Tiiu ban Khoa hoc V$t ligu NGHIEN ClJtJ C O N G NGHE TAI C H E C H A T THAI C 6 N G N G H I E P M ^ DIEN VA CHE BIEN SAU KHOANG SAN QUANG NIKEN VA DONG Ph^m Dire T h i n g va Tap thg Phong Cdng nghf k[.]
Tiiu ban: Khoa hoc V$t ligu N G H I E N ClJtJ C O N G N G H E TAI C H E C H A T T H A I C N G N G H I E P M ^ DIEN VA CHE BIEN SAU K H O A N G SAN QUANG NIKEN VA D O N G Ph^m Dire T h i n g va T a p thg Phong Cdng nghf kim loai Vien Khoa hgc vat lieu, Vien Hdn Idm Khoa hgc vd Cong nghe Viet Nam 18 - Hodng Quoc Viet, Cdu Gidy, Hd Ngi Email: thangpd@ims.vast.ac.vn Tom tat Niken va dong la kim loai chien luge co tim quan ttpng hang dau phyc vy cho phat triin cdng nghiep va nhiiu mat ciia ddi sdng va nen kinh te qudc dan Nude ta c6 nguon tai nguyen vl dong va niken kha phong phii, bao gdm ca quang nguyen khai trir va nguyen lieu thii cip (ba thai ma dien, veit lieu niken va ddng tai sinh), dd nguygn lieu thii cip phat sinh hang ngan tin mdi nam De xu ly mdi trudng friet de can tdi che thu hdi cac kim loai nang, nho lam giam tac nhan gay nhiem chinh tii cac kim loai Tap thi Phong Cdng nghe Kim lo^i da nghien ciiu tiianh cdng cdng nghe tai che ba thai ma dien theo phuang phap tbiiy luyen ket hpp dien phan Cac kit qua dat dugc tao ca sd khoa hpc cdng nghe dl phat ttiln ip dung cho nghien ciiu che bien^sau khoang san quang niken va ddng Bai bao gidi thieu cac ket C[ua nghien cuu ndi bat ttong qua trinh xtr ly tai che ba thai ma dipn va qua trinh dilu che kim loai ddng va niken tii nguon quang sunfua da kim san co ttong nude NGHIEN C t r u VE XU" LY TAI C H E BA T H A I C O N G N G H l £ P MA CROM, NIKEN Nganh cdng nghiep ma crom, niken tuang ddi phat ttien d Viet Nam va tao mpt lugng Idn chat thai cdng nghiep nguy hai d cac dang chii yeu la ran va long Cac chat thai deu chiia mdt lugng ion hoac nguyen td kim loai nang de hoa tan nhu Cr, Ni, Cu, Mn, Zn Dac biet ttong chat thai ran (cdn ggi la ba thai) phan cac nguyen to kim loai cd the len tdi 40% tdng khoi lugng chat thai khd Mac du la chat tiiai cdng nghiep nguy hai, nhung ba thai ma dien chiia nhieu nguyen td co gia tri kinh te cao nbu Ni, Cr, Cu nen cd the coi la ngudn nguyen lieu thii cap cd gia tti can phai xii ly tai che thu hdi cac kim loai Tu nam 2006 Vien Khoa hpc Vat lieu da dupe giao chu tii de tai khoa hpc cdng nghe cip Vien KHCNVN 2006-2007 (cip BO): "Nghien ciru cong nghe xir ly vd tdi sir diing bd thdi ran cong nghiep ma cram, niken" Qua dd xay dung va phat trien budng nghien ciiu xii ly tai che ba thai cdng nghiep ma crom, niken nham thu hdi dugc cac kim loai cd ich la niken kim loai dien phan va mgt sd san pham khac nhau, nhd giam thieu dugc cac tac nhan dpc hai tii cac kim loai nay, gop phan xii ly mdi trudng cac chit thai cudi ciing Y tirong khoa hpc Ba thai ran sau ma la mdt hdn hgp muoi va cac dxyt, cac hydrdxyt ciia cac nguySn td ke tten Cac hop chit tucmg ddi d l dang hda tan ttong dung dich axit Do d6 s6 ap dung phuang phap thuy luyen de tach khdi ba thai Trudc tien hoa tach chiing bang dung dich axit cd cac ndng dp khac nhau, ta se thu dugc dung dich cac mudi kim loai Dung dich mudi sau hoa tach khdng the dem dien phan true tiep d l thu bSt ky kim loai sach nao Can phai tach rieng muoi chiia Ni vdi dp sach can thiet d l cung c ^ cho di?n phan tiep theo Dac biet ohai luu v loai bd cac hgp chat chiia Fe va Cr - hai 256 Tuyin t$p Hdi nghi Khoa hgc ky ni$m 40 nam ViSn Hin tam KHCNVN - Ha Ndi, ngdy 07/10/2015 nguyen td chinh can ttd qua trinh dien phan Ni sach Mudn vay can dxy hoa mudi Fe'", Cr^"^ mudi Fe^'', Cr^~, sau dd nang dp k i l m ciia dimg dich boa tach len PH > de chuyen hoa chiing v l dang hydrdxyt bi ket tiia va tach khdi dung dich de thu dugc dung dich sunfat niken sach Tu dung dich dieu che mudi cacbonat baza niken NiC03.nNi(OH)2 va dich dien ly NiS04.7H20 chiia 25-35g Ni^^/lit Tiin hanh di?n phan mudi cacbonat bazo niken NiC0j.iiNi(0H)2 ttong dich dien ly NiS04.7H20 de thu dugc niken kim loai didn phan cd sach tten 99.5% Phirong p h a p nghien ciru 2.1- Phmmg phdp hod cong nham hod tdch bd thdi, khu tap chdt vd diiu che nguyin Hfu diin phdn - Ap dung cac ket qua nghien cuu hoa cdn^ nghiep de de phuang budng nghien ciru xti ly boa tach cac chat , khii cac tap chat khong mong mudn va che tao nguyen li$u dien pban true tiep: Hinh Sa cong nghg dieu che nguyen lieu dien phdn thu hoi tit ba thdi Ba thai ran sau ma la mdt hon hgp mudi va cac dxyt, cac hydrdxyt ciia cac nguyen td ke tten Trudc tien boa tach chiing bang dung dich axit cd cac ndng khac nhau, ta se thu dugc dung dich cac mudi kim loai Cac phan ling hoa tan xay theo kieu nbu sau: Ni(0H)2 + H2SO4 = NiSO^ + 2H2O (1) Fe(0H)2 + H2SO4 = FeS04 + 2H2O (2) 2Fe(OH)3 + 3H2SO4 = Fe2(S04)3 + 6H2O , (3) , Sau loc tach dugc dung dich sau boa tach, tiin hanh bd sung chat kiem yen de khii cac tap chit mudi chiia sat va crdm theo phan iing : Fe2(S04)3 + 3NaHC03 = Fe2(C03)3-i' + 3NaHS04 (4) 257 Tiiu ban: Khoa hoc Vgt lieu Cac can khu hydroxyt sit, crdm dugc loc tach ra; dung dich sau khu va Ipc chiia chii ylu mudi cua ion niken Tu dung dich sach chiia ion niken cd thi dilu cbl nguyen lieu dien phan la dung dich dien ly NiS04.7H20 vdi ndng dp 100 - 250g/lit va mudi c i p ngudn ion Ni * cho dung dich dien ly NiC03.nNi(0H)2 theo cac trinh bi nhu sau : -1- K i t tiia dung dich sach sau boa tach : NiS04 + NajCOa ~> Na2S04 + NiC03.nNi(0_H)2 i , x^^K + Hoa tach mudi cacbonat bazo niken so cip bing axit dac de dieu che dung dich niken sunfat ndng cao de lam dung dich dien ly : NiC03.nNi(0H)2 + H2SO4-^-NiS04 + H2O , 30% theo phmfngphap sau: - Nimg sunfat hoa axit dac o nhiet dp cao din 300°C va hoa tach cac san phim stmfat hoa thu dupe dung dich sunfat ciia cac kim loai - Sunfat hoa bing phuong phap hoa sinh (vi sinh vat) de hoa tach lin t6i 80-85% tong lupng niken va dong sten Phuong phap da dupe nghien ciiu cong phong thi nghiem - Sunfat hoa sten thiet bi chiu axit, nhiet va ap suat cao theo phuang pbap autoclave (otocla) Phuang phdp n^y se dupe tiin h^nh nghien ciiu thdi gian tdi CO cac thiet bj autoclave Kit qud phdn tich SEM-EDX mdu Sten chat licgng cao Analysis F i t t i n g C o e f f i c i e n t : 0.3075 Element: (keV) Mass% O K 0.525 2.07 Al K 1.4B6 0.28 Si K 1.739 0.25 P K* 2.013 0.42 S K 2.307 20.55 Ca K 3.690 0.19 Fe K 6.398 27.71 Ni K 7.471 39.08 Cu K 8.040 9.44 Total 100.00 Moi lien kf giSa ty If thu hoi niken va dSngphff thu^ vao tdng ham Iif^g cia ching sten Eri:or% 0.24 0.23 0.20 0.17 0.13 0.20 0,38 0.85 II-» St " %(Ni*Cu) Trong Sten _ 264 Tuyin t$p Hgi nghj Khoa hgc ky niem 40 nSm ViSn Han lam KHCNVN - Ha N6I 07/10/2015 b- Bieu chi dung dich niken sack theo vd nguyen lieu diin phdn tu- dung dich chira ion niken scich (dieu chi theo quy trinh cong nghe cua bdng doc quyen sdng chi 7859 cua Vi^n KHVL): - Lam sach dung dich sunfat kim loai va dien phan thu hdi ddng : + Budc : Khii ion sit (Fe^^, Fe^"^ khdi dung dich sunfat (theo quy trinh cdng nghe ciia bang dpc quydn sang che 7859 cua Vien KHVL) + Budc : Dien phan vdi mat dp ddng nhd, thu hdi dupe ddng kim loai Dung dich sunfat cbi cdn cbiia chii yeu niken sunfat + Ket tiia dung dich sunfat niken sach bang soda Na2C03 thu dupe mudi cacbonat bazo niken NiC03.nNi(OH)2 + Che tao dung dich dien ly vdi ham lupng niken dat >30g/Ut tu san phdm cacbonat bazo niken c-Bi^nphdn nguyen lieu dd dwac chi t^o thdnh kim loai niken : Dien phan mudi cacbonat bazo niken ttong dung dich dien ly niken sunfat de thu hoi niken kim loai dien phdn theo quy trinh cdng nghe cua bdng ddc quyen sdng che 7859 cua Vien KHVL) d- Tinh mdi vd tinh khoa hoc : - Da xac dinh dupe cdc che dp nau luy?n sten ttong Id dien hd quang tir tinh quang va cac loai ttp dung ttong nude Da tim quy luat phu thupc ciia ty le thu hdi vao chat lupng yeu cau ciia sten S%(Ni-(-Cu) Tii dd xay dung dupe quy ttinh cdng nghe nau luyen tinh quang vdi tdng ham lupng £%Ni+Cu) >6% ttong Id dien hd quang cac loai sten vdi chat lupng (tdng ham lupng Ni vd Cu) va ty le thu hdi khdc Cd the nau luyen sten vdi chat lupng dat hang r%(Ni+Cu) dat tdi 50% Tuy nhien quy trinh ndu luyen sten cd the coi la tdi uu X(Ni+Cu) » 40% vdi ty I? thu hdi >95% - Da nau luyen thii nghiem tdn tinh quang dac xit vdi bam lupng I%Ni+Cu) >6% sten vdi chdt lupng I%(Ni-i-Cu) a 30%, ty le thu hdi dat 98% Kdt qua hoan toan cd the dp dung vao sdn xuat Cd the ndng chat lupng ciia sten vdi S%(Ni+Cu) dat tdi 40-50% tiiy theo nbu cdu cua khdch hang - Da nghien ciiu dieu che dung dich niken sach vd nguyen lieu dien phdn true tiep de dien phan che tao niken kim loai - Tinh todn so bp cbo thdy chi phi nau luyen thap, cd khd nang dat hieu qua kinh te cao nhu mong mudn Ddu tu ca ban thap, day chuyen ttang thiet bi cd the tu che tao ttong nude e- Bdo tqo : da dao tao 01 thac sy ttong giai doan 2013-2014 f- Cong bo : - Da dang tai 10 bai bao - Dang ky va da dupe chap nhan don xin cap bang sdng che ve phuong phdp hda tdch niken sten dung dich sunfat theo quyet dinh sd 38176/QD-SHTT 29/06/2015 NGHIEN CUtJ LUYEN KIM BONG TlT TCvTI Q U ^ G DONG SUNFUA Vung Tdy Bdc Viet Nam cd trii lupng ddng tuong ddi Idn, khoang tten 2.2 trieu tan ddng sach Dac diem quang ddng d cac vung md khu vuc Tay Bac Viet Nam chu yeu la cdc khoang sunfiia nhu chalcopyrit, chalcocit Ngoai tru md ddng Sin quyen trii lupng khoang tdn vdi tten 100 trieu tan quang, cdn lai da sd la cac md nhd le trii 265 Tiiu ban: Khoa hgc Vat liSu lupng khoang vai chuc ngan ddn vai chuc van tdn ddng niun rai rac khip vung Tay B^c (Lao Cai, Son La, Lai Chau, Hda Binh, Yen Bai, Dien Bien ) Do vay vi?c dlull day chuyen che bien quang ddng Idn chi cd d md ddng Sin Quyen Lao Cai Con cac md nhd thi chi khai thac, che bien so sai va bdn tinh quang thd Trudc tinh hinh do, Tap thd nghien cuu tdi chii tti da tap trung nghien ciiu phuong phap thiiy luy?n moi nhdm che bien sau quang sunfua ddng de dp dung cho cdc md quang nhd nhu da neu tten Y tudng khoa hoc - Chuyen hda tuih quang sunfua cac hop chdt de hda tan dang sunfat ddng CUSO4 hoac atacamite Cu2Cl(OH)3 - Hda tdch tinh quang da chuyen bda bang axit sunfuric, thu dupe dung dich sunfat ddng so cap - Ch6 bidn tidp sunfat ddng so cap theo each : + Chidt thu hdi dich sunfat d6ng sach dd cung cap cho day chuyen di?n phan kim loai ddng + Kdt tiia dung dich sunfat ddng so cap bang chat kiem, thu dupe hop chat atacamite sach Chd bidn atacamite tinb the sunfat ddng chat lupng cao dung cho chan nudi (bd sung vi lupng), thudc chdng nam nham bao v? th\rc vdt va nudi trdi^ thiiy san Tinh mdi, tinh khoa hoc va k^t qua d^t Avr^c a- Da nghien ciiu de quy trinh cdng nghe chuyen bda chancopyrite thanli atacamite theo cac phan ung sau: I I E s )JK 2-Ttieta scale - OB - Attvanc^ -iiib|ri-M.iMn-T(ngni.iui '»«iHnin-(^Mi-SGa-riT«aK.aiBr L M L inwr.itosAK-i W m lte-Mca»C10tOHB.T»2J».0rt,1-«B.1TWff.U Kit qud phdn tich XRD mdu tinh quang sau chuyin hoa atacamite Vdi su bd sung tham gia cua chiing vi sinh ttong quang vang goc Cao Ram-Luc^ Scm-Hda Binh, cac qua trinh chuyen bda tten dupe dien nhanh chong, toe ^ 266 Tuyin t$p Hgi nghj Khoa hgc /q? ni$m 40 nSm Vien Han lam KHCNVN - Ha Noi, 07/10/2015 hang tri?u Ian so vdi qua trinh phong hda ttong tu nhien Ket qua la sau 30 sunfua ddng ttong tinh quang dupe chuyen bda den 95% • 2FeS04 + I/2O2 + H2SO4 -> Fe2(S04)3 + H2O • CuFeS2 + 2Fe2(S04)3 ->• C11SO4 + 2S° + 5FeS04 • S** + Fe2(S04)3 + 4H2O -> 2H2SO4 + 6FeS04 • CU2S + Fe2(S04)3 -> CUSO4 + 2FeS04 + S** • Fe2(S04)3 + 2H2O -> 2FeS04(OH) + H2SO4 • 2CUSO4 + c r + FeS04(0H) + H20_-> Cn^CKOH)^ + FeS04 + 2HSO4' b- Da nghien ciiu dd quy trinh che bidn atacamite sach tinh thd sunfat ddng CUSO4.5H2O - Qua trinh che bien atacamite thdnh oxit ddng theo phan iing : Cu2Cl(OH)3 + NaOH + Q -»• 2CuO + NaCl + 2H2O - Chd bidn oxit ddng dung dich sunfat ddng sach sau dd kdt tinh thdnh tinb thd: CuO + H2SO4 ->• CUSO4 + H2O; CUSO4 + 5H2O - » CUSO4.5H2O Sdn xudt thir nghiem sunfat ddng Vi$n Khoa hpc Vat lieu vd Tap the thuc hien de tdi da ddu tu xay dung du dn sdn xuat tiiu nghi?m tinh thd sunfat dong tir quang ddng sunfua md Sao Tua theo cac trinh t\r cdng d o ^ nhu sau : > Xay dvmg cac ttang thiet bi chii ydu dd luyen va chd bidn quang Du an da xdy d i ^ g dupe day chuyen thiet bi che bidn quang dong sunfua sunfat ddng: > Chuydn hda tinh quang sunfua ddng hpp chdt d l tan : Tinh q u ^ g sunfua cd ham lupng dong tten 20% dupe phdi ttpn vdi cdc chdt phu gia vd mam vi sinh de chuyen bda tinh quang ve dang dd hoa tan la sunfat ddng Qud trinh chuyen hda dupe thuc hien ttong thdi gian 45-60 d dieu kien dp suat vd nhiet dp "phdng" theo cdc phdn iing ndu d muc 2a > Hda tdch tinh quang sau chuyen hda Qud trinb hda tach tinh quang chiia atacamite va nhieu tap chat khdc (chii yen Id sat) dupe thyc hien theo phan iing : Cu2Cl(bH)3 + 2H2SO4 = 2CUSO4 + HCl + 3H2O 2FeS04+ H2SO4 + I/2O2 = Fe2(S04)3 + H2O Fe2(S04)3 + H - = 2Fe(OH)34'+ 3SO4" Qud trinh hda tach thu dupe djch sunfat ddng sach (da khii tap chat sat) ham lupng 20-25g/lit Cu vdi ty 1? thu hdi dat tten 90% tdng lupng ddng cd ttong tinh quang > Che bien atacamite tii dung dich sau bda tdch : 2CUSO4 + Cl" + 2NaOH + H2O = Cu2Cl(OH)3-l- + NajSO* + HSO4" Qua trinh chd bien thu dupe atacamite Cu2Cl(OH)3 cd dp sach cao, ttdn 98% Chuyen hda atacamite thdnh oxyt ddng > Qud trinh chuyen hda atacamite oxyt ddng dupe thuc hien theo phan ling sau : Cu2Cl(OH)3 + NaOH = 2CuO>l- + NaCl + 2H2O , t" >95"C > Qud trinh chuydn hda atacamite thu dupe oxit dong sach cao ttdn 98% > Hda tach oxyt ddng va chd bidn thdnh tinh thd sunfat ddng - Qua trinh bda tach oxyt ddng dupe thuc hien tiieo phan iing : CuO + H2SO4 = CUSO4 + H2O 267 Tiiu ban: Khoa hgc V$t lieu Qua ttmh hda tach oxyt ddng dupe thyc hien d nhiet dp t** > 95 C - Qud trinh kdt tinh tmh thd sunfat ddng duac thuc hien theo phdn iing : CUSO4 + 5H2O = CUSO4.5H2O, t°