TAP CHl KHOA Hpc & C 6 N G NGHg CAC TRU'QNG DAI HpC K f THU^T * S6 89 - 2012
T 6 N G H O P P O L Y M E A L U M I N O S I L I C A T Ttr CAO LANH VA DUNG DJCH NajSiQ, SYNTHESIS OF A L U M I N O S I L I C A T E POLYMER FROM K A O L I N A N D NajSiO, SOLUTION
La Thi Vinh
Trudng Dgi hgc Bdch Khoa Hd Ndi
Nh^hi itgAy 29 thing 12 nam 2011, chip nhfn dSng ngfiy 8 thing 6 nSm 2012
T 6 M TAT
Bdi bdo ndy trinh bdy mdt sd kdt qud nghidn cOv thu dugc khi sO' dgng cao lanh tinh PhO Thg cd chua 37,37% AtgO^d Chd tgo polyme nhdm siiicat bdng cdch nung ndng cao lanh tu 66CfC ddn 71&C tn^ng 6 gid sau dd cho phdn Ong v&l dung dich NaiSiOj. Thdnh phdn dung dich Na2Si03 gdm:
NajO = 9.21%: SiOi = 37.48 %: H20 = 53.31%. Anh hudng cda nhidt dd phdn Ong. thdi gian phdn Ong, thdi gian nung cao lanh. tdc dd khudy trdn ddn hidu sudt tdch nhdm dS diugc nghidn cOv. Thdnh phdn dung dich phdn Ong dugc chudn bi (100ml NajSiOj * 15ml H2O + lOg kaolin), kich thu&c hgt cao lanh s 0.1mm Khd ndng tdch nhdm khdi cao lanh dugc tinh todn nhd ph&n tich thdnh phdn dung di(^ sau phdn Ong vd hidu sudt tdch nhdm Idn nhdt dgt dugc khodng 99%. Phd hdng ngogi (IR), phdn tich nhidt khdi lugng (TG), phdn tich nhidt vi sai (DSC) dd dugc sd- dgng Od nghidn cOu cdu trde vd khd ndng bdn nhidt ctia polyme.
ABSTRACT
This paper shows the study msults of using of kaolin containing 37 37% /U3O3 in Phu Tho of Vietnam for the production of aluminosilicatepolymer by calcination at from 66CfC to 71(fC forth then reacted with sodiumsilicate solution. The composition of sodiumsilicate solutkin includes: Na20=9.21%;
Si02 = 37.48 %; HjO = 53,3)%. The effects of reaction temperature (4<fC to 7(fC), reaction time, time of calcination and stiring speed on alumina extraction ware studied. The ratio of readkin composiUon was prepared (100ml Na2Si03 + 15ml H2O + lOg kaolin), particle size of kaolin s 0,1mm. The alumina extraction from kaolin was calculated by analysing soiutkjn compositkyns after reaction and Oie maximum extraction was about 99%.lnfrared (IR) and TG, DSC ware used lo study structure and heat resistance of polymer.
Keywords; Alumina extraction, Sodiumsilicate solution, kaolin, aluminositicate, polymer
1. T 6 N G Q U A N Hifn nay ehit kit dinh trfin co sd polyme r, , . , ;• . A L-i. >i L Aluminosilicat di dugc nghien cihi va dng Polyme Aluminosilical dupe bifil dfin nhu . . . . . , . . . ; . . ,t .,r -. U-. I -. J- 1. • J . L^. - =. a\"ie ^ha rpng rii a mgt sd nuoc tren the giai.
mft chat ket dinh su dyng Irong che tgo cac vit A w - . M J i.-- • '• ' 1. • ... , . „i ; . , , . , O Vi(;t Nam, cic nghien cuu ve long hgp va hfiu xay dyne.Cau true cua po yme logi niy . . - . • -Ti-- • » . , . , . ,. . . . T . , - . , / . ,-. ^ - ^ ung dyng cua loai vat lieu nay van con mai, chu
dirge hmh thanh tren co so cic cic lir difn S,0. ^^^ , ^^„ ^1,. g j , va AlO. vo, cong thirc: Mn[-(SiO,)z- bio niy di cfip djn qui trinh t6ng hgp polyme
A10,ln.wH20..rong d6 M 14 kim 10,1 kiem Na. Aluminosilicat tir Caolanh vi d i g « K hay kiem tho Ca: n la muc dp da trung ^^^,550 „|,4,„ ^,|,^ ^ ^ ^ . ^5 ^ ^^i„
. . n . r n . . . .. IA I T •; U^)l^ 1A« k ~ - DL.. •l...A„ ..A_ " f o r nhi?t [2].(3].
ngung: z li 1, 2, 3 ho$e Ion hon. Phu thupc vio ti Ip SiO^/AbO] CO ba lo,i don vj mfit xich co
so khac nhau: 2. NGUYEN LIF.II VA PHUONG PHAP CHUAN Bl
Polysialate (PS), -Si-O-Al-0-.
SiOj/AhO, = 2, tuong ung vol ti Ip Si/ANl; " ^ a u cao lanh nguyen khai dupe say kho. nghien mm den kich thirdc hat duoi Polysialate-siloxo (PSS),-Si-0-Al-0-Si- 0.1mm dung dl phin tich thanh phin hoa hpe 0-. Si02/Al20, - 4, ling voity I9 Si/Al=2; vi ciu true pha.
Polysialate-disiloxo (PSDS). -Si-O-AI-O-Si-0- „ j - u .i.- • ,. , . . u- c - r , cr\ ,A, r^ £ . • •• .• i- - DuHg dich thuy tmh Ong mua tren thi S1-O-, S1OVAI3O3 - 6, tuong ung vol ti Ip , . . . ; , fx . . % . , "
e - , . , , , , . & b * truong co thanh phan: Na^O = 9,21%;
' ^ - Si02=37,48 % ; HiO - 53,31%; khdi lupng
TAP CHi KHOA Hpc & C6NG NGHf CAC TRUtiNG DAI HpC Kt THU^T * S6 89 - 2012 rifing d = 1,36 gam/lit. Dung djch thuy tinh ldng
dugc pha loing bang nudc theo ty If lOOml dung djch NajSiOs + I5ml H2O dCing dl phin dng vdi cao lanh d cic diiu kifn khic nhau.
- Khi ning tich nhdm khdi cao lanh dl tgo polytne dugc dinh gii thdng qua phin Ifch thinh phin AI cd trong dung djchlhu dugc sau phin dng vi quy ddi vfi dgng AI2O3.
3. K £ T QUA VA THAO LU^N
Thinh phlhi hda hge miu cao tanhsir dyng trong nghifin cini dugc cho d bing 1,
Thinh ph4n pha cua cao lanh dugc thfi hifn qua phd nhilu xg tia X (XRD) trfin miy Advance-Bruker vdi gde qufit iCr 5° din 60°. Kfit qui XRD thu din;;rc cho thfiy trong cao lanh ehda chCi ylu Ii cic khoing Kaolinite Al2(Sii05KOH)4, Kyanite A^SiOj, ngoii ra cdn cd Halloysite Al2Si205(OH)4 vi khoing Hydrogen silicate HiSijOvihinh I). Cic thinh
phin pha rin cdn Igi trong cao lanh cd thi nim d dgng vd djnh hinh hofc tgp chdt vdi him lugng nhd.
Nghifin cdu inh hudng cua nhift df nung cao lanh din khi ning tich nhdm, chdng tdi di lim thi nghifm vdi cic diiu kifn:
- Nung cao lanh d cic nhift df: deO^C, 670°C, eSO^C, 690°C, TOO^C, 7 lO^C trong 6 gid.
- Thye hifn phin img vdilOOmI dung djch Na:Si03 + I5ml nudc + lOg cao lanh di nung, tiin hinh khuly trfn d 60 - TO^C trong 4 gid.
Lugng dung djch trong binh phin thig ludn dupe duy Irl d mde khdng ddi. Sau phin Omg, Ipc tich dung djch, riia sgch bi dl thu hdi hfit phin ch^t tan vi djnh mfrc dung djch trong binh 250ml dl xic djnh hifu suit tich nhdm. Kfit qua hifu sudt tich nhdm phy thufc nhift df nung eao lanh dugc cho d bing 2.
Bdng I. Thdnh phdn hda hgc mdu cao lanh Phu Thg
Thanh phin Ham lirpng {%)
SiOj 43,79
Al.O, 37,37
FejO, 1,94
TiOi 0,38
CaO 0,77
MgO 0,89
K2O 1,11
NajO 0,02
Mat khi nung o850°C
4,10
FaoJty of Chemistry. HUS. VNU, 08 ADVANCE-Bruker - Mau 2
2-Theta - Scale
Hinh I. Gidn do XRD mdu cao lanh Phu Thg
Ti>P CHf KHOA HQC & C6NG NGHf CAC TRUdNG D^I HpC Kt THU^T* S6»-20I2 Bang 2. Hi^u sudt tdch nhdm phg thudc nhi(i
dd nung cao lanh Nhift do nung
cao lanh ("C) erio 670 680 690 700 710
Hifu suit tich nh6m (%)
49.11 53.42 59,45 60,75 61,44 99,09 Nhin vio bing 2 ta thdy khi ting nhift df nung caolanh iCr ddO^C din TlOV khi ning tich nhdm line vi dgt gii trj Idn nhdt d 710'^C, diiu niy cd thfi ly giii li do khi dd caolanh Igo dugc nhChig cdu true x6p, thufn Igi cho qui trinh xim nhfp vi tuong tic cua cic ion hogt tinh trong dung djeh Na2SiO) vdi caolanh. 6 7I0°C khi ning tich nhdm cao nhit. diiu niy li do d 710''C khoing trong cao lanh chuyin hda ihinh melacaolinit (Al203.2Si02) tgo nfin khoing 20% id xip lim cho cao lanh hogt tfnh hon vi dl tich nhdm han[4j,[6]. Kit qui niy tuong duong vdi mSu cao lanh 29,4% AljOj nung d 600V trong 1 gid sau dd lich bing dung djch HCI 3M [5].
Khao sat inh hudng cua thdi gian nung din kha ning tich nhdm di chpn mSu caolanh nung d 710°C vdi thdi gian luu khic nhau (4 gid, 5 gid, 6 gid, 7 gid). Qui trinh phin ung dugc tien hinh tuang ty nhu tren.Ket qua nhfn dugc d bang 3.
Bdng 3.Hi4u sudt tdch nhdm phg Ihugc thai gian nung cao lanh
Thdi gian nung eao lanh (gio)
4 5 6 7
Hipu suit tich nhom (%)
72.81 74.53 99.09 87.46 Tir bing 3 la thay khi nung eao lanh d 710''C trong khoing 4 dfin 5 gid Ihl kha ning tach nhdm gan nhu khdng ddi, trong khoing 5 dfin 6 gid cho kha ning tich nhdm ting Ifin vi dat cao nhai ung vdi thdi gian 6 gid. difiu niy cd the ly giai li do vdi thdi gian luu nhu tren dam bao cho khoang kaolinit chuyfin hda lot
thinh melacaolinit lim cho cao lanh hogt tinh hon, nung liu hon 6 gtd thI khi ning tich nhdm Igi glim, dllu niy cd thi Ii do qui trinh kfio dii thdi gian nung lim cho khoing melacaolinit bj gii hoi, CO ngdt vi vfy giim khi ning hogt tinh ciiB nguyfin tCr AI trong khoing[4),[6].
Nghifin cihi inh hudng nhift df phin iimg din khi ning tich nhdm.di su dyng mau thi nghifm vdi lOg cao lanh nung d 710 C trong 6 gid phin ling vdi (100ml dung djch NajSIOj + 15ml HjO)d cic nhift df ( 4 0 ^ 5 0 ^ dO'C, 70^C) trong 4 gid.Kll quidugc cho d bang 4.
Bdng 4. Hl^u sudl tdch nhdm phg thudc nhift dg phdn ung
Nhift dO phin umg(«C)
40 • 50 60 70
Hifu suit lich nhdm (•/.)
38.77 43,94 96.94 94,35 Qui trinh nghifin cuu inh hudng cua nhift df phan ung din hifu sudt tich nhdm eho thdy ban dau khi ting nhift df phan ung tir 40°C din SO°C thi hifu suit tach nhdm hau nhu khdng ddi, khi nhifl dg ting troi 50°C thi hifu sudt tich ting, difiu niy cd thi ti do d mgt nhift dp thich hgp hogt tfnh cua pha Idng dgt gia trj Idn nhdt. vi vfy khi ning tuong tic cua pha long vdi pha rin lot nhit va hifu suat tich nhdm Ihu dugc cao nhit. Q gii trj nhift dp nhd hofc Idn han gii trj nhift dp thich hgp hogt tinh cua pha Idng deu giam do vfy hifu suit tach nhdm nhd hon.
Nghifin cuu inh hudng ciia thdi gian phin ung den khi ning tich nhdm, da khio sat phan ung Irong khoang thdi gian tu 2 dfin 5 gid.
Trong qui trinh phan ung ludn gifl' the tieh ciia dung djch khdng ddi. Ket qua dugc cho d bang 5.
Bang 5.Hi^u sudt tdch nhom phu thugc thdi gian phdn img
Th6i gian phin ung (gid)
2
J
4 5
Hieu suat tach nhom (%)
31,02 35,32 95,65 94,78 Nhin vao bang 5 nhgn thay ung vdi thdi gian khudy 4 gid cho hieu suit tich nhdm cao
TAP CHl KHOA HpC & C6NG NGHf CAC TRlTdNG D*I HpC Kt THlI^T * S6 89 - 2012 nhdt. Kfio dii thdi gian klluly qui 4 gid thi hifu
suit tich nhdm hdu nhu khdng ddi. 0 thdi gian diu khi ning tich nhdm tftng theo thdi gian vl khi dd cic phan Cmg chua dgt din cin bing.
Nghifin 6d-u inh hudng tic df khudy trfn din khi ning tieh nhdm, chdng tdi dfi llln hinh Ihi nghifm vdi mSu cao lanh nung d 700''C trong 6 gid, phin dng d nhift df 60^C vdi tic df khudy 400. 500, 600. 700, 800 (vdng/phut).
Kfit qua dugc cho d bing 6.
Bdng 6.Hi$u sudt tdch nhdm phg ihugc tde dg khudy trdn
Tie at) khuiy trOn (vdng/phlit)
400 500 600 700 800
Hifu suit tich nh6m (%)
74,11 78,41 95,65 95,22 95.65
tyc tang tic df khudy Ihl khdng lim ting Ihfim khi ning tich nhdm,
Nghifin ciiij cdu triic polyme tdng hgp dugc bdng phd hdng ngogi (hinh 2) nhfn thdy cd cic pic dao dfng nhdm (O-H) dfc trung cho phin tir nudc, pic dao dfng nhdm (Al-O-Si) djic trimg cho phin td polymealuminosilicat, ngoii ra cdn cd cic vai i!mg vdi cic nhdm dao dfng (Al-0),(Al-0H)vi(Si-0)[7].
? 0.
Kfit qui thu dugc cho thiy ban diu khi ting tdc df khudy thi khi ning tich nhdm ting, difiu niy la do khi ting tdc df khudy Iron sfi lam ting kha ning tifip xuc giiJa pha Idng va pha rin vi vfy tde dp phan img ting. Tuy nhien khi Idc dp khuiy da du de cho cic hgt cao lanh phan tin dfiu trong toin khdi dung djch mi vin tifip
(HiOwM
9
Ni'"^ShO-Al''-0-).
Hinh 2. Pho IR mdu polyme thu dugc khi phdn img vdi tde do khudy 600 vdng/phut d bdng 6
Hinh 3- Phd TG. DSC mdu polyme thu duac khi phdn img vdi tdc do khudy 600 vdng/phut a bdng 6
T^P CHf KHPA Hpc & C6NG NGHf CAC TRUdNG D^l HpC Kt THU^T * S6 89-2012 Nghifin cihi khi nfing bin nhift ciia
polyme qua phin tfeh nhift khii l u ^ g vi nhift vi sai (TG, DSC) nhfn thdy m3u polyme cd khi ning bin nhift din 900''C (hinh 3). Qui trinh nghifin cdu cQng nhfn thdy cd 2 pic thu nhift d khoing SO'C vi llO^C Cmg vdi qui trinh bay hoi ciia nudc. 2 pic tda nhift d 7D0°C vi 850°C cd thi do qui trinh chuyin pha tgo nfin.
Qui trinh nghifin cCm biin tinh hf polyme niy tim vft lifu ming phii chju nhift dS dugc dl cfp trong cic bii bio chiing tdi di cdng bl trade diy [2. 3],
4. KtTLU-^N
1. Di nghifin ciiii thinh phdn hda hgc vi thinh phdn pha mSu cao lanh Phii Thg, kit qui thu dugc cho thdy mSu chda chu ylu Si02 vi AljOj d dgng cic khoing Kaolinite Al2{Si20sXOH)4, Kyanite A^SiOs, Halloysite Al:SiiOs(OH)4 vi Hydrogen silicate HiSijOy.
2. Da nghifin c<iu inh hudng ciia nhift df vi thdi gian nung cao lanh din khi nfing tich nhdm, kit qui thu dugc cho thdy khi nfing tich nhdm Idn nhdt dgt 99,09% tgi nhift df nung 7I0''Ctrong6gi&.
3. Dfi Nghifin ciiru inh hudng nhift df phin dng din khi nfing tich nhdm, kit qua cho thdy khi ning tich nhdm Idti nhdt dgt96,94%
ling vdi nhift df phin img dO^C trong 4 gid.
4. Dfi nghifin cuu inh hudng thfri gian phin ting vi tdc df khudy din khi ning tich nhdm, kit qui nhfn dugc cho thdy khi ning lich nhdm cao nhdt dgt 95,65% s£ui 4 gid phin ung d tic df khudy tir 600 - 800 vdng/phut.
5. D3 nghifin cCru cdu true yi khi nfing chju nhift cua polyme thu dugc bfing phi hdp thy hing ngogi (IR) vi phin tich nhift TG, DSC.
TAI Llfl) THAM KHAO
1. M. Criado, A. Femandes-Jimenes, A. Palomo, "Alkali activation of fly ash: effect of the SiOz/NaiO ratio", Microporous Mesoporous Mater 106, 180-19! (2007).
2. La Thi Vinh, La Vin Binh, Anh hudng cua chdl biin tinh den cdu true cua hf polyme vd co Aluminosilicat, tap chi Khoa hgc vi cdng nghf eac trudng dgi hgc ky thuft s6 58, 1 lO-113 (2006).
3. La Thfi Vinh, La Vin Binh, Che tgo vi biin tinh vgt lifu polyme vd co Aluminosilicat lim chat phii bao vf, tgp chi Khoa hgc va cdng nghf cie trudng dgi hgc kj thugt sd 59. 85-87 (2007).
4. Nguyen Vin Dung, Cong nghf san xudt gom sd, Nhi xudt ban Khoa hgc vi KJ thuat (2009) 5. A.A. Al-Zahrani and M.H. Abdul-Majid, Extraction of Alumina from Local Clays by Hydrochloric Acid Process, Eng. Sci., Vol. 20 No.2, pp: 29-41 (2009)
6. H- Rahier, J. F. Denayer, B. Van Mele, Low-temperature synthesized aluminosilicateglasses.
Journal of Materials Science 38 (2003)3131 - 3136
7. Bhaskar J. Saikial, Gopalakrishnarao Parthasarathy. Fourier Transform Infrared SpectroscopicCharaclerization of Kaolinite from Assam andMeghalaya, Northeastern India, J. Mod.
Phys.,2010, 1,206-210
Dia chi lien h^: La The Vinh - Tel 0912540041; Email: [email protected] Vifn Ky thugl Hda hpc -Trudng Dgi hpc Bich khoa Ha Npi Sfi 1. Dgi Cd Vift, Hai Bi Trung. Ha Npi
