BO GIAO DUG VA DAO TAG DAI HOG QLOG GIA HA NOI TRGONG DAI HOG KHOA HOG TGNHIEN DANG THI HANG KHAO SAT KHA NANG TACH LOAI PHOTPHAT TIJf fl DUNG njCH NUOC B A N G V O I , M U O I SAT (III) CLORUA, NHOM SIJNFAT VA CfNG DUNG DE XLf LY NUOC THAI CUA CONG TY SLPE PHOTPHAT VA HOA CHAT LAM THAO Chuyen nganh: Hoa V6 co Ma so: 1,04.01 LUAN VAN THAG SY KHOA HOG HOA HOG Nguai hirorng d^n khoa hoc: TS NGO SY Ll/ONG i *^^•ML^: •: cunA 'ot - ; I I V HA NOI-2001 MUC LUC Tn M6 DAU PHAN A TONG QUAN Chirorng I Trang thai photphat tir nhien va anh hirong 1.1 photphat doi voi moi trircmg Giai thieu so lirac ve cac muoi photphat 1.2 Trang thai photphat tir nhien 1.3 Vong tuan hoan ciia photphat tir nhien 1-4 Anh hirong cua photpho doi vai moi truong nircfc Chirorng II II Tinh hinh nhiem nirac va nirac thai Nha may supe photphat Vai net ve vai tro niroc sach va tinh trang nhifim niroc II 1.1 Vai tro ciia niroc sach 11.1.2 Tinh trang nhiem niTOc II.2 11.2.1 11.2.2 11.2.3 Nuac thai Cong ty Supe photphat Lam Thao Giai thieu so bo ve Cong ty Supe photphat Lam Thao So nguyen ly cong nghe san xuat supe photphat Nguon nuoc thai cua Cong ty Chirong HI Cac phirang phap xur ly nirac thai chiira photphat III.I Cac phuong phap tach loai photphat niroc thai III.LI Phuong phap sinh hoc III 1.2 PhacTng phap hap phu III 1.3 Phuong phap dien hoa III-2 Tach loai photphat tir nuac thai theo phuong phap ket tua 111.2.1 Tach loai photphat b^ng cac muoi canxi 111.2.2 Dijng muoi nhom de tach loai photphat 111.2.3 Dung muoi Fe-^"" de tach loai photphat III.3 Ghirong IV Muc dfch va cac noi dunz n 83 Tir bang 28 va hinh 25 chiing toi thay rang ndng Ca-* biui dau lang tir 100 den 240 mg/l (ti le Ca/P lang tir 1.94 den 4,65) dan den hieu sual lach loai tang Song hieu qua cua qua trinh lach loai la giam so v(iri ti-uimg hop mau khao sal khong chua SiF,; va F : Vdfi ty le Ca/P=2.() vdi dung dich chi co mat ion PO,' , hieu suat tach loai pholphat dat 95% c(3n \oi dung dich co mat them F (.50mg/l), SiF,;- (l()()mg/l) hieu suat chi dat 54.85% Mudn hieu suat tach loai P O / dat 95% phai dung lU(.mg voi tUcmg iJng xai ty le Ca/P = 3.SS lang 94% b Khdo sdt ndng dp F lai Nong F" tong cong lai sau xir If duoc xac dinh thet) phutmg phap quang nhu muc V.3.5.2.C Ket qua thUe nghiem duoc dua IrcMi bang 29 Bang 29; Ndng CaiOH), ion F' lai sau tdch loai PO/ CO nong khdc STT CV.(mg/l) O (mg/l) 100 57,10 \2M 120 50.80 22.00 140 42.90 34,14 160 36.30 44,27 200 31.50 51,64 220 30.30 53.7^; 240 29.30 55,4S being H'/r uich loai F Tir bang 29 chung toi thay rang co mat ion F" va SiF^," thi sau qua Irinh tach loai ion PO_j^" bang CalOH)^ nong ion F" lai la kha cao Hieu suat lach loai tinh theo F^ la thap: hieu suat tach loai photphal dat 95% thi hieu sual lach loai F moi dat 51.64% VL2J Khdo sdt dnh hudng cua ion F (lOOmgll) vd SiF/ (24H0mgll) a nong dp cao a Khdo sdt dnh hudng cua juhii; han dau C\i(()ll)2 den hicu sual uich loai pholphai Chiim: toi chuAn bi mau khao sal c(') nong ban dau la 40mgP/l lOnmF/h 2480 mgSiF(,"'/l Phan irng duoc ticMi hanh a pH=l(t.^ l^^iu gian S4 phan ung la gio Thay doi nong ban dau ciia huyen phii Ca(OH); lU 2(){)mg/l-l()0()mg/l Nong P O / " cOn lai duoc xac dinh thco phuong phap quang nhu da neu o muc V.3.1.1 c Ket qua duoc dua tren bang 30 Bang 30: Anh hudng cua nong dp Ca(OH), den hieu sudt tdch loai STT C",.-(mg/l) C^ cu the la de tach loai 95% ion PO^' kh(')i dung dich nuoc khong co mat F" va SiF^'" can 103mgCa/l, ihi c6 mat F (50mg/l) va SiF^,~" (lOOmg/1) can phai co huyen phij CaCOH)^ c6 nong ban dau la 2{)()mgCa/l Neu co mat UOmgF/l 24S0mg SiF,-71 thi can huyen phij Ca(OH) CO nong ban dau la 5()()mgCa/l Chiing toi chon nong toi uu de xu If truong hop voi nong ban dau 6()()mgCa/l Hieu sual tach loai PO^^" dat 97,3S% Tuy vay sau tach loai photphat dung dich van lai mot lUcmg ion F" kha Ion De tach loai F kh(')i dung dich triet de hem chiing loi lang luong voi xu ly de tao ket tiia CaF Vice tang luong voi xu ly CO the Ihuc hien bang each tang nong Ca(OM) huyen phu h Khdo sdl dnh hU(hiii ciia pll den c/ua irinh idch loai P()/ han ddu cua Ca(()ll): ndw^ lo lOOOnv^ll Chtin^^ toi ehuan hi dung dich khao sal c(') nong ban dau nhu sdu: nong ion PO4": 40mgP/l F la 10(mg/l) SiF -" la 24X0 (mg/l) NOng X5 ban dau cua Ca"^: 2000mg/l pH ciia dung dich khao sat duoc thay dcSi tu den 10 Nong ion PO/" lai sau tach loai duoc xac dinh theo phucmg phap quang nhu da neu d muc V.3.1.I.e Ket qua thuc nghiem duoc dua a bang 31 Bang 31; Anh hudng cua pH den hieu sudt qud trinh tdch loai SIT pH 8,41 57.95 5,42 72,90 0,51 97,45 0,27 98,65 0,05 99,50 10 0,045 99,75 C 3- (COM la,)(mgP/l) H7o ^ 10 12 pH Hinh 26: Anh hudng cua pH den hieu suat qud trinh tdch loai TxX bang 31 va hinh 26, chiing toi thay rang a pH=8 nong ban dau cua Ca(OH) la 2000mgCa/l thi ket qua tach loai ion chung toi chon pH=8 cho thi nghiem sau 86 P O / ' la rat cao nen c Khdo sdt dnh hucnig nong Ca-* han ddu den qud trinh tdch loai F Chung toi lien hanh khao sat miu nghien cuu co nong F , SiF^' cao gan tuong duong vcri miu that Sau da ket tua SiF,'" dudi dang K.SiF, chiing loi chuan bi mSu nghien cuu co nong ban dau nhu sau : F : 110(mg/l) SiF/": 2480(mg/l), PO^-^ 40mgP/l Thay doi nong ban dau cua Ca-^ tu 2500^4000mg/l Tien hanh phan ung tai pH=8, thoi gian phan ung 24 gio Sau qua trinh xu If nong ion photphat coi nhu duoc tach loai hoan loan Nong ion F t6ng cong duoc xac dinh iheo phuong phap quang nhu muc V.3.5.2.C Ket qua thuc nghiem duoc dua tren bang 32 Bang 32; Ndng ion F ' cdn lai sau qud trinh tdch loai STT C°.^:.(mg/1) C F (c6„ h,) ^nig/1) H7r 2500 27,8 97,39 2750 24,76 97,67 3000 20,71 98,06 3200 15,85 98,52 3400 12,61 98,82 3600 7,30 99,32 3800 6,73 99,37 4000 6.34 99,41 Til bang 32 chiing toi thay rang co mat ion F va SiF/" a nong cao thi nong Ca'"" phai lay du rat Ion moi co the tach loai F" i H ^ jq-uara khoi nuoc thai (gap 30 den 40 lan so voi trutmg h(rp dung dich khong co mat cac ion F va SiF^"") VL2.5 Khdo sdt khd ndng ket hap giua Ca(OH), tdch loai ion PO/ vdi Fe'* vd Al'* de cd mat F vd SiF/' nong cao a Khdo sdt khd ndni^ kei hop giua CaiOli) vd FeCl, de tdch loai ion photphat dung dich nuac Chiinc loi chuan bi mau dung dich nghien cuu c(') nong ban dau 87 P O / - : 40mg/l, F : lOmg/1, SiF,-": 2480mg/l va muoi sat (in) co nong 50mg Fe-*""/] Phan ung duoc lien hanh tai pH=10,5, thcri gian phan umg la gio Thay doi nong ban dau cua huyen phu Ca(0Pr)3 tu 200-600mg/l Nong ion PO/"" lai duoc xac dinh bang phuong phap quang nhu muc V.3.1.I.e Cac ket qua duoc dua tren bang 33 Bang 3 ; Suphu thudc cua hieu sudt tdch loai vdo ndng dp Ca'* cd mat Fe^* (SOmgll) STT C^,, (mgCa/1) 200 0,978 95,11 300 0,462 97,69 400 0,282 98,57 500 0,224 98,88 600 0.154 99,23 C 3- (c6nlao(mg/lP) H% Tir cac ket qua thuc nghiem O bang 33, chiing loi ve thi bieu dien su phu thuoc cua hieu sua't tach loai P04-^ vao nong Ca""^ ban dau Kei qua duoc dua tren hinh 27 100 ^ 200 400 600 800 C°^, (mgll) Hinh 27; Su phu thuoc cua hieu sudt tdch loai vao nong Ca ' cd mdt Fe'* (SOmgll) 88 Tu bang 33, hinh 27 chiing toi thav rane cho them ion Fe'* co nong ban dau la 50mg/l thi hieu qua tach loai qua trinh tach loai PO,'" bang Ca(OH)2 tang ro ret, cu the nhu sau: Neu chi diing rieng mot minh Ca(OH), muon tach loai 97% ion PO,-" can huyin phu Ca(OH), co 600mgCa/l Khi cO mat ion Fe^* nOn- 50mc/l chi can dung huyen phu Ca(0H)3 300mgCa/l (giam di lan) Neu chi diing huyen phii Ca(OH), c(3 nong 200mgCa/l thi hieu suat tach loai chi dat 77,65%, song cho them ion Fe^* co nong 50mgFe/l thi hieu suat dat toi 95% Tir chiing toi thay neu diing them 50mg Fc'*l\ thi chon nong Ca(OH) toi uu cho qua trinh lach loai POy'" la 3()()mgCa/l b Khdo sdt khd ndng tdch loai ion PO/' \di tdc nhan Ca(()H) vd muoi nhom Chung loi chuan bi m l u khao sat co nong ban dau PO,'": 40msz/l F': lOmg/K SiF^/': 24S{)mg/l va dung dich muoi nhom c(') nong SOmgAk^""/!, dieu chinh pH den gia tri 10,5, thoi gian phan ung gio Thay doi nong ban dau cua huyen phu Ca(OH)-, tu 200^600mgca/I Nong ion PO^-^" lai dung dich duoc xac dinh theo phuong phap quang nhu muc V.3.1.I.e Ket qua duoc dua bang 34 Bang 34; Su phu thuoc cua hieu sudt tdch loai vdo nong Ccr^ CO mat Al^^ (SOmgll) H% STT C° , (mgCa/1) 200 2.276 88,62 300 1,600 91,25 400 0,760 96,10 500 0,428 97.86 600 0,088 89 j 99.5f) Tir ket qua bang 34 bieu difin thi sir phu thuoc kha nang tach loai vao tac nhan Ca(OH), va AUSO,), Ket qua duoc dua tren hinh 28 X 200 400 600 800 C °^: (mgll) Hinh : Su phu thuoc cua hieu suat tdch loai vdo ndng dp Car* cd mat Al'* (SOmgll) Tir bang 34 va hinh 28 chung loi thay rang neu them muoi Al'"" 50mg/l thi hieu suat tach loai P O / " tang ro ret, cu the neu chi dting neng Ca(OH)-, voi nong 200mg/l Ihi H=77,65%, co them muoi AP"" voi nong 50mgAl/l thi H=88,62% Song so sanh hieu qua ciia viec them Al'^ va Fe'* la thay su co mat cua ion Fe'"" dat hieu qua cao hon so voi su co mat ciia ion Al "" Qua khao sat kha nang sir dung Ca"* (huyen phii Ca(0H)3), Al"* (dung dich nhom sunphat) va Fe^* (dung dich FeCl,) de tach loai ion P O / " de lach loai ion PO^'" khoi dung dich nuoc chiing toi rut ket luan: - Khi dung dich chi co mat ion PO/*' ca ion Ca-^ Fe'"" va AP"" deu cho hieu qua tot - Sir CO mat cua cac ion F va S i F / ' co anh huong ro ret den kha nang tach loai pholphat ciia ca ion Tuy vay de lach loai khong chi P O / " ma ca F va SiF -" thi viec sir dung Ca-''se thuan loi hem Ca"* co kha nang lao ket tiia ft tan vdi F dang llora apalit (Ca,u(PO/(,F.) vii canxillorua CaF, VI vav xir ly mau nuoc thai ciia Cong ly supe photphal va hoa chat Lam Thao chiinc loi chont ac nhan ket liia la huyen phii Ca(0H)3 90 VL3 Khdo sdt khd ndng su dung vdi de tdch loai photphat thdi Cong ty supe photphat khdi nude Ung dung cac ket qua nghien curu de tach loai ion pholphat mau nuoc thai Cong ty Supe photphat \ a hoa chat Lam Tliao Nong dn cac ion theo ket qua phan tfch mau nuoc thai Cong ty sau klii da loai b('n SiF,- bang KCl, nhu da trinh bay o bang Chung toi tien hanh xu U photphat mau nUOc thai ciia Cong ty bang cac tac nhan Ca(OH),, Ca(OH), + F e d , Ca(OH),+AK(SO,),.lSH.O Cac tac nhan duoc them vao dung dich mau nuoc thai o dang ran hoac dung djch, co nong Ion cho the tfch them vao la nho, de khong anh hUi'mg nhieu den phan nuoc thai VI.3J Tien hdnh xuli bdng tdc nhan CaiOH), Chiing toi lien hanh thf nghiem nhu sau: Lay chfnh xac lOOml mu'-ic thai, them vao 5ml huyen phij Ca(OH)-, co chira 65()()mgCa/l khuay deu, dieu chinh pH den gia tri 10,5 thoi gian phan ung gio Loc loai b(') kcl ti'ia, nong ion PO^^ dung dich duoc xac dinh bang phUcmg phap quang va ket qua duoc dua tren bang 35 Bans 35: Ket qud tdch loai ion PO/' hdng tdc nhan CaiOH) The lieh nirOe thai (ml) CV.(mi:/l) 100 300 0,57 97,80 100 300 0.60 97.69 100 300 0,61 97.65 STT 1' ^ H'A •' Tu bang 35 chi'ing toi thay rang nong iln ion PO^^" lai nvMc thai la rat thap; diroi ngirfyng cho phep theo TCVN 5945-1995 song nong ion F dm lai Irong niroc loc la rat hm De c(') the loai b(') ion F diroc loi hofn chiin^^ toi lang luong Ca(OHK \\\m^^ qua trinh xir If Chiing l6i lien hanh ihf nuhiem nhu sau: Lay chfnh xac lOOml nin'vc thai, ihem tir iir ().2X(g) CaO i7i('ri nun^^ da duo'c nuhicn khuay deu va dieu chinh pll \c gut Iri X.O ih(yi yian phan Une 24 uio* loc b("> ket liia Nong F lai duoc xac dinh bang phUtVim phap quang nhu da neu (V muc \ \ v 1 c Ket qua dU(fc dUa Ircn 91 bang 36 Bang 36: Ket qud ion F cdn lai sau tdch loai ion PO/ hdng tdc nh an Ca(OH), STT V muic thai (ml) m(.o(g) H7r F- I lao( m g / l ) 100 0,2 S 6.56 W.47 00 0,2S 6,73 99.36 100 0.2S 6.59 M9.37 Tir bang 36 chung loi thay diing knrng voi h'm ngoai kha nang lach loai P04^", kha nang tach loai ca F" \ai hieu qua cao: hieu sual lach loai F dat >99%, nong F lai ~6mg/l VI.3.2 Tien hdnh xu li bdng tdc nhdn Ca(OH), vd FeCl, Chung loi lien hanh thf nghiem nhu sau: Lay chinh xiic lOOml nin'tc thai, IhcMTi 5ml huyen phu chura 6500mgCa-7l 2.5ml dung dich FeCl, c(') nong 215()mgFe/l, khuay deu Chinh pH ve gia tri 10.5, \W\ gian phan irng giO Nong ion PO^*" lai phan nuac loc ductc xac dinh biing phuofng phap quang nhir muc V.3.1.1 c Ket qua dirac dua tren bang 37 Bang 37: Ket qua tdch loai ion PO/ FeCL STT ' iiirnc iliai hdng tdc nhdn Ca(OH), vd c ( a HVr (ml) (mg/l) (mg/l) (mg/l) 100 155 25 0.49 9S,11 100 155 25 0.4S MS 15 100 155 25 j ().4V 9S.11 VL33 Tien hdnh xu li nudc thdi vdi lac nhdn Ca(OH) va mudi nhdm Chung loi tien hanh thi' nghiem nhu sau: Lay chinh xac lOOml uxu'ic thai, cho \ a o coc c(') dunu lich 25()mL ihem -^3ml huyen phu Ca(OH) chua ')1 65()()mgCa-^/l, 2,5ml dung dich muoi nhom cO chua l()75mgAl/l Khuay deu dieu chinh pH den gia tri 10,5 phan untz trone ihOi eian izia Nong ion PO4 lai dung dich duac xac dinh bang phmrng phap quang nhu da neu a muc 5.1.1 c Ket qua duac dua tren bang 3H Bang 38: Ket qua tdch loai ion PO/ bdng tdc nhdn Ca(OH) vd mudi nhom STT c V H7r uirrtc ibai (ml) (mg/l) (mg/l) (mg/l) 100 200 25 0.60 97,69 100 200 25 0,56 9S.60 100 200 25 0,55 98,63 Tir ket qua bang 37 va 3K chiing toi thay tien hanh xu li' nUcVc ihai \«\ tac nhan Ca(OH) va FeCl, cung nhu Ca(OH) va Al.(SOj, kha nang Uich loai dat hieu qua cao 93 ^^ KET LUAN Da khao sat kha nang dung Ca-^ \V* \a Fe*" de lach loai P O / khOi dung dich nuoc Ket qua thuc nghiem cho thay sir c() mat cua ion F va SiFf,- can \xa ro ret den kha nang lach loai P O / ciia ion Cac ket qua khao sal kha nang dting voi (Ca(OH).) de Uich loai ion PO_,'" lir dung dich x\uac da cho thay co the sii dune voi de tach loai mot cach CO hieu qua ion PO4-' truong hop c(') mat ion F \'a SiF,/ Co the su dung cac ion Ai^"", Fe^"" de lam tang kha nang tach loai POy'' cua voi dung dich nuoc tiarong hop nong F va SiF^," Ion Da tien hanh xu ly mau nuoc ihai cua Cong ly Supe photphal Lam Tliao Phu Tlio CO nong P long cong la 26,6 mgFVK F": 59.5mg/l SiF^V • l^-l-" mg/l Ket qua cho thay sir dung cac dieu kien xi'r ly la: pi = 10,5; voi: 3{)()mgCa/l t=4h hieu suat lach loai VO,' dat 97,7^'^., nong P O / lai sau tach loai la (),59mgP/l Khi luong voi tang len 19()()mgCa/l ihi nuoai PO,^" ca F" va SiF.~' cun^ da ^\XK^c tach loai, nonj^: P lonu conu giam tir l()55mg/l xuong 6.7mg/l Su CO mat Fe^^ voi nong 25mg/l qua trinh lach loai PO^^ Ur ninVc thai, da lam ^iam Immu voi can thiet ti^r 3()()irmCa/l xuonu ^15()mi:Ca/l Con diing Al*"^ \a\ nong 25mg/l thi li^nig voi can thiet da giam lir 30()mgCa/l xuong ^2()()mgCa/l 94 TAI LIEU THAM KHAO I Tieng Viet L Bao cao danh gia tac dong moi truong tai Cong ty Supe photphat va hoa ehat Lam Thao VTnh Phu - 12/1995 Dang Kim Chi Hoa hoc moi tructng NXB Khoa hoc va Ky thuat 1999 Hoang Nham Hoa Vo co T.2, NXB Giao due 1999 Tran Van Nhan Giao trinh cong nghe va xu If nuoc thai NXB Khoa hoc v a K y thuat 1999 Tran Hieu Nhue Thoat nuoc va xu If nuoc thai cong nghiep NXB Khoa hoc va Ky thuat 1999 P.P Koroxtelev Chuan bi dung dich cho hoa hoc phan tfch (ban dich tieng Viet Nguyen Trong Bieu hieu dmh va bien tap) NXB Khoa hoc v a K y thuat 4-1974 Tieu chuan Viet Nam Quyen tap I - Chat luong nuoc 4-1995 II Tieng Anh Abovv-Elela, El-Kamah S L Aly E M., Abou-Talcb H I Management of wastewater from the fertilizer industry; Water Sci Tech., V 32, n 11, 1995, p - Buftle J Importance of speciation methods in analytical control of water treatment processes with application to pluoridc removal from wastewater Water research, V 14, n 1, 19K5, pp 7-23 10 Comelis W Jansen Process for the removal of lluoride from waste water USP, No 5, 106, 509, Date of patent Apr 21, 1992 11 Desmond F Lawler and donald H Williams Equalization tratization modeling An application to lluondc removal Watei' Res., V IS, No 11, pp 1411-1419, 1984 12 Diane Halterman Manganese remtwal from aqueous industrial waste 95 ... 11.2 Nirdc thai Cong ty Supe photphat Lam Thao 11.2.1 Gi&i thieu sabq ve Cong ty Supe photphat Lam Thao Cdng ty supe photphat Lam Thao Phii Tho la mot cdng ty Idn, cd tac dung to km sir phat trien... tach loai photphat bang voi, sat (UI) clorua, nhom sunfat tir dung dich nuac va ap dung cac ket qua khao sat duac de xu ly mau nuac thai ciia Cong ty Super photphat va hoa chat Lam Thao - Phii... Lam Thao Giai thieu so bo ve Cong ty Supe photphat Lam Thao So nguyen ly cong nghe san xuat supe photphat Nguon nuoc thai cua Cong ty Chirong HI Cac phirang phap xur ly nirac thai chiira photphat