TgpchiKhoah^TrudngDgihgcCdnTha Phdn A: Khoa hgc Tunhiin, Cdng nghi vd Mdi trudng: 34 aO}4): 45-50.
Tap chl Khoa hoc Tru'cJng Dai hpc Can Thd website: sj.ctu.edu.vn
LOAI ION BONG (II) BANG TRO T R A U
Doan Van Hdng Thien', Pham Hda Thai", Pham Thi Me', Ld Diic Duy' va Nguyin Minh Nhut'
' Khoa Cong nghe, Trudng Dgi hoc Cdn Tha . ^
Thdng tin chung:
Ngdy nhdn: 07/06/2014 Ngdy chdp nhgn: 30/10/2014
Title-
Removal of copper (11) ions by using rice husk ash Tiir khda:
Tro trdu. hdp phu. ion Cu(II) Keywords:
Rice husk ash, absorption, Cu(II) ions
ABSTRACT
Rice husk ash was obtained after burning of rice husk in the air. The rice husk ash was then calcinated at 65(yC for 1 hour to produce activated rice-husk ash (RHA). The main composition of RHA was is activated silica which can be used to remove Cu(II) ions by batch adsorption method. The IR spectra. XRD patterns, SEM images and BET adsorption were used to determine the silica structural composition and characteristics of RHA. In this research. The RHA was applied for the removal ofCu(II) ions using by anbalch adsorption method. The batch adsorption v\'as used in this research. The factors affecting the absorption of Cu(II) ions under investigation includedeffects of the main parameters were investigated, including: pH, adsorbent amounts, contact time and the initial concentration ofCu(II). The maximum adsorbtion capacity of RHA for Cu (11) ions was 4,1 mg/g.
Vo trdu dugc d6t chdy ngodi khdng khi, sau do sdn phdm duac nung trong Id nung a nhiet do 650°C trong thdi gian 1 gia. Sdn phdm tro trdu (RHA) ihu duac chua nhiiu silica tinh the vd duac dng dgng cho vi$c loai bo ion Cu(II) bdng phuang phdp hdp phi^i. Cdc phuang phdp phdn tich pho hong ngoai (FTIR), phd nhiiu xa tia X (XRD), dnh dudi kinh hiin vi di$n tir quel (SEM) vd hdp phu BET dugic su dung de xdc dfnh thdnh phdn cdu triic silica Irong RHA vd cdc dgc tinh cua RHA. Be hdp phii gidn dogn dirge lien hdnh de khdo sdt khd ndng logi bo ion Cu (II) trong nghien cuu ndy.
Cdc yiu to dnh huang den qud trinh hdp phu dugc khdo sdt gom co: pH, lugng chdt hdp phy, thai gian tiep xuc vd nong do ddu cda ion Cu(II).
Dung lugng hdp phjj cue dgi cua RHA doi vdi ion Cu(II) la 4,1 mg/g.
1 GIOTITHIPU
Kim lo^ ning (KLN) la mpt Uong nhttng tdc nhin ldn gay d nhiem mdi trudng do do vdn dl loiti tru ion KLN dang Ud nln cip thilt hiln nay (Iqbal, et ai, 2009, Mance, 1987, Momodu, et al, 2010).
Trong so tit ci cie ion KLN thi ddng la ion diin hmh nhdt vi cd mdt d hdu bet cic loai nude thai.
Ion d^ng cd rdt nhieu Uong nude toai cic nhi may san xuat di?n tu, luyen kim vd xi ma (Farooq, et ai, 2010, Gupta, 1998). D6ng li mdt nguyin to vi
lupng cdn thilt cho cay Udng nhung d ndng dp cao nd Ud nen dpc hai ddi vdi ngudi, d^ng vit va ciy cdi (Brewer, 2009, Maksymiec, 1998). Hip phy Id phuong p h ^ cd nhieu uu diim va dupe su dyng rpng rii do xd ly nhanh, dl chi tao thiit hi va die biet la cd lpi ich vl kinh tl. Than bo^it tinh la chat hdp phu thudng dupe su dung nhung tii ddt tiin va do dd xuat phat tir ngudn phe toii phong phu cua ngdnh ndng nghiip (Biomass) vd Uau ducrc coi la ung eir viln sdng gii nhdt (Bogdanov, et ai, 2012, Chungsangunsit et al., 2009). Trong vd Uau ed
Ti^ chi Khoa hgc Trudng Dgi hgc Cdn Tha Phdn A: Khoa hgc T\t nhien, Cdng nghi vd Moi trudng- 34 (2014): 45-53 chua ham lupng ldn ngi^ln t6 Si vi toi khi dupe
dot v i nung, vd triu si biln toinh uo triu cd chira nhilu silica (SiOj) vdi cic dang tou hhto khic nhau (Delia et al., 2002, Kalapatiiy, et ai, 2000, Xiong, et al., 2009). Vifc tao toanh cic d^ng toia hinh phu thupc rat nhieu vao diiu kiln nung vdi hai todng sd quan trpng la nhiet dp vd todi gian nung (Ngo, 2006, Patel, et ai, 1987, Ramzanianpour, et al., 2009). Silica vd dinh hinh ed cau true xdp va cd dien tfch bl mit rieng ldn hon silica tinh thi do dd se hip phu tdt hon (Ngo, 2006, Stallons. et al., 2001). Do viy, RHA da dupe dng dyng lam chit hdp phu cac hpp chit hOu co uong nude (Daud, et ai, 2010, Mahvi, et ai, 2004, Manique, et ai, 2012) va vin ^k hip phu ion KLN cung dupe khdo sat qua (El-Said, et ai, 2010, Johan. et ai, 2011).
Tuy nhiin, nhftng sdn phim Uo triu toudng cd nhftng dgc tinh khdc nhau do qui triito chl t£to khdc nhau trong mSi nghien cuu. Vi vdy, d dl tai niy chdng tdi nghiin cdu chl t^o sin pham Uo uiu chiia nhiiu silica vd dinh hmh cd ciu true xdp vd be mit rilng Idn di iing dung hip phu ion Cu^*
Uong dung dich.
Trong nghi6n curu nay, ion KLN duac chon la ion ddng (II), chit h i p phu la RHA thu duac tiJr vo triu thong qua nung v^ co diiu khiln qua trinh nung d l thu dugc RHA chua nhilu silica v6 dinh hinh. Ion d6ng (II) hip phu tren be mat silica dupe khSo sat qua cac thdng sd pH, thai gian h i p phu, lirgng tro triu va ndng dd ion dong ban dau.
2 T H V C NGHIEM 2.1 Hda chat vi vit lieu
Dung djch mudi ddng (!I) chuan vdi ndng dp 1000 mg/L, axit elohydric (HCI), nabi hidroxit (NaOH) dupe mua tCr cdng ty Merck (Diic). Vd triu dupe lay tii huyen Cdng Long, tinh Tra Vinh.
2.2 Phinmg phdp diiu che tro trau RHA 100 g vd trdu dupe nia va khuiy voi nude cat Uong 2 gid, sau dd dupe khuay vdi dung djch HCI 1 M trong 60 phut vi phoi khd rdi dem ddt d ngoai khdng khi cho din khi chiy hit uiu sdng tou dupe vd trau sau khi ddt chua nhiiu carbon. Vd uiu sau khi ddt dupe nung ttong Id nung d nhiet dO 650 "C trong todi gian 60 phut tou dupe sdn phim Uo ttiu RHA.
2 J Khao sat be mat va eau triie RHA RHA duoc quan sat bl mat bdng kinh hiin vi dien tu quet SEM, xdc dinh toanh phdn rtodm chuc bing phuong phap do phd hdng ngoai IR, khdo sat cau tnic todng qua do nhiiu xa tia X (XRD). Tiin haito do BET xac dinh dien tfch bl mat rieng cua RHA.
2.4 Hap phu dang nhiet theo md hinh Langmuir
Hap phu dang nhiet la yeu td quan ttpng nhat Uong qua ttinh nghien ciiu, dupe tiln hdnh bing cae thi nghiem hip phu sd dung ndng dp ion Cu(II) ban diu toay ddi tii 25 din 125 mg/L d pH dupe in dmh ngiu nhien pH = 4 luong RHA l i 0,5 g va todi gian tiip xiic 60 phiit. Dung lupng hip phy (mg/g) dupe tinh toan toeo phuang tritto:
C - C , „
a =
(1)Trong dd: Qe Id dung lupng hdp phy, mg/g Co, Ce lan lupt la ndng dp Cu(II) ban ddu vd sau hip phu, mg/L
V la till tich dung dich Cu(II), mL W la khdi lupng RHA su dung, g 2.5 Nghiin cihi anh hirdng ciia cae thdng s6 Hap phu be gian doan dupe tien hdnh de ngliien cuu dnh hudng cda eic todng sd chinli cua qui Uiito hap phy. RHA dupe cho vao coc ehua 50 mL dung dich Cu(n) vdi ndng dp 27,6 mg/L. Sau khi khuiy tu d tdc dd 250 vdng/phdt d nhiit dd phdng, cdc dung dich dupe ly tdm d tdc dp 6000 vdng/phut Uong 20 phut v i pban dung^dich toujjjoc de_m_^di ditto luong bang phuang phap'phd hdp thu nguyin tii AAS.
Anh hudng cua lirang RHA: 0,5; 0,8; 1,2; 1,5 g RHA dupe SIX dung cbo cdc toi nghiem tai pH = 4 va todi gian tiep xiic li 60 phut.
Anh hudng cua pH: pH dupe toay ddi tu 2 den 5 va dupe dieu chinh bang dung dich NaOH 0,1 N va HCI 0,1 N. Thdi gian tilp xuc li 60 phiit ung vdi 0,5 g RHA.
Anh budng ciia thdi gian tiep sue: Cic thi nghiem dupe tiln hinh d pH = 5, todi gian tilp xiie thay ddi tft 20, 40, 60, 90 va 120 phiit ung vdi lupng RHA la 0,5 g.
Tup ciii Khoa hgc Trucmg Dgi hgc Cdn Tho Phdn A: Khoa hgc Tu nhiin, Cdng nghi vd Mdi Irudng: 34 (2014): 45-1.5/
3 KET QUA VA THAO L U ^ 3.1 Cau true, tinh cbit va thanh phin RHA 3.1.1 Kit qud dnh kinh hien vi dien tu quel (SEM) Hinh 1 biiu dien inh tro triu dudi kinh hiin vi
diln tii quet (SEM). Ddi vdi RHA, bi mit cd rit nhilu Id xdp so vdi fro triu phy phim vdi bi m|t nhin bdng, it Id xop. Qua dd, chdng ta cd thi tiln dodn rang dien tfch hi u4t cda tto Uiu tong hpp cao hon diln tich bl m^t ciia tto ttdu phy pham.
Hinh I: Anh SEM bi mait cua tro trau diiu chi: A. dd phdng d^i 1.500 lan, B. dp phdng d^i 15.000 lin;
eua tro triu ph^i ph|mLC..Bp phdng dai 1.500 lin, D. Dd phdng dai 15.000 lin 3.1.2 Ket qud do pho hong ngogi IR
Hinh 2 biiu dien phd hdng ngoai IR eua RHA.
Phd IR cho toay cdc mui dac trung cho cdc kiiu dao ddng khdc nhau cua cdc nhdm chuc bi mat.
Nhdm - OH tuong iing vdi mui 3468 cm"'. Dao
ddng hda Uj ciia nhdm siloxan (Si-O-Si) ftjong ling vdi mui 1111 em"'. Dao dpng cua nhdm Si-OH tuong ung vdi mui 803 cm"'. Biin d^ng gdc Uong nhdm siloxan (Si-O-Si) tuang img vdi mui 465 em"'.
Tgp chi Khoa hgc Trudng Dgi hgc Cdn TTur Phdn A: Khoa hgc Ttr "hiin, Cdng nghi vd Mdi irudng: 34(2014): 45-53
Hinh 2: Phd hong ngoaii IR ciia RHA 2.1.3 KitqudXRD
Hinh 3 biiu diln phd itoi^u xg tia X (XRD) cua Uo Uau. Pho XRD cda RHA vd eua Uo ttiu phy phim diu xuit hiln mdt peak rdng d gdc 26 = 15^
30° die tnmg cho cau Uuc vd djnh hinh cua SiOi- Tuy nhiin doi vdi tto trau phy phim thi tai ddy
cung xuat hien peak nhpn d goc 29 = 22,14° vd 22,2"die tnmg cho cdu ttuc tinh toe cOa SiOi Uong khi do d RHA toi chi cd 1 peak duy nhit 29 = 15-^
30°, khdng cd peak die trung ndo khic. Tu ddy kit luin ring RHA chiia chu yeu la S'lOi vd dinh hinh edn tto ttdu phu pham chda ci Si02 vd dirdi hinh va SiOi tinh toi.
Hinh 3: Phi XRD ciia: (a) Tro trau phu phim, (b) tro trau tdng hop
48
Tgp chi Khoa hgc Trudng Dai hgc Cdn Tho Phdn A: Khoa hgc Tu nhiin, Cdng nghi vd Mdi Irudng: 34 (2014)- 45-53
3.1.4 Kit qua do BET
Hinh 4 biiu diln kit qui hip phu BET cua nita len hi mdt tto trdu. Kit qui tou duoc cho thiy miu tto trdu phy phdm cd di^n tich hi m^t rieng la 28,35 mVg ttong khi bi mat rilng cua RHA do
dupe li 146,4 m^/g. Kit qui nay hoan toin phii hpp vdi gii touylt ban diu va kit qui phin tfch phd rtoieu xa tia X. Diln tich bi mat rieng ldn cua tro uiu tdng hop se mang lai hieu qui hap phu ion ddng(n).
BOOOO TGCOO T . 3 f i n GBDOa E 4 a n saxa seooG _ SZMO T 40X0
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Hinh 4: f>6 thi hap phiJi BET ciia N: len bl msit tro triu: (a) tro triu phu phim; (b) tro trau t6ng hpp 3.2 Ket qua khao sit inh hirdng cua cac
thdng so cua qua trinh bap phu 3.2 I Anh hudng cua lugng chdt hdp phu Hinli 5 biiu diln sy dnh hudng cua lupng Uo
ttiu dieu che den bilu sudt hip phu. Tft di toi, dl nhdn toiy ring khi lupng RHA tang thi hipu suit hdp phy cung ting toeo do be mit edn ttdng cua RHA. Hieu suit hdp phu eao nhit dat 81% tuang ftng vdi 1,4 g tro triu.
Tgp chi Khoa hgc Trudng Dgi hgc Can Tha Phdn A: Khoa hgc Tu nhien. Cdng nglii vd Moi irudng: 34 (2014): 45-53
0,6 0,8 1,0 Lifffng RHA (g)
Hinh 5: Syanh hirdng cua lirpng RHA den bieu suatva dung lupng hap phu 3.2.2 Anh huong cHapH
Hinh 6 bilu diln ^ih hudng cua pH lln hieu suit hdp phy. Khi pH tang tft 2 din 5 ldm cho hieu sudt hap phy tang do d pH thip toi nong dd ion H*
cao, xiy ra sy c?nh Uanh hap phu ion H"*^ vdi ion Cu^^. Thi nghiim khdng dupe tiln hdnh d mdi trudng kiem vi se xdy ra ket tiia Cu(OH)2 . Nhu v^y pH tit nhit cho qui Uinh hip phy ion Cu-MapH = 5.
Hinh 6: Anh hudng cua pH lln hieu suit bap phu
3.2.3 Anh hudng cua thai gian tiip xuc ^ ^ ^^° todi gian tilp xuc va sau dd dat trang todi can bing sau 40 phut. Trang toai cin Hinb 7 bieu dien inh hudng cua todi gian tilp bdng duoc giii fliicb do ion Cu (II) chilm ddy bi xdc vio bipu suit hip phu. Hiiu suit hdp phy ting n,^ tro uiu.
Tap chi Khoa hgc Trudng Dgi hoe Cdn Tha Phdn A: Khoa hgc TV nhien, Cong nghi vd Moi irudng: 34 (2014): 45-53
30 60 Thiri gian liep xuc (plitSt)
Hinh 7: Anh hirdng ciia thdi gian tiep sue lln hiiu suit hap pbiji C, _ 1 C, 3.3 Ket qua nghiin cuu hap phu dang
nhiit theo md hinh Langmuir (2)
Hinh 8 bilu dien dudng cong hap phu cdn bang cua ion Cu (II). Ndng suit hdp phy Qc phu thupc vdo ning dp can bang Ce- Tu dudng cong hdp phy ein bdng, phuang Uinh hdp phu ding nhiit theo md hinh Langmuir dupe toilt lap. Phuang Uinh Langmuir dupe chuyen sang dang tuyln tinh:
Trong dd, Ce Id ndng dp liic dat cdn bdng cua ion ddng (mg/L). Qe li dui^ lupng hip phy liic d£it can bang (mg/g). Qn, la dung lupng hip phy eye dai (mg/g). KL la hang sd cua md hinh Langmuir (mg/L).
30 60 90 Ce (mg/L)
Hinh 8: Hip phu cin bing cua ion Cu(ll)
Tgp chi Khoa hgc TrudngDgi hgc Cdn Tha Phan A: Khoa hgc Tu nhiin. Cdng nghi vd Mdi irudng: 34 (2014): 45-53 Hinh 9 bieu diln dang myln tinh ciia phuang
frinh hap phu Langmuir, Phuong trinh tuyln tinh dupe suy ra tii kit qui thi nghiim hip phu can
C
bang cua ion Cu(n): —^ = 0,245Cg + 6,844 vdi
he sd tuong quan fl =0,994. Ddi chilu vdi phuong trinh (2), nang suit hdp phy cyc dai eiia ion Cu(II) li Qn, = 4,1 mg/g vi he sd eua phuong trinh Langmuir la hang sd K L = 0,036.
30- 25- t 20-
W 15- 10- 5-
^
y = 0,24Si -1- 6,844 ^ S R ' = 0,994 ^ y ^
^ y ^
•
1 1 1 1 1 r 1 • 1 1
40 60 Ce (mg/L) Hinh 9: Dang tuyen tinh ciia
4 KETLUviN
RHA dupe dilu chl bang phuong phip xu ly nhiet d ^S^°C trong todi gian 60 phut. Sin phdm RHA thu duoc chua chu yeu li SiOj vdi be mat nhieu Id xop va diln tich bi mdt rilng ldn ban so vdi Uo uiu phu phdm. Ket qui hip phu thu dupe nghi?m diing tiieo rad hinli Langmuir. Cac thdng sd chinh da duoc khio sit bao gdm pH tdi uu la 5, thdi gian dat hdp phu cdn bdng sau 40 phut va bilu suat hap phy tang khi tang lupng RHA. Nang suit hip phy eye dai la 4,1 mg/g.
Ldi CAM TA
Chung tdi xin chin toinh cam on sy tai tto kinh phi tii di tdi sinh viln 2013, Trudng Dsii hpc Cdn Tha vd sy ddng gdp y kiin qui' biu tft cac thdy co Uong Bp mdn Cdng nghi Hda hpc - Trudng Dai hpc Cin Tha.
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