higher content of eleents thn those derived fro fly sh generted fro burning only col. It s lso found tht incresing NOH concentrtion of the solution used in zeolite synthesis cused incresed content of the individul eleents. Keyords: zeolite, trce eleents, synthesis, solutions 1. INTRODUCTION eolite synthesis fro fly sh cn be chieved by severl ethods: clssicl lkline hydrotherl conversion of fly sh, lkline fusion folloed by clssicl lkline conversion of fly sh, dry or olten slt conversion, to-stge synthesis. The hydrotherl synthesis of zeolites fro fly sh is the ost idely used ethod. Hydrotherl synthesis is hysicocheicl rocess conducted in n lkline solution under tosheric or incresed ressure (in tht cse the rocess is crried out in n utoclve). Hydrotherl synthesis consists in rocessing ixture of fly sh nd hydroxide (usully sodiu or otssiu hydroxide) under defined conditions of teerture nd ressure. Additives, such s sodiu chloride or otssiu chloride re lso used. The rocess involves lso filtrtion, shing nd drying of the resultnt teril. The Corresonding uthor. E-il: ktrzyn.noinsk@olsl.l

2 6 dzisł Adczyk, E Mkosz, Ktrzyn Noińsk rocess durtion, ccording to the literture, rnges in the vrious ethods fro fe hours to fe dys, or even ore thn ten dys. The rocess teerture rnge is lso ide: fro bient teerture u to severl hundred degrees Celsius. The higher rection teerture, the shorter rection durtion y be [1-4. In soe of the zeolite synthesis ethods solution is generted fter the rection nd fter shing of the teril obtined. No studies hve been crried out before to deterine the cheicl/eleentl coosition of the generted solutions. These solutions y contin eleents tht re not resent in the synthesized teril. Deending on the concentrtion thereof, they y ose n environentl hzrd. The urose of this study s to estblish the content of selected eleents in solutions fored fter the synthesis of zeolitic teril bsed on fly sh. 2. SAMPLING AND TESTING METHODS Fly sh sles ere tken fro to ulverized fuel-fired boilers t the Rybnik Poer Plnt: one boiler fired solely ith col (W) nd one co-fired ith col nd bioss (lnt nd ood bioss 8-9%) (Tble 1). To synthesis tril runs ere executed using the hydrotherl ethod ith lkline ctivtion under the folloing conditions: synthesis durtion 6 h, synthesis teerture - 170, fly sh quntity 100 g, ter quntity 600 L, NOH concentrtion 2M nd 3M. A "blind" synthesis run s crried out for corison. The conditions of the rocess ere identicl s in the to revious tril runs, but lkline ctivtion s not lied (NOH concentrtion 0M). Sle designtions re given in Tble 1. Tble 1. List of sles of solutions fter zeolite synthesis (nubering ccording to the reserch ln). Sle no. NOH concentrtion Boiler fired ith col Boiler fired ith col nd bioss 0.00M M M 5 19 After ech synthesis the teril obtined s shed ith the se ount of ter, enbling thereby corison of the eleentl contents of the

3 Trce eleents in solutions fro zeolite synthesis 7 solutions. Distilled ter s used both in the synthesis rocess itself s ell s for shing. The folloing eleents ere deterined in the solutions: Fe, Cr, Ni, Cu, n, Pb, Ti, V, Mn, Cd, Mo, B, C, Si, Al, N, K, Mg, Sb, As. Deterintion s crried out by ens of inductively couled ls toic eission sectroscoy (ICP-AES) on JY 2000 sectroeter. 3. RESULTS K, N, C, Mn, Mg nd Fe ere the ost nuerous eleents found in ll solutions. The eleents concentrtions ere resectively: K (verge concentrtion 571 ), N (v. conc. 179 ), C (v. conc. 53 ), Mn (v. conc. 39 ), Mg (v. conc. 52 ) nd Fe (v. conc. 19 ). The concentrtions of other deterined eleents found in the solutions ere belo 10 nd included: Cr, Ni, Cu, n, Pb, Ti, V, Cd, B, Si nd Al (rys. 1-4). The loest content of eleents s deterined in the solutions fro "blind" synthesis run (ith no NOH ctivtion). There is certin reltionshi beteen the content of individul eleents in the solutions nd the tye of fuel used (col, col nd bioss co-firing), irresective of NOH concentrtion (Figs. 1-10: in the cse of col nd bioss co-firing - higher content of Fe, Mn, C, Mg, V, Mn, C, Mg, N, K, Pb, B, Ti nd Al, s cored to firing ith col only, in the cse of col firing - higher content of n, Cr, Cd nd Si, s cored to col nd bioss co-firing. For such eleents s Ni nd Cu there is no cler reltionshi beteen their concentrtion in solutions nd the tye of fuel used (col, col nd bioss co-firing). There is certin reltionshi beteen the occurrence of Mo, Sb nd As only in solutions fored in the course of the synthesis fro fly sh generted during col nd bioss co-firing: Mo is resent only in sles nos. 18 nd 19, tht is in solutions fored in the course of synthesis in 2M nd 3M NOH solution, Sb nd As re resent only in the solution fored in the course of synthesis in 3M NOH solution. The results of eleent content deterintion in solutions fored in the synthesis of zeolitic teril lso indicte tht the content thereof deends on

4 Content Content 8 dzisł Adczyk, E Mkosz, Ktrzyn Noińsk the NOH concentrtion in the ctivting solution, irresective of the tye of fuel burned (Figs. 1-4): 3M NOH solutions hve higher concentrtions of Mn, Mg, Cr, Cd, N, K, B nd Ti thn the 2M NOH solutions, 2M NOH solutions hve higher concentrtions of C, Ni, Al nd Si thn the 3M solutions. For eleents such s V, Cu nd Pb there is no cler reltionshi beteen their concentrtion in solutions nd the concentrtion of NOH in solutions used in the synthesis rocess. The decrese of Si nd Al content ith incresing NOH concentrtion (in solutions used in the synthesis) found in solutions fter the synthesis y be n indictor of incresing efficiency of zeolite crystlliztion in the synthesis rocess. At the se tie incresing N content is observed hen NOH concentrtion is incresed, hich suggests tht soe sodiu does not rticite in the synthesis rection. 30 Stężenie NOH 0.4 Stężenie NOH Fe n Cu Cd 0 Sybol róbki Sle sybol 0.0 Sle sybol Sybol róbki Fig. 1. Content of Fe, n, Cu nd Cd in solutions fter zeolite synthesis fro fly sh fro the Rybnik Poer Plnt.

5 Content Content Content Content Trce eleents in solutions fro zeolite synthesis Stężenie NOH Stężenie NOH N K Cr Ni V 0 Sybol róbki Sle sybol 0.0 Sybol róbki Sle sybol Fig. 2. Content of N, K, Ni, Cr nd V in solutions fter zeolite synthesis fro fly sh fro the Rybnik Poer Plnt. 80 0M Stężenie NOH 2M 3M 6 Stężenie NOH Mn C Mg 4 2 Pb B 0 Sle sybol Sybol róbki 0 Sle sybol Sybol róbki Fig. 3. Content of Mg, C, Mn, Pb nd B in solutions fter zeolite synthesis fro fly sh fro the Rybnik Poer Plnt.

6 Content 10 dzisł Adczyk, E Mkosz, Ktrzyn Noińsk Stężenie NOH Ti Si Al. 0.0 Sle Sybol sybol róbki Fig. 4. Content of Ti, Si nd Al in solutions fter zeolite synthesis fro fly sh fro the Rybnik Poer Plnt. 4. CONCLUSIONS The folloing conclusions cn be drn fro the study of results of eleentl nlyses of solutions fored in the course of zeolitic teril synthesis fro fly sh generted by burning col or by co-burning col nd bioss t the Rybnik Poer Plnt: solutions fored fter zeolite synthesis fro fly sh generted by co-burning of col nd bioss hve higher content of eleents thn those derived fro fly sh generted by burning col only, incresing NOH concentrtion of the solution used in zeolite synthesis cuses incresed content of the individul eleents, decrese of Si nd Al content ith incresing NOH concentrtion (in solutions used in the synthesis) in solutions fter the synthesis y be n indictor of incresing efficiency of zeolite crystlliztion in the rocess. REFERENCES 1. Adczyk., Biłeck B.: Możliości syntezy zeolitó z oiołu EC Żerń. esz. Nuk. Pol. Śl., z. 256, 15-21, 2003.

7 Trce eleents in solutions fro zeolite synthesis Adczyk., Biłeck B., Hlski M.: Hydroterln syntez zeolitó z oddó leniskoych elektroni Łzisk, Prce Nukoe Głónego Instytutu Górnict, seri Górnicto i Środoisko, Berkgut V., Singer A.: High ccity ction exchnger by hydrotherl zeolitiztion of col fly sh, Alied Clz Science, Vol. 10, , Buklk D., Mjchrzk-Kucęb I., Nok W.: Wły zści Si i Al. oiele lotny n torzenie się frkcji zeolitoych tyu N-P1, Częstocho Querol X., Pln F., Alstuey A., Loez-Soler A.: Synthesis of N-zeolites fro colfly sh, Fuel 8, 1997, Sztekler D., Mjchrzk-Kucęb I., Nok W.: Anliz łsności cheicznych oioło lotnych od kąte syntezy eolitu N-A, III Ogólnoolski Kongres Inżynierii Środoisk, Ściubidło A., Mjchrzk-Kucęb I., Nok W.: Wły skłdu cheicznego oioło lotnych n efektyno rocesu syntezy eolitó N-X, III Ogólnoolski Kongres Inżynierii Środoisk, Tnk H., Mtsuur S., Hino R.: Fortion rocess of N-X zeolites fro col flysh, Journl of Mterils Science 39, Tnk H., Furus S., Hino R.: Synthesis, Chrcteriztion, nd Fortion Process of N-X eolite fro Col Fly Ash, Journl of Mterils Synthesis nd Processing 10, 2002, Włek T.: Adsorcj SO 2 i NOx n złożu zeolitó syntetycznych otrzynych z oiołó lotnych (SO 2 nd NOx dsortion on bed of synthetic zeolites obtined fro fly sh), Ph.D. Thesis, Institute of Environent Protection Engineering, Wrocł University of Technology, Wrocł, PIERWIASTKI ŚLADOWE W ROTWORACH PO SYNTEIE EOLITÓW S t r e s z c z e n i e W rtykule rzedstiono zści ybrnych ieristkó ostłych roztorch o syntezie teriłu zeolitoego n bzie oiołu lotnego. Próbki oiołu lotnego ochodziły z Elektroni Rybnik z dóch kotłó yłoych: olnego czysty ęgle i ze sółslni ęgl z biosą. Przerodzone bdni ykzły, że yższe zści ieristkó ystęują roztorch orekcyjnych, ostłych o syntezie oiołó ochodzących ze sółslni ęgl z biosą, niż roztorch o syntezie oiołó będących rodukte slni czystego ęgl. Stierdzono ondto, że rz ze zroste stężeni NOH roztoru zstosonego do syntezy zeolitó zrst ilo oszczególnych ieristkó.

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