Thong tin khoa hpc cpng nghe m d
NGHIEN CAU sur DUNG KHOANG APATIT DE XUT LY CAC KIM LOAI NANG TRONG DUN THAI QUANG DUOI CHI - KEM
Minimization of the environmental pollutants has been considered as a forced task in the mineral mining industry. Up to now, there have been many effective treating processes;
however, the process with using the natural available materials has many advantages, in this paper, the authors represent the research results from the utilization of the appetite mineral for treating the heavy metals in the sludge from zinc - lead tailings
KS. NGUYEN THI LAI ThS. UMI VAN BINH
Viin Khoa hpc vi Cdng nghd Md - Luydn kim Bien t$p: ThS. Hoing Minh Hiing
1. Mo* ddu
Khai thdc, e h l biln khodng san ndi chung vd khai thdc c h i biln quang chi - kem ndi ridng id ngdnh cdng nghipp mang tinh ddng iyc thiic d l y sy phdt triln kinh te - xa hpi cda q u i c gia, cda viing khodng san. Tuy nhien, tdc dpng tieu cyc cua nd Id nguy co va tnj'c tilp anh hydng tdi mdi trydng cua cdc vimg khodng san. Khai thdc, e h l bien chi - kem cd nhieu nguy co tdc dpng tidu cyc tdi mdi trydng nhy vipc dya ien mat d i t eac khodng vat se bj nhipt dd, dp I m tdc ddng iam tdng kha nang hda tan vao nydc cua cac chat ddc hai; qua trinh iam gidu qudng chi - kdm dua ra mdi trydng mdt lyeng idn bun thai cd chO'a cdc hda chit dung trong tuyin quang, vv.. Vipc xir \i d l giam thilu cac chit cd nguy ce gay d nhiem mdi trydng neu tren Id nhiem vy bit bupc trong ngdnh cdng nghipp khai khoang. Cd nhilu phyong phdp xir iy cdc chit gdy d nhiem, song, viec sir dyng cdc loai nguyen lipu cd san trong t y nhien Id mpt phyeng phdp cd nhieu yu dilm.
Nam 2014, trpng khudn kho chyong trinh khoa hpc cdng nghd cua Bd Cdng Thyong, Vidn Khoa hpc vd Cdng nghp Md - Luyen kim (VIM- LUKI) da de xuit va dyec chip thuan cho triln khai d l tai 'Nghidn ciru si> dijng khoang apatit ai xir ly cic kim lo$i nfing trong bun thai qu$ng audi'. Myc tieu cua de tdi id nghiSn cu'U kha ndng irng dyng khodng apatit cua Vidt Nam d l xir iy kim loai trong biin thai qudng dudi tir qud trinh e h l bien quang Cy t h l , d l tdi da thCi' nghipm xir ly' qudng dudi cua nhd mdy tuyin qugng chi - kem.
2. M l u nghien ciru
Mdu sy dyng trong qud trinh nghidn ei^u cua
d l tdi g l m : qupng dudi chi - kdm vd khodng ap- atit ily tai md apatit Lao Cai.
2.1. Miu qusng dudi chi - kdm
Mdu qupng dudi chi- kem dyec i l y tpi 2 h i thai qudng dudi thude XI nghidp chi - kem Lang Hich (Thai Nguyen) vd Xi nghiip chi - kem Che D i n (Bao Kan). Sau khi ily m l u vd phan tich cdc thdnh phin khodng vpt, thdnh phin hda eua m l u qudng dudi XI nghipp chi - kem Ldng Hich vd Xi nghipp chi- kem Che D i n cho thiy quang dudi chi- kem Lang Hich va chi - kem Che D i n cd thdnh phin khodng, thdnh phin hda tuong ty. Do thdi gian va kinh phi cd han, ndn Nhdm nghien ciru da lya chpn qupng dudi chi - kem Che Den idm d l i typng nghien ciru.
22. Mau v$t lidu khoing apatit
Vat lidu apatit bao gdm apatit 1, apatit li, apatit iii, apatit IV vd Tang sdt duec lly tai khai trydng va nhd mdy tuyin cua Cdng ty TNHH MTV Apatit Viet Nam, Lao Cai.
3. T h i l t bj, v?t tu" SU' dyng trong nghien CLPU
Thilt bi, vat t y chinh sy dyng trong nghidn cO'u bao g l m : May llc/trpn VIMLUKI - CIE32;
bd thiet b| nghien cu'U dpng opt; mdy khuly gia nhipt UnlEquip (My); may phdn tlch quang pho Droll 2800 (My); mdy dp pH (My); mdy dp dp dan didn (V); cdn ky thudt; tu sly (DO'c)...
4. T h i l t k l nghidn ciru vd cdc phu'O'ng phap nghien ci>u
Theo nghien cCru cua cdo nuoc tren t h l gidi, apatit cd kha ndng xii' ly t i t cac ion Pb; Cd; Zn;
Mn... Tuy nhien, trong khudn k h i thei gian vd kinh phi cd hpn, d l tdi tdp trung xii' ly hai ion
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Thong tin khoa hpc cdng nghe m o
Bing 1. Cic phuang in nghiin ciru khi ning xir ly ion Pb: Zn bing vit lidu apatit tw nhiin
L
Cwa3<hdiul^
PUniMPto'IhlplI;
Hinh LSadi md phdng quy trinh nghiin c&u lua chpn vit lieu Apatit cd khi ning xu'if ion Pb: Zn
tii uu trong phdng thi nghiim ehinh trong quang dudi ohi- kem Id ion Pb va ion Zn.
4.1. Nghidn ciru Iwa chcin v$t lidu apatit - Miic tidu nghien ciru: Nham lya chpn loai vdt lipu apatit cd khd ndng xir ly cdc ion Pb vd Zn hipu qua nhlt vd kinh t l nhlt.
- Phuung in nghien ciru: So dd md phdng phyong dn nghien cu'U lya chpn loai vat lipu ap- atit cd khd nang xir ly eac ion Pb vd Zn dypc trinh bay e hinh 1.
Pha dung dich chudn cd nong dp Pb: 3960
|jg/l; Zn: 105200 ng/l tu' hda chit Lead (11) ac- etate trihydrate (Pb(CH3COO)2.3H20 £ 98%;
Zinc chloride ZnCh 2 98%.),
Sir dung 30g apatit (khd) moi loai va 150 ml dung dieh chuin, dya vdo binh phan u'ng (sir dung chai thiiy tinh dung tioh 300 mi, ed nap day). Dung dich chuin vd vat iieu apatit dypc tilp xuc deu trong binh phan irng bang thiet bi lie. Thl nghidm duec tien hdnh trong thei gian khoang 8h d l dam bao phan irng diin ra hoan todn. Mdu nydc sau dd dyec lly ra dem phan tich pH; ion Pb; ion Zn. Dya tren k i t qua nghien ciru so bd nay lya chpn loai apatit cd kha ndng xCr ly cac lon Pb va Zn t i l yu.
4.2. Nghien ciru kha nang xir ty qu$ng audi chi - kem bang v$t lidu apatit tir nhien aS chon - MIJC tieu nghien ciru: Nham khao sat kha nang xu' ly cdc lon Pb va Zn blng vat lipu apatit ty nhien da chpn d myc 4.1 (apatit IV, Tang sdt);
xdc dinh Iueng apatit tdi yu de xu' ly qupng dudi ehi kem va thdi gian xu' ly tdi yu.
- Phuvng phap nghien ciru:
Qua trinh nghien cu'U kha nang xu' ly cdc ion Pb va Zn cd trong quang dudi chi- kem bang vat lipu apatit iV va Tang sdt t y nhien dypc tien
Phwong in nghiSn cu'U
Phyong dn 0 (ty Id 0 %) Phyong dn 1 (ty Id 2 %) Phyong ^n 2 (tyld10%) Phyong in 3 (tyld20%) Phyong dn 4 (ty 1$ 50%)
Khdi luvng qu$ng
dudi fg, khd)
30 30 30 30 30
Khdi iirgng apatit iV/Ting sdt (g. khd)
0 0,6
3 6 16
Tan suat iiy mau (h)
0 24;
48; 98 Thdng so phin
tich
pH; Pb;
Zn
hanh theo cd hai phuong phap: (1) Phyong phdp me vd (li) Phyong phap cdt.
a) Phyong phap me:
Phuung in thi nghidm:
De xdc dinh kha ndng xir ly cdc ion Pb va Zn ed trong qupng dudi bang eac vat lieu khoang apatit ty nhien (apatit IV vd Tang sdt), Nhdm de tai tiln hdnh 4 phyong dn thi nghiem, chi tilt ede phyong an thi nghiem dyoc trinh bdy trong bang 1.
SO' dung 30g m l u quang dudi Che Don (tinh theo trpng iypng khd), va ty lp phin tram tyong U'ng nhy tai bang 1 vd 150 ml nydc c i t dya vdo binh phan irng (sir dyng chai thuy tinh dung tich 300 ml, ed nap day). Hdn hop qupng dudi, apatit, nude c i t dyec tilp xuc deu trong binh phan irng bang thilt bi llc/trpn VIMLUKI - CIE 32. Thl nghiem dypc tiln hdnh trong thdi gian 96h. Mau nydc sau do dypc i l y ra phdn tlch tpi cac thdi dilm 24h; 48h; 72h vd 96h. Dya tren k i t qua nghien ciru nay ddnh gcac ion Pb vd Zn trong
•quang dudi chi kem cua vpt lipu apatit ty nhidn (apatit IV, Tang sdt).
b) Phyong phdp opt:
- Myc tidu nghien ciru:
Sau khi nghidn ciru kha ndng xCr 1:^ ion Pb va Zn theo phyeng phdp me, lya chpn phuongan ty Id tiln hanh nghien ciru dpng cdt d l md phdng dilu kipn g i n vol thyc t l hen.
- Phirong in nghidn ciru:
Cd hai phyong an nghien cu'U d l i vdl
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Thong tin khoa hoc cong nghe mo
phu'ang phap cot la: (i) Mo phong phu'ang phap xi> ly tru'C tiep bang trgn hon hap qugng duoi va vat li$u apatit v^ (ii) Mo phong phu-ang phap su dyng apatit nhu- mot lap chong tham.
5. K§t qua va binh luan
5r1: Ket qua nghidn cwu Iwa chon v$t ll$u ap- atit tl/ nhien
NUO'C cai NirtfL i4l I " I am mjfV
mm
Hinh 2. Sa dd m6 phdng quy trinh nghidn cCfu dang cot khd ndng xCf ly ion Pb; Zn trong qudng dudi b^ng
Apatit IV/Tang sdt tw nhidn O bu'O'c thi nghiem nay da tien hanh l<hao sat kha nang xi> ly ion Pb va Zn biing cac loai vat lieu apatit I, apatit II, apatit III, apatit IV va Tang sot tren m l u gia djnh dung djch Pb: 3690 pg/l;
2n: 105200 pg/l.
Ket qua cho thay rang, hi0u suat xu' ly ion Pb va Zn cua cac loai vat lieu apatit sau 8h xCf ly deu cao, cu t h l Pb >97%; Zn >80%, tuy nhidn, xet ve gia tn kinh te quang apatit I, apatit 11, apatit III CO gia tn kinh te cao. Quang apatit loai I sau khi khai thac du'gc du'a vao su" dung ngay cho cdng nghiep san xuM phan bon. quang apatit loai II sau khi khai thac du-ac du'a vao su- dyng cho san xuk phan lan nung chay, con quang ap- atit loai III du-gc du'a vao xu'ang tuyen nang ham Iu'ang de du'a vao san xuat phan bon. Quang ap- atit IV va Tang sot hien nay chu'a du'gc su" dung, gia tri kinh te khong cao, do do, nhom nghien CU'U lu'a chpn apatit IV va Tang sot de nghien CU'U lam vat lieu XLF ly ion Pb; Zn.
5.2 Kit qua nghien cwu kha nang xw ly' qu0ng duoi chi- kem bdng v$t lieu apatit tw nhien
5.2.1. Doi vol apatit IV tw nhien
- Ket qua nghien CLKU theo phu'ang phap me cho th^y:
(i) Ham lu'gng ion Pb giam ti> 50 -g/l xu6ng du'o'i ngu'&ng phat hien (khong phat hien du'gc) tCr sau 72h thi nghiam va duy tri 6n djnh den het 96h nghidn CLPU a nguang khong phat hi?n du'gc, dieu do cho thiy, hi?u qua xCe ly ion Pb
cao, dgt tren 90% g tat ca cac phu'ang an ty 10.
(ii) Ket qua cho thay, ngay sau 24h, ham lu'gng ion Zn khong phat hien du'gc, tuy nhien tang nh?
sau 48h. Tai 72h v^ 96h nghien ciru, h^m lu'gng ion Zn 6n djnh a khoang 200 - 400 pg/\. Di4u do cho thiy ham lu'gng ion Zn da giam tren 60% so vd'i ham lugng ion Zn ban dau a tat ca cac phuang an ty l# theo me tuang duang nhau,
- Ket qua nghien cuu theo phuang phap cpt cho thay:
(i) Vdi cac ty l# 2%, 10%, 20% va 50% thi den h^t ngay thu 11 ham lugng ion Pb deu giam a muc khong phat hlpn dugc (< 1 mg/l).
(ii) Ve ca ban ket qua nghien CLPU mo phdng ky thuat trgn tnj'c tiep hay su dung apatit lam lap chong tham khong co su khac nhau ro ret doi vd'i vat lipu apatit IV t u nhien, vo'i cac phuang an ty lp cung khong thay, co su khac biet ve hieu qua xu ly;
(iii) Vdi cac phuang an ty le khac nhau (2%;
10%; 20% va 50%) va ap dung ca ky thuat tron true tiep va l^m Id'p chong thlm thi kit qua sau 9 ngay thi nghiem hieu suit xu ly ion Zn >50%
va den 11 ngay nghien cuu thi hipu suit xu ly Zn dgt tren 90% g t i t ca cac phuang an ty le.
(iv) Ket qua nay cung phu hap vdi cac phuang an nghien cuu xu ly ion Pb va Zn trong qugng duoi blng Apatit IV theo phuang phap me.
5.2.2. Doi voi tang sot tw nhien
- Ket qua nghien cuu theo phuang phap me cho thiy:
(1) Chi sau 24h thi nghiem, ham luang ion Pb da giam xuong muc khdng phat hien dugc va duy tri ket qua nay cho den 96h nghidn cuu. K i t qua nay cho thiy hipu suit x u ly ion Pb bang Tang sot cung cao tuang t u nhu vdi xu ly bang Apatit IV t u nhien, hipu suit xu ly ion Pb deu dat tren 90% sau 96h nghien cuu
(ii) Ham lugng ion Zn giam tu 1130 pg/l xuong muc 100 - 500 pg/l chi sau 24h thi nghidm (hieu suit dat tren 50%). Tuy nhien, sau 48h, ham lugng ion Zn da giam xuong muc khong phat hlpn dugc va duy tri cho den hit 96h nghien cuu. Nhu vgy, CO t h l thiy rang, hieu suit xu ly da dgt tren 90% g toan bp cac phugng an ty le.
- Ket qua nghien cuu theo phuang phap cpt cho thiy:
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Thong tin khoa hoc cong nghe mo
(1) Sau 9 ngdy nghien ciru e cdo phyong dn ty Id khde nhau vd kJ thudt xif i j md phdng khac nhau deu cho k i t qua; hdm Iueng ion Pb d i u dydi ngy&ng phdt hien hoac x l p xi ngyong phdt hidn. Sau 11 ngay nghidn ciru thl hdm iypng ,on Pb d mirc khdng phdt hlpn a l l vdi cdc phyeing dn nghien cim.va ky thudt xir ly, dilu dd cho thiy hidu qua xy 1* ion Pb cao (2 90%) sau 11 ngdy nghien ciru khi sy dyng Tang sdt t y nhidn.
(11) Sau 9 ngdy nghien cCfu, hdm lyeng ion Zn da giam nhyng cdn dao dpng chya I n djnh. Tuy nhidn, say 11 ngay thi ham lyeng ion Zn d i u d mirc khdng phdt hidn 6 todn bd cdc phyong dn ty Id vd ky thuat xir ly (trpn tryc tilp hay iam ldp ching thlm). K i t qua ndy tyong t y doi vdi apatit IV ty nhien cho thay k i t qua xir ly ion Zn cao (>
90%), chi sau 11 ngdy nghidn ciru. Ky thuat trpn tn/c tilp va ldm Idp ching t h l m khdng anh hydng tdi k i t qud xu' i j .
6. K i t l u l i n
K i t qua nghien ciru trong phdng thl nghipm ve kha nang sir dung vdt lidu khoang apatit Ldo Cai d l xir ly cdo ion kim lopl linh dpng od trong bun thai quang dudi chi - kem dd thu duec mdt sd k i t qya nhy sau:
- Oa |ya chpn dypc 2 trong so 5 iopi vdt lipu apatit cd sSn trong nydc de Idm vat lidu xif ly ion Pb vd Zn trong quang dudi ehl - kem dd Id apatit IV vd Tang sdt;
- Ba khao sat duec kha nang xir iiii cdc ion Pb vd Zn trong quang dudi chi - kem bang vdt lieu apatit IV va Tang sdt. Qua trinh nghien ciru t i l n hdnh theo phyeng phdp me trong 4 ngay va theo phuong phap cpt trpng 11 ngdy;
- Hipu qua xir iy ton Pb vd Zn: 0 oa phyeng phdp nghien ciru ( m l va cdt) d i u che hipu qua xy ly cac Ipn Pb vd Zn cd trcng quang dudi ehl - kem cao, hipu suit xir ly ion Pb; Zn d i u tren 90%. Boi vol phyeng phdp me thl thdi gian xii IJ nhanh hon (4 ngdy), cdn d l i vol phyeng phdp cpt Id khpang 11 ngdy tren ca vat lipu apattit t y nhien va biln tinh. Tuy nhidn, qud trinh xu' i j ion Pb diln ra nhanh hon ion Zn;
- Ty Id xir ly: Vdi ty ip 2 - 10% vpt lipu apatlt/qudng dudi (tinh theo trpng lyeng khd) la du kha nang xir \)i ham lyeng cac ion Pb vd Zn iinh dpng cd trong qudng dudi ehl - kem vdl hipu suit dat £90%,
Nhdm nghidn ciru oung da md phdng qua trinh xir iy ode ion kim I09I trong qu|ng dudi chi - kem blng vdt lidu apatit t y nhien theo hal k5 thudt: Trdn tryc t i l p vd phdn t i n g . K i t qua nghien ciru cho thiy, triln vpng ung dyng vao thyc t l Id r i t Idn. N l u dyec d i u t u thCr nghidm tren quy md Idn thl cd t h l xif 1;^ cac lon kim logi trong bun thai qudng dudi bang vpt lipu apatit ty nhien theo hal kJ thudt chinh: (i) Ky thupt x * IJ tnj'c tilp bang cdch trpn tnj'c t i l p vdt lipu khoang apatit vdo bai thai qudng dudi b| d nhilm kim lopi ndng, vd (il) Ky thudt sir dyng vdt lieu khodng ap- atit ldm ldp ching t h l m nhy mpt ldp Idt ddy va thdnh h i thai qudng dudi./.
Tdi li^u tham Ithio:
1. T r l n Tuin Anh va nkk, Bde diim khoang v$t - aia hda vi nguon goc cic mo chi - kdm cau tnic Ld Gam, miin Bac Vidt Nam. Tap chi Khoa hpc v l trdi alt, tr393-408.
2. Nguyin Xudn Hal (2012), Nghidn ciru dpng thai va od dfnh kim topi n$ng cd ape tinh cao (Cd vi Pb) trong dat 6 nhiim bang nhitng hap chat xir If tv nhidn. Bao cdo k i t qua de tdi hop tae theo Nghj dinh thy c i p Nhd nydc vdi Lien bang Nga. BHQGHN.
3. Richard F.McFariin et al (1994), [mmobiilza- tion of Pb from contaminated water, soils, and wastes by phosphate rock.
4. James Conca et al (2002), Treatability Study of Reactive /Materials to Remediate Ground Water contaminated with Radionuclides, Metate and Nitrates in a Four-Component Per- meable Reactive Barrier. Groundwater Remedi- ation of Trace Metals, Radionuclides, and Nutrients, with Permeable Reactive Barriers.
eds. D.L. Naftz, S.J. Monison, J.A. Davis, and C C . Fuller, Academic Ptess, 16. P 5, 23.
5. James L Conca. PIMS - Remediation of metal contaminated waters and soils.
6 Judith V. Wright, vd nkk. Project title: In Situ immobilization of heavy metals in apatite minemi formulation.
6. Judith Wright, Ph.D.PIMS, Using Apatite UTM: How it works to remediate soil & water
7 Judith Wright; Bryony Hansen, and James Conca. PIMS: an Apatite II Permeable Reactive Barrier to Remediate Groundwater Containing Zn, Pb and Cd.
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