170 Khao sat hf gel polyme dl phan each nuoc trong cac giing khai thac KHAO SAT HE GEL POLYME DE PHAN CACH NUOC TRONG CAC GIENG KHAI THAC NGAP N U O C TANG MONG MO BACH HO Nguyin Phuang Tiing, Nguyen[.]
170 Khao sat hf gel polyme dl phan each nuoc cac giing khai thac KHAO SAT HE GEL POLYME DE PHAN CACH NUOC TRONG CAC GIENG KHAI THAC NGAP N U O C TANG MONG MO BACH HO Nguyin Phuang Tiing, Nguyen Thj Phuang Phong Nguyin Hoang Duy, Pham Viet Hiing va Nguyen Qudc Hiing Phdn vien Khoa hpc Vat lieu tai Tp Hd Chi Minh TOM TAT Bdng phirang phdp thir nghiem chai kin vd thir nghiem bdu quyin nita, cdc tdc gid da buac ddu lira chgn dugc hai hi gel Id cdu triic ciia hdn hgp phdi trdn hai dgng polyme gdc aciylamit khdc vd hi chdt tgo ndi HMTA/PhAc cd thai gian tgo gel vd dp bin nhiet phii hap di icng dung phdn cdch nude tdng mdng md Bgch Hd Phuang phdp thdng ke quy hogch hod thuc nghiem dugc sir dung da rdt him ich di thie nghiem vd tdi im hod qud trinh tgo gel Cdc hiiu irng tuang tdc giica ndng dp polyme vd chdt tgo ndi din thdi gian gel hod vd dp bin gel dd dugc thiet lap vd dua dugc phirang trinh hdi quy phu hgp tdt vai cdc kit qud thuc nghiem Thai gian tgo gel tdi da Id 13 gia vd dp bin gel tdi Id 100% ciia hi gel sau giir 32 ngdy a nhiet dp 140°C da buac ddu ddp irng dugc yiu cdu ky thudt ddi vai vdt lieu ngdn cdch mrac sir dung cho tdng mdng md Bgch Hd DAT V A N D E Hien tugng ngap nude cae gieng khai thac sau mdt sd nam ap dung che bam ep nude de tri ap lye via dang la mdt van nan nghiem trgng nganh edng nghiep khai thac dau tren the gidi, nhat la cac gieng da khai thac d giai doan thir cap Cac bien phap de kiem soat lugng nude ddng hanh, ndi chung thudng dugc xep nhu la kiem soat mirc phii hgp, dugc lya chgn tren co sd nguyen nhan ngudn nude va phuang phap xam nhap vao viing can day gieng Sy lya chgn cae phuang an xir ly bao gdm xir ly phan each nude va cai thien tham tuomg ddi (cdn dugc ggi la cai thien tham bat ddi ximg) day chiing tdi chi di sau vao xir ly phan each nude Cd nhieu cdng nghe dugc sir dung de phan each nude cac gieng khai thac, dien hinh la bom nhet xi mang Tuy nhien, cau triie ciia xi mang, khd cd the tham nhap sau vao via, da ngan dugc nude thi cung ngan ludn dau va kbd phye hdi trang thai gieng ban dau neu qua trinh xir ly cd sai sdt Tir sau nhirng nam 1980 cdng nghe xir ly bang gel gdc polyaerylamit (homo-, CO-, ter-polyme ehira acrylamit) de phan each nude dugc phat trien va sir dung rdng rai tai cac md dau tren the gidi Do nhirng tinh chat uu viet cua minh, cac he gel gdc polyaerylamit cang dugc phat trien da dang va hieu qua [4] Md Bach Hd, noi cd than dau d mdng thudc loai ldm tren the gidi va ldn nhat d nude ta da dugc khai thac tir nam 1988, cdng nghe bom ep nude de giii ap suat via dugc sir dung vao nam 1993 va den 1995 bat dau cd hien tugng ngap nude d mdt sd gieng thude tang mdng Den sd lugng gieng khai thac bj ngap nude cang nhieu, mire Tuyin tap bao cao Hgi nghj KHCN "30 nam Dflu Viet Nam: Co hgi mdi, thach thde moi" 171 ngap nude cang trim trgng Tim tdi va ap dung cac cdng nghe each h' dugc cac khoang ngap nude gieng khai thac giam khai thac nude ddng hanh la mdt \eu cau birc thiet tir chi cd mdt vai gieng d tang mdng md Bach Hd bi ngap nude Tuy nhien, nhirng dieu kien dac thii ciia tang mdng md Bach Hd nhu; nhiet cao (140 150°C), collector la da granit nirt ne, v.v nen cho den mac dii da trien khai mdt sd cdng nghe (rat cdng d nhirng Igai md hinh khae tren the gidi) chua cd qua trinh xu ly phan each nude cho ddi tugng cdng [1] Nhieu he gel gdc polyaerylamit da dugc cdng bd cac tai lieu [2-4] Trong dd mdt sd he gel dugc de xuat img dung via nhiet cao [4 5] Cac he na>' bao gdm: gel gdc polyme, phenol formaldehyt, lignilsulphonat copolyme styren-butadien dugc tao ndi vdi peroxit hu'u co va he gel gdc polyaerylamit vdi he chat tao ndi gdc phenol/formaldehyt De giam ddc hai ciia he phenol/formaldehyt ngudi ta da diing nhieu hgp chat it ddc hai hon thay the phenol va formaldehyt he chat tao ndi Vi du nhu formaldehyt cd the thay the bdi hexamethylene tetramine (HMTA) glyoxal, hoae 1- 3hoac 5-trioxane Cac hgp chat thay the phenol bao gdm phenyl acetat phenyl salicylat hoae hydroquinon hay mdt sd chat khae [6] Tuy cd kha nhieu tai lieu cdng bd ve cac he gel dugc cho la ben d nhiet cao nhung cho den nay, chua cd mdt cdng bd nao ve thir nghiem gel d nhtrng dieu kien tuong ty nhu d tang mdng md Bach Hd (nhiet gieng 140 - 150"C, da chua - granit niit ne hang hde, ap suat cao, mudi cao v.v ) Dya tren cac dac thii ciia ddi tugng sir dung, chiing tdi tien hanh nghien cu'u thii' nghiem de dua he dung dich tao gel tdi uu dap img dugc cac yeu cau ky thuat de ciia XNLD Vietsovpetro ddi vdi vat lieu phan each nude Cac thu nghiem dugc tien hanh theo phuang phap thu nghiem chai va Ihu nghiem dudi ap lye nito (Hinh 1) Thdi gian gel hda dugc danh gia bang each quan sat trang thai gel tao theo chuan Marathon Ben canh dd, thiet bi kinh hien vi dien tir quet dugc sir dyng de khao sat hinh thai hgc cac gel tao Tren ca sd mdt sd he dung dich gel dugc lya chgn tir bai phuang phap thir nghiem vira neu chimg tdi sir dung phuang phap tdi uu hoa thyc nghiem de dua he dung dich tao gel tdi uu viia dap img dugc thai gian tao gel va ben gel sau 32 giu' d nhiet 140°C, vii'a dam bao dugc gia nguyen lieu canh tranh dua img dung cdng nghiep Hinh 1: He thong thii nghiem gel dudi ap luc nito 174 Khao sat hf gel polyme de phan each nude cac gieng khai thac Phenol va formaldehyt tuong ddi de dang tao ndi vdi cac polyme Tuy nhien, cd ddc tinh eao nen hien da ban che sir dung cac hda chat tren gian HMTA da chimg minh dugc kha nang thay thi formaldehyt nhieu urng dung PhAc duge de xuat de thay thi phenol cd ddc tinh thip Khi phdi hgp PhAc vdi HMTA da keo dai dugc thdi gian tao gel ea viing nhiet cao, cho san pham gel cirng va ben viimg Co che tao gel dugc de xuat theo so dd Hinh Chudn bi mdu: Dung djch polyme duge cho vao dng thuy tinh (khoang 1/3 the tich dng), sau dd eho vao lugmg cin thilt chit tao ndi hoae tryc tiep hoae d dang dung djch dam dae Thdng thudng dung djch dam dac ciia chit tao ndi dugc hoa tan nude da dugc khir ion dl dl dang cho vao dung djch polyme Dung dich ldng hoae dam dac ciia chit tao ndi dugc cho vao dung djch polyme bing micropipet Ong thiiy tinh chira dung dich tao gel dugc loai bing each syc nito 10 phut rdi mdi day nap Cac dng thuy tinh dugc ii d nhiet ein thilt tu dilu nhiet va sau dd giir 32 d nhiet I40°C Dac biet, toe tao gel dugc ghi nhan sau mdi gid dau tien, sau mdi tuan dau tien va sau mdi tuan thang dau tien Ca ehudi cac he dung djch tao gel dugc xay dung va thir nghiem theo ciing mdt each nhu vay Cac miu khao sat thiet bj dudi ap lye nito cung dugc chuan bj tuong ty nhu da trinh bay d tren Cae dng nghiem chju nhiet cd dung tich 15ml dugc nap khoang 1/3 the tich dung djch tao gel rdi de binh nhd bang inox cd nap van vdi gioang kin Tren nap ed lap van thdng vdi binh nito Cho vao cac binh inox mdt chut nude de tao mdi trudng truyen nhiet Ap lye nito dugc giir sudt qua trinh khao sat la 7atm, bao dam nude va dung djch tao gel khdng bj sdi viing nhiet thir nghiem Gia nhiet tir 35°C den 140°C theo tdc l°C/2 phiit Cac mau (dugc lay sau timg gid d dau tien, timg d tuan dau tien) duge de ngugi rdi giam ap, md va khao sat tde tao gel bang each quan sat theo chuan Marathon Loai bd cac mau da quan sat xong de de phdng shock nhiet Mau cudi ciing dugc quan sat sau giir 32 d nhiet 140°C Tren co sd cae mau da duge khao sat va lya chgn cd thdi gian tao gel, ben nhiet ciia gel tao dap iing dugc yeu cau ky thuat ciia XNLD Vietsovpetro cho vat lieu phan each nude [8], chiing tdi sir dyng phuong phap quy hoach hoa thyc nghiem dl dua phan hdn hgp tao gel tdi uu Do hdn hgp tao gel bao gdm dung djch polyme cation CPAM, polyaerylamit non-ion NPAM va he tao ndi HMTA/Phenylaeetat, ndng eiia mdi loai polyme va ndng cua mdi chat tao ndi thii nhat (HMTA) va chit tao ndi thu (Phenylaeetat) deu cd nhiing anh hudng rieng din thdi gian tao gel va bin nhiet eiia gel tao TOI UtJ HOA Tdi uu hoa va kiem soat qua trinh gel hoa ddi hdi su hieu biet viing vang vl su tac ddng ciia cae yeu td thyc nghiem din cac tinh chit cua gel tao Phin mim thdng ke viet bang ngdn ngii lap trinh Pascal da dua cac md hinh toan hgc dya tren cac dir lieu dap img Ham dap img duge d day la thdi gian tao gel va ben gel Thdi gian tao gel duge xac djnh nhu la thdi gian can thiet de dung djch tao gel dat dugc miic cimg G theo chuan Marathon Do ben gel dugc xac djnh theo hai tieu chuan (a) lugng nude tach tir he gel va (b) ciing cua gel Vdi mau gel ran, eiing, khdng chuyen dgng lip 175 Tuyin tap bao cao Hgi nghj KHCN "30 nam DSu Vift Nam: Cff hgi mdi, thach thde mdi" nguge va hoan toan khdng tach nude thi cd ben la 100% Polymer sir dung cae thye nghiem la hdn hgp CPAMrNPAM theo ty le 2:1 Dua vao mdt sd kit qua thir nghiem so bg, chiing tdi chgn cae bien sd thyc nghiem nhu sau: (a) Nong polyme (Zl) biin thien tir 1% den 2%; (b) Ndng HMTA (Z2) biin thien tir 0,1% din 0,4%; (c) Ndng PhAc (Z3) biin thien tir 0,25% din 1% Nhimg bien sd duge gia djnh la khdng ddi bao gdm qua trinh ii tir 30°C den 140°C (vdi tdc gia nhiet la 5°C/10 phut va giu- d 140°C 32 ngay) De thyc hien quy hgach can 2^ = thyc nghiem (3 yeu td), mdi yeu td bien thien theo mirc, mirc tren la +1 va mirc dudi la 1, sau dd thyc hien thye nghiem yeu td toan phan Bang 1: Cac bien so va ham dap ung cho qua trinh gel hoa Cdc yen lo md hod Thiiv nghiem } gio- }; % - 18.5 62 - - 11.0 90 - + - 15.5 A4 + + - 8.5 92 A5 - - + 12,0 75 A6 + - + 11.5 88 A7 - + + 10.0 82 A8 + + + 6.0 90 A9 0 12.00 90 AlO 0 12.10 88 All 0 12.10 92 X, X| X, Al - - A2 + A3 Vdi, X = • 80 AZ Phuong trinh hdi quy duge eho bdi: Y= bo+ b,X, + b2X2+ b3X3+ b,2X,X2+ b,3X,X3+ b23X,X3+ b,23X,X2X3 (1) Cae he sdbdi quy bo, b|, b2, , b|2, bn.i_n dugc xac djnh theo cdng thirc: A^' N^ N J=l vdi m, i, i': sd thii ty yeu td i, i', m = k Kiem tra tinh y nghia cua eae he sd hdi quy Gia trj trung binh tai mirc co sd dugc tinh theo cdng thiic: Ii: i=] (m la sd thi nghiem d tam) m 176 Khao sat hf gel polyme dl phan each nude cac giing khai thac T(y Yy Phuong sai tai hien: S^ • m-l Tinh eae gia trj t theo cdng thiic: b , '^^S, 'u'-s h s =-^ ^, yfN Cac he sd hdi quy ed y nghia tj, tjp > t(p_t) vdi t(p t) dugc tra ciiu tren bang thdng ke theo chuan Student Kiem tra su tuomg thich cua phuong trinh hdi quy vdi thue nghiem theo chuan S' ' Ficher: F - s: y{Y-Yy , Vdi 6"; la lech chuan du S] = ——'•—'•—, dd N - sd thue nghiem; he sd hdi N -\ quy cd y nghTa; Y^ va Yj la cae gia tri thye nghiem va tinh toan tai thi nghiem thir i [9, 10] Tir cac sd lieu Bang 2, cac tinh toan tren may tinh (sir dyng ngdn ngu- Pascal) da nhan nhirng ket qua sau: Thdi gian gel hoa Vdi bo = 11,625; b, = -2,735; b2 = -1,625; bj = -1,75; b|2 = -0,375; bi3 = 1,25; b23=-0,25; b,23 =-0,5 to= 130,7; t, = 26,7; t2= 18,3; t3= 19,7; t,2 = 4,2; t,3= 14,1; t23 = 2,8; t,23= 5,6 O day ti2, t23 < 4,3, dd cac he sd bi2, b23 khdng cd y nghia Phuong trinh hdi quy tim dugc la: Yi = 11,63-2,38Xi-1,63X2-lJ5Xi'^l,25XiXi^-0,5X^X2X3 (2) Do ben gel Vdi bo= 83,0; b, - 7,0; b2 = 4,3; b3 = 0,8; b,2= -3,3; b,3= 1,8; b23= -2; b,23 = to= 117,4; t, = 9,9; t2= 6,0; t3= 1,1; ti2 = 4,6; t,3= 2,4; t23- 2,4; t,23 = 2,8 day t3, ti3, t23, ti23 < 4,3 dd cae he so b3, b|3, b23, b|23 la khdng ed y nghia Phuang trinh hdi quy tim duge la: Y2 =83,0+ 7,0X1 + 4,3X2 - 3,3X,X2 (3) Dl khao sat sy tuomg thich ciia phuong trinh (2) va (3) vdi thyc nghiem, phan tich Ficher's F da dugc thuc hien Tir cac sd lieu Bang 1, cac tinh toan da cho kit qua sau: FthLTc nghiem (thoi gian tao gel) = 12,83; F,h^rc nghiem (do bin gel) = 5,81 Ddi vdi fl = va f2 = va d mire cua p = 0,05 gia trj eiia Ficher F tir bang thdng ke chuin la Fo,o95 (4,2) =19,3 177 Tuyin tap bao cao Hgi nghj KHCN "30 nam D5u Vift Nam: Cff hgi mdi thach thuc mdi" Boi vi Fiiurc nuhiem < Fp-icher- Cac pHuong triuh hdi quy tim dugc (2) va (3) cho thdi gian tao gel va bin gel la phii hgp tdt vdi thuc nghiem Phuang trinh (2) cho thiy ring thdi gian tao gel giam cac ndng cua polyme, HMTA PhAc gia tang Trong dd ben gel lai gia tang ciing trgng dieu kien nhu tren (phuong trinh (3) Cac sd lieu Bang cho thay thi nghiem sd gan viing tdi uu Do dd 20 thi nghiem khae da dugc tien hanh de tim dieu kien tdi uu cho he dung dich tao gel Nhu vay, chiing tdi chgn viing lan can: Zl (ndng polyme, %): 1,4 - 1,6; Z2 (ndng HMTA, %): 0,2 - 0,3; Z3 (nong PhAc, %): 0,4 - 0,6 Bang 2: Ma tran qu>' hoach thuc n ghiem ctia qua trinh tao ^el theo Box-Hunter ST Xo T X, + + + + + + + + - + + + - + - + + - - + - + + - + X2 Xi X,2 X,3 X23 Xi' Xf -' / (Gelation Xi nine) + + + + 100 - + + + 8,2 92 + - + + + 11,5 99 - - + + + + 11,6 90 + - - + + + + 8,5 95 + - - + - + + + 9.0 90 - - + + - - + + + 11,6 93 + - - - + + + + + + 12,0 85 + -1.682 0 0 2,828 0 9,5 85 10 + + 1,682 0 0 2,828 0 10,5 95 11 + -1,682 0 0 2,828 15.3 95 12 + + 1,682 0 0 2,828 9,2 98 13 + 0 -1,682 0 0 2,828 11,5 90 14 + 0 + 1,682 0 0 2,828 12,0 100 15 + 0 0 0 0 12 99 16 + 0 0 0 0 12.3 98 17 + 0 0 0 0 12 99 18 + 0 0 0 0 12.5 98 19 + + 0 0 0 0 12.2 99 0 0 0 0 12,0 99 20 + Y(Gel strenglh) Phuang trinh hdi quy mu (theo Box va Hunter): = b„ + b,X, + b2X2 + + b„X„ + b,2X,X + + b,„,„X,„,„ + b, ,X,- + + b„„X„„- (4) day: b =^