BO GIAO DUG VA DAO TAG DAI HOG QUOG GIA HA NOI TRUONG DAI HOG KHOA HOG Tl/NHlfiN DINH XUAN LOG Ngliien ciiu ung dung tinh chat ky nuo^c ciia axit MDV doi voi qua trinh nghicn clinker vii tang thori gian biko quiin xi inang. LUAN VAN THAC SY KHOA HOG HOA HOC Chuyen nganh : Hoa vo ca Ma so : 01.04.01 'L^JOt Huong dan khoa hoc : TS. Nghiem Xuan Thung P(iS.TS.Phan Van 1 uong Ua noi 2000. J Mue luc Ph;lM A Chircng 1 I.I. 1. 1. 1. 1. 1. 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 2.1 T 1 2.} 2.4 2 "^ 2.r) 3 3.1 3.2 3.3 3.4 3.5 4 .4.1 .4 2 .4.3 .4.4 .5 .5.1 .5.2 .5.3 .6 .7 .7.1 .7.2 .7.3 .7.3;i .7.3b .7.3c .7.3cl .8 1.8.1 1.8.2 1.8 ^ 1.8.4 1.8.5 I .8.6 Lcri ma daii Tung quail Xi maiig pooclang Khai iiiem Thanh phaii hoa hoc ciia clinker xi mang CaO SiO, Al,0, Fe^O, MgO Kicm Thanh ph;1n khoang hoa ciia clinker xi inang pooclang Alit Belit , Canxi Ahiniinal cciii I1IZIIZZIIZZZ^^\Z^ I'ha tlmy tinh Qua Irnih hydrat hoa ciia xi mang Phan iVng hydrat hoa cua khoang Alit Phan ung hydral hoa cua khoang Belit Phan ung hydrat hoa cua khoang TricaxiAluminat Phan I'rng hydral hoa cua khoang Tetra caxi Fcroaluminat Cac he so ca ban cua clinker xi mang pooclang He so bao hoa voi LSF Modun .Silic SM Modun iihom AM Qua truih san xuflt xi mang pooclang Nghien xi mang pooclang Thach cao Cac loai phu gia khac Oic vcu to lien quan den qua trnih nghien Do min Kha nang nghien cua vflt lieu Phuong phap nghicn Cac chflt tro nghien C.ac tinh chA't co ly hoa cua da xi mang va cac yen to auh hmyiig den no Do mill T\ le iiuo'c/ xi mang Thoi gian iiiiih ket Cirofiig do \ a mac cua xi mang Su to;i nhiet khi doiig ran Do on diiili the tfch Tiaiig 1.2 ' 3 3 3 3 3 4 4 4 4 4 5 5 5 6 7 7 7 8 8 9 9 10 10 10 1 1 1 1 13 13 1^ 13 13 14 14 14 15 15 15 15 16 19 20 1.8.7 Do ginm mac luc lini kho ban quan 20 1.9 Cac loai phu gia tra nghicn xi mang 21 1.9.1 Tro xi 1.9.2 Phu gia Puzolan 22 1.9.3 Cac loai axil beo va chat hfru co khac 23 ChU(tng 2 Vai tro cua phu gia ky nirac doi vai xi mang 27 Chircyng 3 Cac phirang phap hoa ly nghien curu xi mang 34 3.1 Phaang phap phan tfch hoa hoc xac djnh cac thanh philn khoang hoa ciia xi mang 34 3.1.1 Xac dinh lugng SiO. trong xi mfing 34 3.1.2 Xac dinh ham lirgfng Fe;0, 35 3-1 -3 Xac dinh ham liraiig Aip, 35 3.1A Xac dinh ham krcrng CaO ^ 36 3.1.5 Xac dinh ham lagng CaO tir do ' 37 3.2 Phirong phap phan tfch nhieu xa tia X 38 3.3 F^hucrng phap phan tfch pho hong ngoai 39 3-4 Phirong piiap phan Ifch nhict 41 3.5 IMian Ifch cap hat bang quang pho laser 43 l^han B Thac nghiem ^^ C hUitng 4 Nghien ci'ru anh hirong cua axit beo MDV den tfnh nang ciia xi mang pooclang ^^^ 4.1 Doi tintng va phirang phap nghicn cihi A^ 4-2 Aiih hiring cua ham lirang phu gia dei] do min cua xi mang ^(^ 4.3 Anh huang ciia ham lirang phu gia den do ky nirdc cua xi mang 50 4.4 Xnh hirang cua ham lirang phu gia den chat lagng xi mang khi bao quan 5 I 4-4.1 £)Q hut am theo thai gian bao quan 51 4-4.2 £)Q \ on cue theo thai gian bao quan 54 4.5 Arih hirang cua ham lugng phu gia deii do deo lieu chuan ciia xi mang _^ _ _ ^ ; •" • _ ^ "^ ^ !Sh 4.6 Anh hirang cua ham hrgng |)hu gia den qua lilnh dong h(.)c dong ran cua xi mang ^^ 4-7 Xiih hirang cua ham lirgng phu gia den cirang do cua xi mang 59 Chirang 5 Danh gia xi mang co phu gia ky nuac bang cac phirang phap hoa ly hien dai . ^ 5-1 Phan tfch nhieu xa Ranghen 5-2 |>|ian tfch nhiet vi sai DTA IMian ifch bang quang pho hong ngoai Phan tfch bang kfnh hien \i dien tir Phan tich cap hat bang laser -^ Ket luan -j 5.3 5.4 5.5 63 67 69 60 Mo ddu Xi mang la vat lieu quan Irong hang dau Irong nganh xay dung, chi'nh vi va)' nganh cong nghicp san xual xi mang dUdc coi la mol U'ong nhu'ng nganh mui nhon cua mol nii^c. San Iticfng lieu ihu xi mang hang nam ciia moi nuac la mol Irong nhung chi lieu cho la ihay loc do phal Iricn kinh Ic ciia dal nuo'c do. 0 Vicl nam Irong qua Irlnh kicn ihicl dal nuac ,nhu cau sir dung xi mang cho xay dung hien nay la 18 Iricu Ian va duyc du doan lang Irung blnh khoang 10 - 15%/ nam Irong mUoi nam lai. Dc ihu'c hien khoi lirong xay clu'ng lo 16'n Irong nhung nam lai, chiing la can lang dang kc khoi luo'ng xi mang va nang cao chal luang xi mang. Irong dicu kicn lir nhicMi voi khf hau nhict doi nong am, mua nhieu, vice san xual, bao tiuan. van chuycn, luu kho laii ngay moi sir dung, nhal la xi mang \\i\ khong dong bao. ihl van dc cai Ihicn va nang cao chal hro'ng xi mang la ral buc ihiel. Tu nhung ycu cau cap ihici do, vice nghicn cii'u va sil dung phu gia xi mang ki nuoc co mot vai Iro ral c|uan Irong . Do la mol giai phap khoa hoc ky ihual lam hiCMi doi mol so liiih chal ciia xi mang, be long va vij'a be long iheo quan diem Uic dung cua niriV cV cac giai doan khac nhau Irong san xual va sir dung loai vai lieu nay. Clu can mol luong phu gia hiru co* ral nho (vai phan nghln) cho vao khi nghicn clinker, co ihe cai Ihicn va nang cao chal \via\\\i sii' dunu ciia xi man^^ () kicMi X6 lir nam 1947 - 1949 da nghicMi ciiu va chc lao diro'c xi manu ki nir(')c.dCMi nam 1950 da dira vao san xual cong nghicp. Sau niiv cac nha khoa hoc LicMi Xo da nghicn cu'u sii' dung nhieu loai phu gia ki nu'(')"c va cac dac dicMii ky ihual ciia xi mang ki nuac Irong vu'a, be long dicing trong cac cong Irinh \a\' du'nu. 0 nu6c ta tir tmoc tai nay co vai tac gia da nghien cuu sir dung phu gia ki nuac vai cac muc dich khac nhau nliu phu gia K3CS tir cac loai dfui khoang, dau thao moc nliam cai tieii tuili chat cua xi mang [ 3,16,17 ] . Tliay dirge tarn quan trong va tinh thofi sir cung nJiu" muc dich cua van de neu tren. Trong pham vi cua de tai chiing toi khac sat , nghien ciiu^irng dung \oa\ phu gia axit beo MDV vao xi mang pooclang Biit san nh^m dap li'ng yen cdu da n§u do. PHAN A Tong quan CHU()N(, 1: XI MAN(J POOCLANC; 1.1. Khiii iiiciii : Xi mang la ten ggi chimg ciia mol nhcim hgp chat ket dfnh v6 co\ cci kh;i nang ngung ket, dong ran khi ket hap voi nuov. Xi mang pooc lang la san pham nghien min ciia clinker v('yi pini gia thach c lo (3 -5%) Clinker o dang hat dirge san xiiai bang each du vc nung cho den kcl khoi o I450"C/ hon hgi") chi'ra da voi va Alumosilicat (dai set, xi lo cao ) rhacli cao c(i tac dung dieii chinh Ihoi gian ninli ket cua xi mang . tioiig khi nghien min de dieii chinh Ifnh chat va ha gia thai h nguoi ta cho thcMii khoi'nig L5'/ phu gia boat linh nhu" Puzolan, Iro, (rcpcn. . khoang 0,1 - 0.5';^ pini gia tro" nghien uhir axil beo, mo" dong \al, dfui thirc \a( va 10',^ phu gia lio nhn c;it. thanh anh, da \6i. [ 7 | . Xi mang dirge phat minh va san xua't tir dfiii the ky 19 tai Anh. do nhu'ng uu (hiMU noi bal nhu cuong i]o cao. dong liin nhanli ucu xi mang pooc l;tng da tio thanh chat ket dfnh cjiian Irong nhal Irong \a\ dung co' ban. 1.2. riuinli pliiin lioii hoc ciui clinker xi inaii^ | 9 Day la yen to cpian trong nhal de danh gia chat I rgng clinkci. Gom co 6 oxit chinh: 1.2 .1 . CaO : chicm t(')'i 63 - 67 ^; va dugv k\ hu u la C. CaO la oxit cpian Irong nhal dc' xi mang co chal u'Ong cao. CaO ph;'ii lien kcl hcl Mvi cac oxit khac.iicii hrgng CaO tir do con 1; i a dang cpia lira sc lam cho da xi mang khong on dinh the Ifch ga\ tac hai cho \i manu. Liroin: CaO lu'n kcl Ion lam xi mang co cuong do cao, dong rfui nhanh. nhirng khi dong ran lai loa nhiet nhi^u nen kern ben hoa. 1.2.2. SiO, : chiem 21-24 '/r, ky hien S SiO, lien kel voi CaO lao thanh khoang Silicat Cac khoang na\ ^'^'^ \ai Iro qnyel (hnh tci'i cii'o'ng do ciia vua xi mang doin cii'ng. Luong SiO, lien kcl l(Vn,vl vay xi mang co cuo'ng do Ion sau 2S nga) dong ran cham. vl toa nhict nh(i khi d(ing ran ncn ben boa ho'n. 1.2 '^. A1,0, chicm 4 - 8 '/r ky hieii A AI,Ojien kcl voi CaO va Fe,()^ tao khoang Aluminat va Aluminoferit canxi, lam cho xi mang co cii'ong i]o phal Irie'n h'lc dilii ao. sau chani dan. Ihoi giim dong ran nhanh, nhiel toa nhieu, toe do toa nliiet Ion. do i\n khi dong ran kcm ben ho;i. 1. 2 .4 . FcO, chiem 2,5 - 3 '^, ky hien F Fe,()^ licMi ket voi CaO tao thanh Feritcanxi 1 oac Alumoferit canxi. Ncii hrgng Fe,0, hi'n, nhiel do ket khoi ciia jihoi lieu gi;'im, do nlvi't pha long nho i.\c tao khoang trong clinkci. Neu Fe,0, ciua h n xi mang co l\ Irong cao. cunng iAi^ Ihap, dong ran cham, toa nhiel lha|), nhung ben hoa. I. : .5 . MgO tir 5 -6 % Neu MuO > 5 - 6'f sc lam xi mang khonu on dinh the lich khi donu ran. \i no o tinnu dune tlich lan thnv tinh Pci iclaz (uion:-, Ca() lir do) . 2 .6 . KiOm chicm 0.1 - \'/< . kv hien KX) Khi cho kiein van clinker thl mot phfin bay di va mol ph;1n o lai tronu clinkci (K.O > Na.O). Day la thanh ph:1n khong mong niuon \i n('> lam giani tto nhol ciia pha long, lam tang dinh bet va lha> doi lor do dong lan cua \i mang. Kicm lac dnng voi SiO, lao gel silicat kicm. co die licli Ion ga\ mat on dnih the lich, khong ben nii'6'c. Ngoai ra con co cac oxit khac nIniTiO, - Mn,() . !',() nhung co anh huong nho khong dang kfi toi xi mang 1.3. riinnh phan khoang cua clinker \i niaiiji pooclang | 4 | I. 3.1. Alit ( (\S ): chiem 4.'S - 70% \)C\\ la khoang (juan Ining niiat cua clinkci. ix) la dung dicli ran ciia ."^C/aO.SiO, CC) lan lAn .^ - 4'/r cac oxit khac. Alit (C.S) lao Ihanh a nhiel do < I2.^{)"C .^C + s = c,s \'a chi'i \cu lao thanh khi co mat |iha h'mg. N(') ben o nhiet do I^^O'C - r)()()"C'. Khi nhiel do nho hon I2.^()"C Ihi C,S = (' + CS Sir bicn doi na\ phu thuoc vao che i.]o lam lanh \ i ^u' c('' mat c;'ic hop chal hoa lan lioim C".S. Tinh chat cua Alit trong xi mang: - Cho \i mang c(') cuo'ng do cao nhal sau 2 < ngay - Ihoi gian dong ket nhanh. dong ran nhai h (sau C,A) - Foa nhiet nhieu khi dong ran - Khong ben Irong moi tiiiong Siinfat \. } .2 . Belil : chiem 20 - .^0'/ (C,S) ?clil la dung dich i;'ui cu;i 2Ca().Si(), CO tan lan 1 - 3'Y cac oxit kh:ic. C,S (2CaO.Si(),) co nhicu daiii: thh hinh: (/C.S , f^C.S , yC,S nhirng chi c6 da ig (K\S la c6 tinh chat kel dinh. dfi) la dang ngiroi ta lAt mong muon co. |iC,S gia b£Mi Ion lai a t" < 650"C. \\C^S kho I6ng hop vi khi lam lanh i/CS -> yCVS va tang the lich 10% lam tang clinker, yC^S khong co linh chA't kel dinh. do vay can |)hai tao on dinh (^C,S qua cac phiron:', pha|i sau: - Hoa hoc linh Ihe: dua vao mol so oxil nhu" N; .O. P,0,, P>0. lam Ihay doi cau In'ic linh the, lam Ihay doi tuih chat ho;i ly ci a C,S. - Vai ly: nang cao ham luong pha long liong clinker hoc chal la\ (K'.S. ngan can sir chnyfen ihanh yC^S. - Nhiel: lam lanh nhanh vu'o'l qua nhiel do hien doi thu hinh \'i khi do c;ic cA'u hue tao thanh rieng re khong kip li)[i ho|^ lai thanh dnng dich r;ui o nhict do cao ncMi khong kip hich ra. Tinh chat ciia Belit trong xi mang: Lam cho xi mang c() cuong do phiil tiien cham nhung sau 2S nga\ I hi gan bang C\S. - Thoi gian dong ket chain - To;'i nhiel nho khi dong riin - Ben trong moi truong Sunfal 1. 3 .3 . Canxi Alumina! : chiem 5 - 15% La dung dich iTni cua C,A (3C\i(). ALO,) co tan lAn 1 - 27rCaO tuy theo luong CaO. C \a che do lam lanh clinkei ma C; nxi Aluminat c(i the o dang C^A,C\A,. Trong clinker xi mang chi'i yeii la C,A. '•' Tinh chal cua Canxi Aluminal: - Lam cho xi mang c(') cu'ong do ph;il tiicn nhai h nhung sau do h| chain l<ii va khong h,nig C,S - Thoi gian dowz kel nhanh nhal - Toa nhiet nhieu khi dong rfin - Khong ben Irong moi Irirong Sunfal 1. .3 .4 . Celil : chiem 10-18% La dung dich lAn ciia C^AF (4CaO.Aip,Fe,0;) ro cac Ihanh phAn khac nhau phu thuoc vao phoi lieu va di^u kien nung luyen C^A.F; C,AF; C,F () day chii yeii la dAF . 1 inh chat cua C,AF : - Lam cho xi mang c6 cuo'ng do thaj") nhal - Thoi gian dong ket cham - Toa nhiel khi dong ran Ihap nhAl - Ben trong moi Iruong Sunfat ho'n C,A I. .^ .5 . Pha thiiy tinh trong clinker : Do C^A, CjAF, C,F (V nhiel do cao -^ hoa King - > lam lanh ~> lao thiiy tinh. Pha Ihuy linh co lAn MgO va cac tap chA't khac do do tuy che do lam kuih ma |iha Ihuy linh nhieu hay fl. Neu phix thiiy linh nh eii thl khi xi mang dong ran se toa nhict nhieu. 1.4. Qua triiili liidrat hoa cua \i nian^ | 2 | Khi hoa Iron xi m;uig \o'i lurtVc. sir khiiech tan cu \ cac h;it kho;uig xi mang co kich Ihiioc nh(i \ao moi Iruong uu'oc \l\ phan ihm hidral hoa cua chiing dicn ra t!ii'(yc lien. Dong thoi iiiroc lAii cong len be mat cua cac hat khoang va phan ihig cua hidral cung xay ra tren be mat cac hat khoang nay. Sau do niitV Iham tian \ao cac hat xi mang h'vn, c|ii;i liui i thiiy ho;i \An ticp line dicn ra. Tlurc Ic cho Ihay tham chi sau 4 nam \an con 15'r C,S chna iham LLKI [...]... kfnh Imin Thni gian bAt dAn ninh ket la khoang thoi gian In" khi bal (lAu nhao Iron xi mAng vdi nirdc d^n khi kim vi^a cAm sAii 3S - 39mm, yeu cAu thoi gian nay khong nho ho^n 45 phut Thoi gian ninh kei xong hay bAI dAii lAn chAc la khoang Ihoi gian tir khi nhao Iron xi mAng vdi nude d€n khi kim vica cAm s Ui I - 2mm Thoi gian nay khoang 104^12 gid L 4 ] 1 X 4 Ciidng do va mac cua xi mAng : Theo... kfch Ihfch thl xi the hien hoal tfnh ChAI kfch thf-h ( dAy la Ca(()H)^, sunfat V si1a voi khi ket hgp v6i nirdfc thl se tao ra lofp m ing tren he mAl xi chAI kfch Ihich se |)ha vo l(y|i mang lam cho xi hoc 16 ho.it tfnh nhu' kho;ing clinkci Ngufri la dua xi vao nguyen lieu hoac lam p iii gia dua \ao khi nghicn clinker Neu liiong xi dua vao khi nghien clinker < \5^/f xi mAng Ihl goi la xi mAng pooclang... Ihl goi la xi mAng pooclang Ihudng Con neu lucrng xi dira vao > I ^% hrong xi mAng Ihl goi la xi mAng xi Yen cAu clinker cd ham lirang C\S va C\A \on vl xi cfin chat kich Ihich va ddng ran cham Ham luong voi tu do cd the tdi 5 - 6% vl : CaO-hH,O^Ca(()H), Xi mAng xi cd Irong luong rieng, do co ngdt do 'oa nhiet, do hcu lanh va gi;l Ihanh nho hon so \'di xi mAng thirdng nhung luong IUKVC lieu chiiAn va... khoang cua clinker Xi mang co ihanh phAn C\S Ion Ihi luong nii'cVc tieu chu An Ion 1 8 3 riidi gian ninh ket Khi Iron \i mAng \'(Vi niioc se xay ra jihan ung Ihuy hoa cua cac khoi'uig liong xi mAng \ ii'a t;io thanh Iheo thoi gian sc mAl ('An tinh deo sau do \\o ncn ciVng ran \ a co the chiu lire dirge Ngirdi ta |4iAi hiet hai loai thoi gian ninh kcl : \5 - Thai gian bAI dfiu ninh kel : la thoi gian tir... hoa Loai phu gia ihi'r nhai nlur paraphin axil stearic hoac mudi canxi ciia axil beo cd phan u Idn khi Iron V vcVi xi mang khong lac dung vdi nd ma Ion lai Irong dd d" dang hon hop co' hoc Lc:)ai phu gia ihu hai la xa phdng hoa lan cua axil beo, axil nhua, hoac axil dau m(') Tuy ban than nd khong ky nude nhUng lai lao ihanh chai ky nude do Uic dung hoa hoc vdi xi mang Loai phu gia ky nude hoa ihugc loai... biic xiic Khi cho phu gia ky nudc vao hie nghien clinker se cd lai: 32 - Tang do min ciia xi mang - TAng nang suat nghien clinker hoac giam thai gian nghien do dd giam tieu hao nang lugng va bi nghien - Chdng vdn cue trong silo chua xi mang - TAng toe do ddng bao Ndi torn lai viee nghien cihi va sir dung phu gia trg nghien ky nudc trong san xuA't va sir dung xi mang cd nhieu uu diem noi bat ma xi mAng... - Thai gian ket thilc ninh ket : la thai gian tii khi Iron nude den khi \ua cirng lai va cd the chiu lire dirge Trong Ihi cong, chi tieu nay phai iiAm ro vl tAt ea cac khAii \'An chuyen, do va dAm be t6ng phai tien hanh xong tiudc khi xi mAng bAt dfiu dong dAc, do do xi mAng phai cd thai gian ninh ket du dai chi cac thac^ tac nay duoc hoan lAl Theo TCVN cung nhir tieu chiiAn the gidi 'hi thoi gian ninh... Thiet bj dong nhSt i I Thach cao • Lo nung clinl . bi lam lanh clinker May dap clinker lay dap Phu gia May nghien Si 16 chCra. u clinker Si 16 chQa xi mSng ^ ^ Xuat xi mSng rdi w p May dong bao '^ r Xual xi m^ng bao. daii Tung quail Xi maiig pooclang Khai iiiem Thanh phaii hoa hoc ciia clinker xi mang CaO SiO, Al,0, Fe^O, MgO Kicm Thanh ph;1n khoang hoa ciia clinker xi inang pooclang. Cirrmg do cua da xi mang va loc do ciing rSn ciia no phu Ihuoc vao ihanh phan khoang clinker, vao do min cua xi mang, do am. nhiel do moi Iruong va Iht^i gian bao quan cua xi mang. Toe