Nghiên cứu ứng dụng tính chất kị nước của axít đối với quá trình nghiền clinker và tăng thời gian bảo quản xi măng

BO GIAO DUG VA DAO TAG DAI HOG QUOG GIA HA N O I 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 uong Ua noi 2000 J M u e luc Tiaiig Ph;lM A Chircng I.I 1.2.1 T 1 2.} 2.4 "^ 2.r) 13 3.1 3.2 3.3 3.4 3.5 14 1.4.1 1.4 1.4.3 1.4.4 1.5 1.5.1 1.5.2 1.5.3 1.6 1.7 1.7.1 1.7.2 1.7.3 1.7.3;i 1.7.3b 1.7.3c 1.7.3cl 1.8 Lcri m a 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 O i c vcu to lien quan den qua trnih nghien Do 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 1.8.1 1.8.2 1.8 ^ 1.8.4 1.8.5 I 8.6 Do mill T\ le iiuo'c/ xi mang Thoi gian iiiiih ket Cirofiig \ a mac cua xi mang Su to;i nhiet doiig ran Do on diiili the tfch 1.2 ' 3 3 4 4 5 7 8 9 10 10 10 11 11 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 1.9.1 1.9.2 Cac loai phu gia tra nghicn xi mang T r o xi Phu gia Puzolan 21 -22 1.9.3 ChU(tng Chircyng 3.1 Cac loai axil beo va chat hfru co khac Vai tro cua phu gia ky nirac doi vai xi mang Cac phirang phap hoa ly nghien curu xi mang Phaang phap phan tfch hoa hoc xac djnh cac philn khoang hoa ciia xi mang Xac dinh lugng SiO xi mfing Xac dinh ham lirgfng F e ; , Xac dinh ham liraiig A i p , Xac dinh ham krcrng CaO ^ Xac dinh ham lagng CaO tir ' Phirong phap phan tfch nhieu xa tia X F^hucrng phap phan tfch hong ngoai Phirong piiap phan Ifch nhict IMian Ifch cap hat bang quang laser 23 27 34 ^^ 4.1 Thac nghiem Nghien ci'ru anh hirong cua axit beo MDV den tfnh nang ciia xi mang pooclang Doi tintng va phirang phap nghicn cihi 4-2 Aiih hiring cua ham lirang phu gia dei] cua xi mang 4.3 Anh huang ciia ham lirang phu gia den ky nirdc cua xi mang 50 4.4 4-4.1 4-4.2 Xnh hirang cua ham lirang phu gia den chat lagng xi mang bao quan £)Q hut am theo thai gian bao quan £)Q \ on cue theo thai gian bao quan 5I 51 54 4.5 Arih hirang cua ham lugng phu gia deii deo lieu chuan ciia xi 3.1.1 3.1.2 3-1 -3 3.1A 3.1.5 3.2 3.3 3-4 3.5 l^han B C hUitng _^ _ 4-7 Chirang 5-1 5-2 5.3 5.4 5.5 ^^^ A^ ^(^ mang 4.6 34 34 35 35 36 37 38 39 41 43 _ ^ ; •" • _ ^ "^ ^ Anh hirang cua ham hrgng |)hu gia den qua lilnh dong h(.)c dong ran cua xi mang ! S h ^^ Xiih hirang cua ham lirgng phu gia den cirang cua xi mang Danh gia xi mang co phu gia ky nuac bang cac phirang phap hoa ly hien dai Phan tfch nhieu xa Ranghen |>|ian tfch nhiet vi sai DTA IMian ifch bang quang hong ngoai Phan tfch bang kfnh hien \i dien tir 59 Phan tich cap hat bang laser -^ Ket luan -j ^ 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 phal Iricn kinh Ic ciia dal nuo'c Vicl nam Irong qua Irlnh kicn ihicl dal nuac ,nhu cau sir dung xi mang cho xay dung hien 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 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 Irong san xual va sir dung loai vai lieu Clu can mol luong phu gia hiru co* ral nho (vai phan nghln) cho vao 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 cac cong Irinh \a\' du'nu nu6c ta tir tmoc tai co vai tac gia da nghien cuu sir dung phu gia ki nuac vai cac muc dich khac nliu phu gia K C S tir cac loai dfui khoang, dau thao moc nliam cai tieii tuili chat cua xi mang [ 3,16,17 ] Tliay dirge tarn quan 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 PHAN A Tong quan C H U ( ) N ( , 1: XI MAN(J POOCLANC; Khiii iiiciii : X i m a n g la ten g g i c h i m g ciia m o l nhcim h g p chat ket d f n h v co\ cci kh;i nang n g u n g ket, d o n g ran k h i ket hap v o i n u o v X i m a n g pooc l a n g la san p h a m n g h i e n m i n ciia c l i n k e r v('yi pini gia thach c lo (3 - % ) C l i n k e r o d a n g hat dirge san xiiai b a n g each du vc n u n g c h o den k c l k h o i o I450"C/ h o n hgi") chi'ra da voi va A l u m o s i l i c a t (dai set, x i lo cao ) r h a c l i cao c(i tac d u n g dieii c h i n h Ihoi g i a n n i n l i ket cua x i m a n g t i o i i g k h i n g h i e n m i n de d i e i i c h i n h Ifnh chat va gia thai h n g u o i ta c h o thcMii khoi'nig L ' / phu gia boat l i n h nhu" P u z o l a n , I r o , (rcpcn k h o a n g 0,1 - 0.5';^ pini gia tro" n g h i e n uhir a x i l beo, mo" d o n g \ a l , dfui thirc \a( va 10',^ phu gia l i o nhn c;it a n h , da \ i [ | X i m a n g dirge phat m i n h va san xua't tir dfiii the k y 19 tai A n h d o nhu'ng uu (hiMU noi bal n h u c u o n g i]o cao d o n g l i i n n h a n l i ucu xi m a n g pooc l;tng da t i o chat ket d f n h cjiian I r o n g nhal I r o n g \ a \ d u n g co' b a n riuinli pliiin lioii hoc ciui clinker xi inaii^ | D a y la yen to cpian t r o n g nhal de d a n h gia chat I rgng c l i n k c i G o m co oxit chinh: 1.2 C a O : c h i c m t(')'i 63 - 67 ^; va d u g v k\ hu u la C C a O la oxit cpian I r o n g nhal dc' xi m a n g co chal u'Ong cao C a O ph;'ii lien kcl hcl Mvi cac o x i t k h a c i i c i i hrgng C a O tir c o n 1; i a d a n g cpia lira sc lam cho da xi m a n g k h o n g on d i n h the Ifch g a \ tac hai cho \ i m a n u L i r o i n : C a O lu'n kcl Ion lam xi mang co cuong cao, dong rfui nhanh nhirng dong ran lai loa nhiet nhi^u nen kern ben hoa SiO, : chiem - '/r, ky hien S SiO, lien kel voi CaO lao khoang Silicat Cac khoang na\ ^'^'^ \ai Iro qnyel (hnh tci'i cii'o'ng ciia vua xi mang doin cii'ng Luong SiO, lien kcl l(Vn,vl vay xi mang co cuo'ng Ion sau 2S nga) dong ran cham vl toa nhict nh(i d(ing ran ncn ben boa ho'n 1.2 '^ A1,0, chicm - '/r ky hieii A A I , O j i e n 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 toa nliiet Ion i\n dong ran kcm ben ho;i F c O , chiem 2,5 - '^, ky hien F Fe,()^ licMi ket voi CaO tao Feritcanxi o a c Alumoferit canxi Ncii hrgng F e , , hi'n, nhiel ket khoi ciia jihoi lieu gi;'im, nlvi't pha long nho i.\c tao khoang clinkci Neu F e , , ciua h n xi mang co l\ Irong cao cunng iAi^ Ihap, dong ran cham, toa nhiel lha|), nhung ben hoa I : MgO tir -6 % Neu MuO > - 6'f sc lam xi mang khonu on dinh the lich donu ran \i no o tinnu dune tlich lan thnv tinh Pci iclaz (uion:-, Ca() lir do) 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 ph:1n khong mong niuon \i n('> lam giani tto nhol ciia pha long, lam tang dinh bet va lha> doi lor 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 co cac oxit khac n I n i T i O , - Mn,() !',() nhung co anh huong nho khong dang kfi toi xi mang r i i n n h p h a n k h o a n g c u a c l i n k e r \ i niaiiji p o o c l a n g | | 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 < I2.^{)"C ^C + s = c,s \'a chi'i \ c u lao co mat |iha h'mg N(') ben o nhiet I^^O'C r)()()"C' Khi nhiel nho hon I2.^()"C Ihi C,S = (' + C S 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 xi mang: - Cho \i mang c(') cuo'ng cao nhal sau < - I h o i gian dong ket nhanh dong ran nhai h (sau C,A) - Foa nhiet nhieu dong ran - Khong ben Irong moi tiiiong Siinfat \ } Belil : chiem 20 - ^0'/ (C,S) ?clil la dung dich i;'ui cu;i 2Ca().Si(), CO tan lan - 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 lam lanh i / C S -> yCVS va tang the lich 10% lam tang clinker, yC^S khong co linh chA't kel dinh 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 , , , 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 l i o n g clinker hoc chal la\ ngan (K'.S can sir chnyfen ihanh yC^S - Nhiel: lam lanh nhanh vu'o'l qua nhiel hien doi thu hinh \'i c;ic cA'u hue tao rieng re khong kip li)[i ho|^ lai dnng dich r;ui o nhict cao ncMi khong kip hich Tinh chat ciia Belit xi mang: Lam cho xi mang c() cuong phiil tiien cham nhung sau 2S nga\ I hi gan bang C\S - Thoi gian dong ket chain - To;'i nhiel nho dong riin - Ben moi truong Sunfal 3 Canxi A l u m i n a ! : chiem - 15% La dung dich iTni cua C,A (3C\i() A L O , ) co tan lAn - 27rCaO theo luong CaO C \ a che 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 A l u m i n a l : - Lam cho xi mang c(') cu'ong ph;il tiicn nhai h nhung sau h| chain l lam lanh ~> lao thiiy tinh Pha Ihuy linh co lAn MgO va cac tap chA't khac do che lam kuih ma |iha Ihuy linh nhieu hay fl Neu phix thiiy linh nh eii thl xi mang dong ran se toa nhict nhieu Q u a triiili liidrat hoa c u a \ i n i a n ^ | | 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 \ a o moi Iruong uu'oc \l\ phan ihm hidral hoa cua chiing dicn t!ii'(yc lien Dong thoi iiiroc lAii cong len be mat cua cac hat khoang va phan ihig cua hidral cung xay tren be mat cac hat khoang Sau niitV Iham tian \ a o cac hat xi mang h'vn, c|ii;i liui i thiiy ho;i \An ticp line dicn Tlurc Ic cho Ihay tham chi sau nam \ a n 15'r C,S chna iham LLKI ^ v - ^ ã ã>>-ã.ãV?ô'>;^:ằằ3ÊJMaK^.ii-; IV! A S T E R S I Z E R ^•vy/Wi Result: Histogram Report Sample Details Run Number: Record Number, 70 D: Mau cement4 -ile: MINH 'ath: C:\SIZERMP\DATA\ ^iotes: Khoa Hoa Measured: Wed Feb 16 2000 11 06AM Analysed: Wed Feb 16 2000 11.06AM Result Source: Analysed System Details Internal ition:5PID Model; Polydisperse lions: None on Type; Volume ameters: = 63.25 um ) 50 55 60 56 73 80 87 96 05 16 27 39 53 68 84 02 22 44 67 94 22 54 88 26 68 13 Volume ln% 0.01 001 0.03 0,04 0.05 0.07 0.10 0.12 0.15 0.19 0.22 0.26 0.29 0.32 0.35 0.37 0.39 0.39 0.38 0.36 0.34 0.31 0.27 0.24 0.21 Measured Beam Obscuration: 25.2 % [Particle R.I, = ( 5960, 3000); Dispersant R I = 1,3300] Residual: Result Statistics Concentration = 0.0230 %Vol Density = 3.000 g/cub cm D (V, 0.1) = 4.72 um D (v, 0.5) = 35 13 um D [3, 2) = 2.91 um Span = 4,783E+00 Size (um) 0.513 0.564 0619 0.679 0.745 0,818 0.898 0,985 1,08 1.19 1.30 1.43 1.57 1.72 1.89 2.08 2.28 2.50 2.75 3.01 3,31 363 3.99 4,38 480 5.27 Volume In% 0,18 0.15 0.12 0.11 0.10 0.11 0,11 0,11 0.12 0.12 013 0.14 0.14 0.15 0.16 0.18 0.19 0.21 0.24 0.27 031 0,36 0,41 0.48 0.55 Size (um) 527 5.79 35 6,97 7.65 8,40 22 10.12 11.11 12,19 13 38 14.69 16 12 17,70 19.42 21.32 2340 25 69 28 19 30.95 3397 37 29 40 93 44 92 49 31 5412 Volume ln% 0.63 0,72 0.83 094 1.07 1.21 1.36 1.51 1.67 1.84 2.01 2.18 234 250 2,64 2.77 2.88 2.98 3.05 3.09 3.11 3.11 3.07 3.00 2,90 2.717% Specific S.A = 6870 sq m / g D(v 0.9)= 172.72 um Uniformity = 1.363E+00 Size (um) 54.12 59 41 65 21 71.57 78 56 86 23 94 65 103.9 1140 125 137 150.8 165 181 199 2189 240 263.7 289,5 317.8 348.8 3828 4202 461.2 506.3 555.7 Volume ln% 78 2.63 2.47 31 15 2.02 1,91 83 1.78 76 1.75 75 1.74 1.70 1.62 1,48 1,28 1.05 0.82 0.60 0.39 0.11 0,00 0.00 00 Mau cement4 Volume (%) 100 ^80 60 ^40 "20 10.0 Particle Diameter (pm) Its Ltd 4-892456 Fax +(44) (0)1684-892789 Mastersizer Microplus Ver 17 Serial Number 3385U-57 100.0 "O 1000.0 p 16 Feb 00 11 C Thermal Analysis Data DTA uV 40.00 20.00 0.00 9r».00C 755.04C 133.17C •20.00 -40.00 J 1 500.00 Teinp[C] 0.00 File N a m e : Detector Type: Sample Name: Weight: Cell: Atmosphere; C o m m ( 3nt: 1000.00 81 18M0 D60 Shimadzu DTA-50 MO 24.90[mg] Alumina Air Dinh X u a n Loc Temp Program Rate H o l d Teri-ip H o l d T i m e [C/min] [C] [min] 10.0 1000.0 0O SHIMADZU CORPORATION INSTITUF O F CHEMIS IRY Tel 4 ^1 iivv} I rhermal Analysis Data 40.00 20.00 •20.00 •40.00 500.00 Teni|)[C] 0.00 Ile N a m e : )etector T y p e : lample Name: Veight: :ell: trnosphere: Comment: 1000.00 B118M1.D60 Shimadzu DTA-50 Ml 27.20[mg] Alumina Air Dinh X u a n Loc femp Program ^ate Hold T e m p C/min] [C] 10.0 1000.0 Hold Time [min] 0 SHIMADZU CORPORATION INSTITUE OF ChfEMISTRY Tel 564 Qy iO d rhermal Analysis Data 40.00 20.00 •20.00 •40.00 500.00 Tein|)[C] 0.00 File N a m e : Detector Type; Sample Name: Weight: Cell: Atmosphere: Comment: 1000.00 B119M2 D60 Shimadzu DTA-50 M2 29 20[mg] Alumina Air Dinh X u a n Loc Temp Program Rate Hold T e m p Hold Time [C/min] [C] [min] 100 1000.0 0.0 SHIMADZU CORPORATION INSTITUE O F CHEMISTRY Tel 564 nl rhermal Analysis Data Di-IGA nig/mill TGA % -0.00 100.00 -0.10 0.20 704.39C 50.00 -0.30 0.40 0.00 File N a m e ; Detector Type: Sample Name Weight: Cell: Atmosphere: Comment 1000.00 500.00 Tcinp[C] 0.00 C118M0.D20 Shimadzu TGA-50H MO 13,74[mg] Alumina Air Dinh X u a n Loc Temp Program Rate Hold Temp Hold Time [C/min] [C] [min] 10.0 1000.0 0.0 ShllMADZU C O R P O R A T I O N INSTITUE OF CHEMISTRY Tel 564 ^ h iCi^ rhermal Analysis Data DrTGA ing/min TGA % -0.00 667.82C 116.76C 0.10 100.00 29.62C -5.481% -0,624n»y 690.76C 0.20 0.30 50.00 0.40 h0.50 0.00 500.00 TeinplC] 0.00 File N a m e : Detector Type: Sample Name Weight: Cell; Atriiosphere: Comment: 1000.00 C120M1.D60 Shimadzu TGA-50H M1 11 [ m g ] Alumina Air Dinh X u a n Loc - V K H V L Temp Program Rate Hold Temp Hold Time [C/min] [C] [mm] 10.0 1000.0 0.0 SHIMADZU CORPORATION INSTITUE OF CHEMISTRY Tel 564 ') < K hernial Analysis Data OiTGA nig/inin TGA % 110.00 0.00 105.00 639.3(iC 120.ri6C 100.00 rO.lO 0.3l8mô -2.957% 665.000 95.00 0.20 ãile N a m e ; )etector Type: Sample N a m e Veight: :ell: atmosphere: Comment; 1000.00 500.00 Temp[C] 0.00 C I 19M2.D60 Shimadzu TGA-50H M2 10.77[mg] Alumina Air Dinh X u a n L o c Temp Program Rate Hold T e m p Hold Time [C/min] [C] [min] 10.0 1000 0.0 SHIMADZU CORPORATION INSTITUE OF CHEMISTRY Tel 4 G,^"^ \ o o o OJ eg o in OJ Ol o CO 0 •• lO CO o ID in in o in LO o in -^ • ro ^ O CO in CN O CN —5 QJ 1QJ ••—• cn U ( D c z i o £ - ^ — rocuo) OJ CO (/) c fT3 lut ion ^ c t/i CD (/) DC o o in • ^ — E numbers (c o o OJ o CD > o o IX) C\i 03 L- CQ :^ ^ O O) o o o CO o o m CO o o o CN o CN CO CO CN O 00 o o o ' • c —i 0) OJ CO h- tn 0) •-< en U ^1— L - r o c t o E " ' ^ ' ^ " ' ^ ^ * ^ Tf tn c tn o (/) lut ion o o o o