Βιομηχανική Ανόργανη Χημεία

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ΑΡΙΣΤΟΤΕΛΕΙΟ ΠΑΝΕΠΙΣΤΗΜΙΟ ΘΕΣΣΑΛΟΝΙΚΗΣ ΠΟΛΥΤΕΧΝΙΚΗ ΣΧΟΛΗ ΤΜΗΜΑ ΧΗΜΙΚΩΝ ΜΗΧΑΝΙΚΩΝ ΤΟΜΕΑΣ ΧΗΜΕΙΑΣ ΣΠΥΡΙΔΩΝ ΧΑΤΖΗΣΠΥΡΟΥ ΚΩΝΣΤΑΝΤΙΝΟΣ ΣΙΚΑΛΙΔΗΣ ΕΠΙΚΟΥΡΟΣ ΚΑΘΗΓΗΤΗΣ ΑΝΑΠΛΗΡΩΤΗΣ ΚΑΘΗΓΗΤΗΣ ΒΙΟΜΗΧΑΝΙΚΗ ΑΝΟΡΓΑΝΗ ΧΗΜΕΙΑ ΣΗΜΕΙΩΣΕΙΣ ΘΕΣΣΑΛΟΝΙΚΗ 2005

Transcript of Βιομηχανική Ανόργανη Χημεία

  • 2005

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    1. 4 1.1. 4 1.1.1. 6 1.1.2. 6 1.1.3. CO CO2 6 1.1.4.

    1.1.5. 8 7

    1.2. H 9 1.3. 2 11 1.4. PSA 12 1.5. 12 2. 14 2.1. ( ) 14 2.2. 15 2.3. 15 2.4. 16 2.5. ( ) 17 2.6. 3 18 3. 19 3.1. 19 3.2. 19 3.3. 20 3.4. 21 3.4.1. 2SO4 21 3.4.2. 22 3.5. 3 23 4. 24 4.1. SO2 24 4.2. SO2 25 4.2.1. 26 4.2.2. 26 4.3. H2SO4 27 4.4. H2SO4 28

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    5. 30 5.1. 30 5.1.1. 31 5.2. 32 5.3. H3PO4 34 6. 35 6.1. 35 6.1.1. 35 6.1.2. 40 6.1.3. 41 6.2. 41 6.3. 42 6.3.1. 42 6.3.2. 43 6.3.3. 44 6.3.4. 45 7. 46 7.1. Portland 46 7.2. Portland 47 7.2.1. 49 7.2.2. 50 7.3. 51 8. 52 8.1. 52 8.2. 52 8.3. 52 8.4. 53 9. 56 9.1. 56 9.2. 57 9.3. 57 9.3.1. 59 9.3.2. 59 61 62

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    1.

    , ( ) (fuel cells). , . , , , , .

    :

    (reforming)

    ()

    CO,

    , CO2 2 (gas shift reaction).

    , / CO , . , : CH4 + H2 CO + 3H2 206 KJ (1) ,

    adminTypewritten TextO

    adminTypewritten Text

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    moles (n>0) :

    /

    , . .., .

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    1.1.1 , ( ) MgO Al2O3, CaO, BaO, SiO2. To NiO, . (.. MgO+Al2O3), 20% . , , , . () , . , , (2S ) . 1.1.2. , , :

    CH4 C + 2H2 (3) 2CO C + CO2 (4) CO + H2 C + H2O (5)

    , , 10 . : / 2.

    1.1.3. CO CO2 CO CO2, (gas shift reaction). , . CO + H2O(g) CO2 + H2 + 41 KJ (6)

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    : 4 CO + Fe3O4 3 Fe + 4 CO2 () (6.1) 3 Fe + 4 H2O Fe3O4 + 4 H2 () (6.2) 350-4500C Fe2O3 : Cr2O3 = 9 : 1. , Zn, Cu, Co .. CO , . 100-300 atm 0-200C. CO 70-800C 1 atm. . CO2 . - - (MEA, DEA, TEA), (CO2, SO2, H2S .). (15-35%) 40-450C CO2 : 2 NH2-CH2-CH2-OH + CO2 + H2O (OH-CH2-CH2-NH3)2CO3 (7) CO2 1000C. 1.1.4. CO CO2 , 250 C (6820 Kcal/mole) 6000C (1675 Kcal/mole) (6) , . (< 4000 C) , , 0. . (1 = 4200C) ( 1 , ,

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    . , . , , , . (. ) (CO+H2O) 1, . 1 . 1.1.5.

    , , 4000C, . , , (= Zn, Fe, Ni), :

    MO + H2S MS + H2O (8)

    H , . MS , (), MO () :

    MS + 3/2 O2 MO + SO2 (9)

    , / =2,5/1 ( ). 7000C 70%. , , , 10000C. , , ( .) 2: 2 1:3. , 800-8500C 4000C . CO CO2, 1.1.3.

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    CO, , 70% 2+2, CO2 (~25-27%) , CO, H2S, O2. , 1800C, . , CO, CO2 1.1.3, H2S , , .

    1.2. H H , .. . NaOH KOH (15%). , . 1,30 V 2-2,5 V . 0,3 m3/ kWh. , . (GaInP2, GaNP .) : (i) ( / ) 1,6-1,7 eV (ii) (iii) . (10-12%). , p- n- . , .

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    1.3. 2 .

    ( ) (Steam Reformer). ( 2+CO2) PSA(Pressure Swing Adsorption) 2 , 75% (3) . 25% (1), , 2, , , 3. 3 (char) .

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    1.4. PSA

    , ( 2+CO2) 3 . () , ( ) CO2, CO CH4 () 2 2 99,99%. 1.5 (fuel cells) , , , , ., , CO ( ) . , , . .

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    , , .. PSA .

    1/27/2006 A.J. Jacobson CMC-UH 23

    Water Gas Shift Reactor

    Fuel Cells

    Hydrogen Production

    CO2Sequestration

    HydrogenSeparation

    Device(PSA, HTM)

    CO2 +H2CO2

    H2CO +H2

    Membrane reactor

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    2.

    . , ( , ) . , , , , .. .

    :

    2 +3 2 23 + 13 Kcal/mole moles (n

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    2.2. , , , 100 1000 atm. 300 atm, , , . , :

    ( )

    .. , , . , , . , , 2/ 2 . 2.3. , . , . . 500-5500 C. , 4000 C (Mont Genis) 6500C(Claude). , . , / .

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    2/2 () . 2.4. , , Fe3O4. , . Al2O3, Al2O3, K2O Al2O3, K2O, CaO MgO. , . , 2/2. 4-10 . , - . - , . , 10-50 . , . 2-5 . , 5300 C , . () . , . , . - . , , , , . ,

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    , . , , ( ). , , , 2/2 . , , . 2.5. ( ) , -- . 15-20 m 1-1,5 m (). , . . ICI (.), 32 +2 , , . , 4000 C. , , , , , , . , . , ... 3 , ( 32 +2). . 500-1500 /. 15 atm. (ICI) . (Fauser-Montecatini, Kellog, Casale, Claude)

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    (, , ) . . ICI

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    KELLOG

    Kellog, . , , (. ). 4 , 32 +2.. , , , .

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    HALDOR-TOPSOE

    Haldor-Topsoe, . ICI, , . , :

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    2.6. 3

    ( ) , . , , CO. CO2 MDEA(--) . ( ) 3( ) CH4 .

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    3.

    , , , . ( ) , ( Ostwald) .

    (Ostwald). , 2, 3 60-70%.. : 2NH3 + 5/2 O2 2NO + 3 H2O Q=907 KJ/mole (1) 2 + 2 22 Q= 112 KJ/mole (2) 3NO2 + H2O 2HNO3 + NO Q= 136 KJ/mole (3) To NO (3) (2). 3.1. / 15,5-27,5% 3 .. , 11,5% .. . , , . 3.2.

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    10% . , , . ( Pt+10% Rh) () 1000 / cm2. , . , . , 0,04-0,6 gr/tn . , 30%, . 1,5 . (50%) , CaO, (80%). , . 3.3. , 8-10 atm. , () - . -, 11,5%.. . , , 8-10 atm, 110-1200 C. (+) 800-9000C, 900-10000C. , , (15 atm), 2500 C - 300 C. 3 55-60%. 2( ) .

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    ~90% 50-55% .. 3. , , (2) 2 Na2CO3 Ca(OH)2. NO . , 3(60%) (50%), 0,15% . , , , , . , , , . 3.4 . 3 60%.., . , (, , ) 96% . 3 , / 68,5%.. , 3 :

    2SO4

    3.4.1. 2SO4 (50-60%) ,

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    2SO4(70-80%) . 3 +2 (68,5% 3) . , 3 (96-98%). , , , . 2SO4 (70-75%) . 3.4.2. 2 , 24 : 22 24 Q= 57 KJ/mole (4) To 50atm = 750C : 224 + 2 + 22 43 Q= 59,5 KJ/mole (5) , 24. 3 98-99% 24 .

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    3.5. 3

    , 3. 3() 3- , . (boilers) , , 2. 3 . 3, ( )

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    4. . , , , , , , ... , , . (50%) , 1/10 , .. , 2SO4 :

    , SO2, . SO2 SO3. SO3 .

    4.1. SO2 () , 2S, , . . 1130C 4440C. SO2 : S + O2 SO2 Q= 296 KJ/mole (1)

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    H , . , ( +). , . , 8-12% SO2 10000C. - - - SO2, . , 2SO4. 4.2. SO2 H : SO2 + 1/2 O2 SO3 Q= 96,7 KJ/mole (2) , . , 4500C , . , . , , . , , , , 80% .. 2 , - V2O5. SO2/O2 , , .

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    . - ( V5+ V4+). 4.2.1. SO2 , V2O5. . , , , K2SO4. V2O5. H 400-6000C. 6000C, , , . 4000C , , V4+, . , , . 4.2.2. SO2 5-10 m 15-20 m. O 4-5 (.. ) . , ( - ) . ( 9% SO2 + 11-12% 2) 400-4500C , (2) 6000C . , 50-600C, , , ...

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    , SO3. .. 5-100C 75%, ~2%. SO2 SO3 99,8%, SO2 , , . 4.3. H2SO4 , SO3

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    4.4. H2SO4

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    ( ) . SO2 , (boiler) , , . SO3 , boiler, H2SO4. , 4 . , . H2SO4 .

    5. , - (75%) - . , ( ), , , .. : () , , Ca5F(PO4)3 , . () , , () , SiO2 , P4. , P2O5 , H3PO4. 5.1. H2SO4, HNO3, HCl,

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    , , . , ,CaSO4.x H2O( x=0, 0,5, 2) , . , , . : Ca5F(PO4)3 + 5 H2SO4 5CaSO4 + 3 H3PO4 + HF (1) , : SiO2 + 4HF SiF4 + 2H2O (2) SiO2 + 6HF H2SiF6 + 2H2O (3) Fe2O3.Al2O3 + 4H3PO4 2(FePO4.AlPO4) + 6 H2O (4) Ca3(PO4)2 + H3PO4 +6H2O 3CaHPO4 . 2H2O (5) (4) (5) , % P2O5. (4), , . , , P2O5 30%. . HF SiF4 (1) (2) , H2SiF6, (3), . H2SiF6, . , CaSO4.xH2O, , H3PO4, () . , . , ( +) , . H3PO4 , .

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    H3PO4, . 5.1.1.

    , , , . CO2, , , .

    x (CaSO4.x H2O), .

    . , CaSO4.0,5 H2O .

    5.2. , () (SiO2) , : 4Ca5F(PO4)3 + 18 SiO2 + 30 C 18CaSiO3 +2 CaF2 + 30 CO + 3 P4 (1) , , P2O5. . P4 + 5 O2 2 P2O5 (2) P2O5 + 3H2O 2 H3PO4 (3) , : 4Fe + P4 4FeP 8 Fe + P4 4 Fe2P (4) 2CaF2 + 3 SiO2 2 CaSiO3 + SiF4 (5)

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    P4 + 6 H2O 2 P2O3 + 6 H2 (6) 2P2O3 + 6 H2O 4 H3PO3 3 H3PO4 + PH3 (7) ( ) , . , , . SiO2/CaO 0,8-1,2 , P2O5/C 2,3-2,6. , . 2-3 . , (1). CaSiO3 (.5) . , ( FeP, Fe2P, .4) . (2, .6 PH3 ,.7 ) . (40-60 KV, =250-3000C) , 20% P4 15% 2 . , , . , . , P2O5 54% 63,7% P2O5 100% H3PO4. , . , , . , , P2O5 H3PO4. , P2O5 , . , ,

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    , P2O5/2. P2O5 . , ( ) , 600 KW/ P4 . . 5.3. H3PO4

    , . , , - . , (), CaSO4, ( 26-32% P2O5). H3PO4 .

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    6. , . N, P, . , Ca , Mg S , Fe, Zn, Mn, Cu, Mo . - , , , . , , . , () , , . , - . . 6.1. 6.1.1 , , . , (, P2O5, K2O) . , ( ) . .

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    80 90 , , , , , ( ), , ( ) .. , .

    , (.. -, - -), (.. -) (.. -,

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    --). . -, PO43-, . . (a) (Na2 HP3O9)n

    (b) [ Na3H(PO3)4]n

    (c) (NaPO3)n

    (d) (KPO3)n

    (e) [ Ca2 (PO4)3]n

    (f) [ (NH4) Cu (PO3)3]n

    (g) [ Na Mn (PO3)3]n

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    : 1. : 2P2O5+2H2O (HPO3)4 +H2OH6P4O13 (1) H6P4O13 + H2O H5P3O10 + H3PO4 (2) H5P3O10 + H2O H4P2O7 + H3PO4 (3) 2. - : 23PO4 H2O H4P2O7 - H2O Hn+2PnO3n+1 -H2O (HPO3)n (4) , , . , , , pH, , . (.. 2 3). , , , , , , , . , . P2O5, ( P2O5+N, P2O5+ K).

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    6.1.2. , - - : 2 Ca5F(PO4)3 + 7H2SO4 3 Ca(H2PO4)2 +7 CaSO4 +2HF (1) 2 Ca5(OH)(PO4)3 +7H2SO4 3 Ca(H2PO4)2 + 7 CaSO4 + 2H2O (2) Ca3(PO4)2 + 2 H2SO4 Ca(H2PO4)2 +2CaSO4 (3) , , , , CaSO4. , . , , , . , (7-25 , ) 15-20% P2O5, , . , , , . , . , , , , , , , , . Ca(Mg)CO3 + H2SO4 Ca(Mg)SO4 +CO2 + H2O (4) Fe2(Al)2O3 + 2H3PO4 2Fe(Al)PO4 +3H2O (5)

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    6.1.3. , , P2O5 : Ca5F(PO4)3 + 7 H3PO4 +5H2O 5 Ca(H2PO4)2 .H2O + HF (1) CaCO3 + 2H3PO4 Ca(H2PO4)2 .H2O + CO2 (2) , , , . , , , 40-50% P2O5. , , , . . 6.2. , ,( P-N) , , : Ca(H2PO4)2 + NH3 CaHPO4 + NH4H2PO4 (1) . , , , , CaHPO4. 3PO4 + 2 NH3 (NH4)2HPO4 (2) (NH4)2HPO4 + CaSO4 CaHPO4 + (NH4)2SO4 (3) Ca(H2PO4)2.H2O +CaSO4 +2NH3 2 CaHPO4 + (NH4)2SO4 (4) ( : NH3/ P2O5). , , Ca3(PO4)2, .

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    6.3. 6.3.1. , (NH4)2SO4, 21% : H2SO4 + 2NH3 (NH4)2SO4 Q= 67 Kcal/mole (1) , , ( ), . . , . , , , : NH3(g) +H2O NH4OH(aq) (2) 2 NH4OH + CO2 (NH4)2CO3 + H2O (3) CaSO4.2H2O +(NH4)2CO3 (NH4)2SO4 + CaCO3 +2H2O (4) , pH . , , CaCO3.

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    6.3.2. , 43, , : 3 + 3 43 Q= 35 Kcal/mole (1) : (35%) . : 43 2 (2) + 22 + 1/2 2 (2) 0 = 300-5000 C. (1) . , . (1) (1-3) 88-98%. , . , , , () , . , , 60% . - NH4NO3. , , 0< 300 C - .

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    6.3.3. (), NH2CONH2, (46%). , . , , . , : 1. (NH2COONH4) : 2NH3 + CO2 NH2COONH4 Q= 38Kcal/mole (1) H () , (150-300 atm) 0= 2000C. , . 2. 0 = 1200 C : Q= 6,8 Kcal/mole NH2COONH4 NH2CONH2 + H2O (2) (2) . (1) , : (3, CO2, H2O(g)) (NH2CONH2, NH2COONH4, CO32-, NH4+). , (, ). 80%. , - , 98% , (), . , , .

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    6.3.4.

    / 2+CO2 CO2.. ( CO CH4 ) , 2 2 , NH3. H NH3 CO2 3. ( ) , -.

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    7. . , Portland, , .. 7.1. Portland , CaO, Al2O3, , SiO2. Portland. Portland ( ) : -, 2CaO.SiO2 (C2S) -, 3CaO.SiO2 (C3S) -, 3CaO.Al2O3 (C3A) -, 4CaO.Al2O3.Fe2O3 (C4AF) , CaO MgO.

    , .

    , CaO , CaO, C3S.

    Portland , 0,8-0,95. : O , S..= %SiO2 / %Al2O3 + %Fe2O3 , , , .. = % Al2O3 / % Fe2O3 ( ) .

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    7.2. Portland Portland : / -

    ()- clinker clinker clinker- - ( 85% CaCO3) , ( , SiO2 Al2O3), (Fe2O3), . , : (35-40% ), . . - clinker. (rotary kiln) 200 m 50 m , . 2-5m 0,5-3 /min. H 1450-16000C , 1-3 . : 1000C (

    ) 5000C 9000 C 1350-15000 C

    , ,

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    . , (clinker)

    , .

    clinker. , clinker 0 10000 C. , clinker, 1500 C. ( ) . clinker--. clinker . ( 2-6% . ) (, , ). , .

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    7.2.1. (+ +, Fe2O3 ..) ( ) 1450 - 1600 ( = 3 6 cm ) (100 , 500 , + 900 , 1350 1600 oC ) ( + 2-6% ) -

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    7.2.2.

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    7.3. , ( ). . - , . : 2(3CaO.SiO2) + 6H2O 3CaO.2SiO2.3H2O + 3Ca(OH)2 (1) 3CaO.Al2O3 + 12 H2O 3CaO.Al2O3.12H2O (2) , ., Ca(OH)2 (1) CaSO4 , C3A () (-- ). (.. ).

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    8.

    ( ) , , . , . . , . 8.1. , (SiO2), (Na2SiO3), (K2CO3), (CaCO3), o (BaSO4), (Na2B4O7.10H2O), ( , NaAlSi3O8, ), , Na2SO4, Pb3O4, H3BO3 .. 8.2. , . Cu2O (), Co2O3 (), Cr2O3 () , . , .. MnO2 . , , . NaNO3, As2O3, NH4Cl. 8.3. Ca, Na, K, Si, B, Pb , , . :

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    . SiO2 , (UV) . , , .. , . . (Pyrex) 80% SiO2 20% B2O3. . . . , , . , , , - , . 8.4. : - ()

    . , ( , , ...) . , . , , . . , 1300-15000C ( ). 600-7000C , Na2CO3, (SiO2), . .

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    -. , , . 0>14000C, , . , . , . . , 0= 1100-12000 C, . , ( ). (). , , . , , , . , , . , .

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    ( ).

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    9.

    , .

    :

    1. (- ) 2. 3.

    () . ( , , .) ( ), Al2O3.2SiO2.2H2O : CO2+2H2O K2O.Al2O3.6SiO2 Al2O3. 2SiO2.2H2O +4SiO2 + K2CO3

    , ( ) (SiO2) , Na2CO3. , (softening temperature) .

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    9.2. : o o ( ) o o ( ,

    , ,

    o [ (.. ), (.. ), (.. ), / (.. , )

    o o () o o

    , , 950 C, , 3Al2O3.2SiO2. . . 9.3. . , . . ().

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    , .

    9.3.1. : (). ( -- ). - . () , 850 10000 C. . 1600-18000C. , . 0= 17000 C . . SiO2 . , MgO, ( 28000 C). (). . . (.. ) . , . .. , , , (glaze slip) . (glost product). 9.3.2. : (). (.. ). , , . 13000 C , . (). . 50% , 25% 25% , 1400-15000 C

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    (.. ). 25% , 45% 30% , 1200-13000C, . , . , (translucency) .

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    A., , , , , 1998 Axelord L., Technology of Ammonia Plants in Catalysis Reviews, Vol.23, 1983 Boynton R.S., Chemistry and Technology of Lime and Limestone Wiley Interscience, 1966 , , , , 1982 Gates B.C., Katzer J.R., Schuit G.C.A., Chemistry of Catalytic Processess Mc Graw Hill, 1979 Henglein F.H., Chemical Technology, Pergamon Press, 1969 Kent J.A.(Ed.), Riegel Handbook of Industrial Chemistry, Van Nostrand Reinhold, 1974 Kingery, W.D., Bowen, H.K. & D.R. Uhlmann,, Introduction to Ceramics, John Willey & Sons, N.Y., 1976. , , , ..., , 1962. .., , , 1972 .., .., , 1985 , ., , , ..., , 1998. .., , - , , 1979 Singer F and Singer S, Industrial Ceramics, Chapman and Hall, London, 1978 Shreve R.N., Brink J.A., Chemical Process Industries, Mc Graw Hill, 1977 Thomas J.M., Thomas W.I., Introduction to the Principles of Heterogeneous Catalysis. Academic Press, 1975 .

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    www.appliedchemical.com scifun.chem.wisc.edu/chemweek/chemweek.html www.psigate.ac.uk/newsite/reference/plambeck/chem1/po1261.htm science.uniserve.edu.au/school/curric/stage6/chem./indchem.html www.hw.ac.uk/cheWWW/research/ geg.chem.usu.ru/commun/chemlib2.htm www.ects.u-3mrs.fr/DOOLDQGB.htm www.wpbschoolhouse.btinternet.co.uk/page01/ExIndChem/ExIndChem.htm www.tuiasi.ro/pages/TU197/ch97.htm bioinfo.weizmann.ac.il :3456/bioscience/urlists/chemist.htm www.enviro-chem.com/plant-tech/default.html www.chemsoc.org/networks/learnnet/key-subjects.htm home/nas.net/~dbc/cic~hamilton/ind.html