Glass Fining

Chemical & Physical Processes in Glass Melting Quality of glass melting process
Buchmayer
Ruud Beerkens TNO Glass Group Eindhoven, The Netherlands

Glass Service
ICG EFONGA Spring School Montpellier 4-5 May 2009
Contents
Overview of processes essential for glass melting Tools of analysis of industrial glass melting Melting-in of Raw materials Kinetics of Sand Dissolution Removal of Gas bubbles & Dissolved gases Evaporation processes Homogenisation
refractory corrosion evaporation: NaOH, KOH, NOx and HBO2, heat transfer water infiltration PbO, NaCl, HF, SO2 etc. melting kinetics foaming fining and redox refractory corrosion
flue gas chemistry
deposition and dust formation
1. Overview Chemistry & Physics of Glass Melting Processes
emissions: Na2SO4, Na2B4O7 and PbO dust HCl, HF, SO2, SO3 , SeO2, HBO2, H3BO3 etc.
4
Side-effects Evaporation from melt Refractory corrosion Combustion & heating Emissions from evaporation & combustion Furnace Raw materials mixed Or Crucible Melting-in of batch chemical reactions/endothermic effects Sand* grain dissolution Removal of bubbles/gases Dissolution of seed (fine bubbles) residue Homogenisation - Diffusion (slow) - Velocity gradients stretching of inhomogeneities
ICG EFONGA Spring School Montpellier 4-5 May 2009 5
Homogeneous molten glass
Parameters for processes in melting

Important parameters:
Heat transfer
viscosity, surface tension, chemical activity, reaction kinetics, gas evolution..
Temperature
Flow characteristics convection in melt, stirring Residence time: time-temperature history Exposure of melt to (reactive) atmosphere and refractory lining
How to assess: Temperatures and flows in glass melt ?

2. Tools: CFD Simulation Models Glass Furnaces

Discretize total volume of furnace in small volume cells (> 1 million) cells LxBxH: (1-10) x (1-10) x (1-10) cm
GRID / mesh
Input data process: pull, batch composition, fuel distribution, air number Input furnace:
Design Wall construction, including insulation
Input glass: viscosity, heat conductivity, density, thermal expansion, electric conductivity, solubility sand, solubility gases, For each volume cell in tank & combustion chamber
Energy conservation Momentum conservation Mass conservation (continuity) for melt and each chemical element Respect electro-neutrality
CFD Simulation Models example: local conservation of energy

( c pT t
) = div ( c T v ) + div ( r
p
grad T ) + q
increase sensible heat
convection of heat
heat conduction
local boosting or cooling
Energy equation, conservation law for energy in each volume element

Results of CFD simulation models

Temperatures at all possible positions
Combustion space Glass melt Refractory
Glass melt and Combustion gas velocities Trajectories (particle tracing) in tank
Thousands of different paths can be identified from charging end to throat or spout
Redox and dissolved gases

Redox state of melt at each position (pO2 or Fe2+/Fe3+)
Residence time distribution

Minimum residence time is of importance for melting process
Glass melt quality indices per trajectory

Trajectory with minimum melting or fining index is decisive for glass
Application of CFD models

For furnace design (lowest energy, highest glass quality)
Optimum depth of tank Position bubblers or dam or burners Size and design of throat Design combustion chamber (LowNOx, less evaporation) Optimum fuel-boosting ratio Temperature profile (energy distribution) Bubbling rate Creation of distinct spring zone to avoid short cut
For optimum process settings
Time-transient (time dependent) for colour or pull change

Optimize colour change process: reduce transition time
Time-transient for process control (rMPC)

Sensors give model continuous new information: model tracking Model continuously gives recommendation for input parameter changes to follow optimum process path (low energy, high glass quality, constant T)
Geometry & Grid for computational fluid dynamics (CFD) analysis of glass furnace
Port Necks
crown
Burner port
tank
Deep Refiner
Batch Boosting electrodes

Example result CFD computation
Temperature contours
12
NOx
End-port fired furnace horizontal cross section at level of burners
Base case
4 inch higher crown
13
NOx
End-port fired furnace vertical cross section at 25 % from furnace length from port
NOx scaling in mole fraction
Base case
4 inch higher crown Burner port Exit port (flue gas) Lower NOx-concentration in exit
Glass melt path with lowest temperature index

Temperatur indexpath i e T = dt doghouse
canal
Temperature course of glass (melt) in typical float glass furnace with minium temperature index
1800 1600 1400 Temperature in oC 1200 1000 800 600 400 200 0 0 2 4 6 8 10 12 14 Time in hours
15
Sensors (short overview)

Combustion gases gas composition:
laser optics electrochemical sensors (oxygen)
Glass melt chemical composition LIBS = laser induced breakdown spectroscopy emf redox / colour parameters t/c
Potentiometry Voltammetry
Type B (mV) (mV)
Alumina rod
Pt / Ni-NiO // ZrO2 // pO2 (glass) / Pt

EMF = RT pO 2 (glass) ln nF pO 2 (ref.Ni/NiO)
Pt measuring electrode
Zirconia cell
Ni/NiOreference mix
16
3. Melting-in of batch
In glass furnaces (industrial)
Kinetics determined by heat transfer through batch blanket
In small crucibles:
Kinetics determined by contact between different batch constituents and temperature
17
Return flow for batch heating Day hopper
Generation blisters from refractory Refining Bubble absorption Conditioning of melt Thermal homogeneity
Hot spot & evaporation
Zone for sand grain dissolution Batch melting 40-60 minutes 80-90 % of net heat flux Return flow from working end
Spring zone & primary fining
18
Scheme of melting process of batch blanket, charging velocity vg (m/s)

combustion space heat transfer gas release
thickness
temperature profile
reaction zone figure 1b glass melt layer
normal batch
reaction zone
Zipfel
glass level
glassmelt flow
heat transferred
figure 1c
19
Detailed re-presentation of the batch melting process in glass furnace

1500
o
Layer glassmelt Dissolution sand grains
melts loose batch
sand grains gas
melting reactions batch
carbonates (soda/lime) gas sand grains
melting reactions dissolution sand grains
glass melt 1400 c.
b. top of batch blanket
bottom side of batch blanket

20
Example: Melting reactions of soda lime (dolomite) silica batch

De-hydratation (100 oC physical bonded water & > 100 oC hydrates)
Important for energy consumption: water evaporation is energy intensive
Solid state reactions, formation of silicates, e.g.: Carbonate route < 900 oC at fast heating rate
Na2CO3 + CaCO3 Na2Ca(CO3)2 +2SiO2 Na2CO3 + 2SiO2 Na2Ca(CO3)2 (melts at 820 oC)
High amount of heat required (550-850 oC)
Na2SiO3/CaSiO3 + 2CO2 reaction enhances > 820 oC Na2SiO3 + CO2 (790-850 oC)
Formation of primary melt phases (alkali rich carbonates), e.g.:

Tm Na2CO3 Tm Na2Ca(CO3)2 Tm K2CO3 = 850 oC = 820 oC = 890 oC
21
Melting reactions of soda lime silica batch

limited kinetics may shift some reactions to higher temperatures Decomposition reactions of (Ca- and Mg-) carbonates: heat required
CaCO3 + heat MgCO3 + heat MgCO3CaCO3 + heat CaO + CO2 MgO + CO2 MgO + CaCO3 + CO2 (910 oC at pressure 1 bar) (540 oC at pressure of 1 bar) (650 oC, 1 bar)
MgO still present up to 1150 oC.
Dissolution reactions of SiO2, e.g. (coarse limestone)

Na2O2SiO2 + CO2 T > 790 oC forms with SiO2 an eutectic melt Or at further heating fast Na2OSiO2 formation (850 oC) limestone decomposes and: 2CaO + (SiO2 + Na2O2SiO2 )eutectic melt Na2O2CaO3SiO2 (> 900 oC) Reactive calcination: Na2CO3 + 2SiO2 Silicate route: Silicate melt + SiO2 silica enriched melt T > 1000-1100 oC Eutectic melt phases are formed above 800-840 oC
Phase diagram for the system Na2O SiO2 showing eutectic sodium silicate melt phases
100 % SiO2
Scheme of melting reactions of soda lime glass batch

1080 oC: T s Na2SiO 3 910 oC : CaCO 3 CaO + CO 2 (gas) o 850 C : T s Na2CO 3 820 oC : T s Na2Ca(CO 3)2 790 oC : T eut Na 2O.2SiO 2 + SiO 2 740 oC : T eut Na 2Ca(CO 3)2 + Na2CO 3 650 oC : MgCO 3.CaCO 3 MgO+CaCO 3+CO 2 (gas) 540 oC : MgCO 3 -> MgO + CO 2 (gas)
Dissolution of SiO 2, CaO, MgO, Al2O 3 e.d. in melt phases primary melts decomposition carbonates solid state reactions volatilisation of water
200
400
600
800 1000 temperature in oC
1200
1400
24
10 Chemical energy consumption rate [kJkgbatch K ]

-1
Overall chemical energy demand

MgCO3CaCO3(s) -> MgO(s) + CO2(g) + CaCO3(s) CaCO3(s) -> CaO(s) + CO2(g)
-1
Na2CO3(s) + SiO2(q) -> Na2OSiO2(s) + CO2(g) Na2CO3(s) -> Na2CO3(l)
Na2CO3(l) + SiO2(q) -> Na2OSiO2(s) + CO2(g) Na2OSiO2(s) + SiO2(q) -> NS(l) CaO(s) + melt
0 600 -2
650
700
750
800
850
900
950
1000
Temperature [C]
Chemical enthalpy of batch reactions for float glass from soda-sand-dolomite and limestone (positive: endothermic effects)
4. Dissolution of refractory type raw material in silicate melt example: sand grains
26
Sand grain Glass melt
CSiO2 100 Ce (T)
Ce(T) = saturation level SiO2 in melt Cb = bulk SiO2 level in melt (depends on amount dissolved sand)
Cb
Moving boundary Diffusion of SiO2 in melt

One-dimensional dissolution in multi-component liquid

Dissolution front
Mass fraction SiO2 in saturated melt: we Multi-component liquid
Dissolving material
w is mass fraction SiO2 in melt
a dissolution we
w x a
SiO2
w e da x a = D dt (1 VA e w e )
28
Mathematical description
(Ready & Cooper 1966)
Spherical symmetry diffusion in 3 dimensions Assuming constant diffusion coefficient in melt Ideal solution, partial molar volume of SiO2 in melt is constant Convection (term u) due to change of partial molar volume of SiO2 in sand versus in melt Moving boundary: dissolving sand is partly staying in volume it came from
Mass flux (j) of dissolved SiO2
J D r R t C u
= mass flux of SiO2 = diffusion coefficient of SiO2 in silicate melt (m2/s) = radial co-ordinate (distance from sand grain centre) (m) = radius sand grain (m) = time (s) = density of melt (kg/m3) = local SiO2 mass concentration (kg/m3) = mass average velocity radial direction due to expansion by dissolution (change in molar volume) (m/s)
Solution dissolution sand grain without forced convection
Effect of moving boundary
a VA Cs Ca
= = = =
actual grain size radius (m) partial specific volume of SiO2 in molten glass (m3/kg) density of sand grain (kg/m3) mass concentration SiO2 in saturated melt (kg/m3)
30
Sand grain dissolution with convection by glass melt velocity gradients & density differences
SiO2
h we ws VA a t s SiO2 D
da = h (w e e w s s ) /(1 VA w e e ) dt
= mass transfer coefficient SiO2 into melt (m/s) = mass fraction SiO2 in saturated melt (depends on T, and glass) (kg/m3) = mass fraction SiO2 in bulk melt (depends on dissolved sand)) (kg/m3) = partial specific volume of SiO2 in molten glass (m3/kg) = actual radius sand grain (m) = time (s) = density of melt (kg/m3) = density sand grain (kg/m3) = diffusion coefficient of SiO2 in silicate melt (m2/s)
31
Mass transfer coefficient

Sh 1 1 h= D + R 2 Sh D t 2
h = mass transfer coefficient (m/s) diffusion coefficient of SiO2 in the molten glass, based on concentration profiles given in mass fraction (D in m2/s) R = t = Sh = grain radius (m), time (s), Sherwood number for mass transfer from spherical grain, 2 + 0.89 {Re Sc + (Gr Sc)3/4}1/3 * = 2 (no convection) = f (R2/3 , D-1/3, (grad v)1/3) (convection flow of the glass melt) = f (R3/4 , h-1/4 , D-1/4) D =
(free convection of surrounding melt relative to the sand grain: v = flow velocity of the melt relative to the sand grain (m/s), = viscosity (Pa.s)
30000 no convection 25000 Dissoltion time in s 20000 v-gradient 15000 10000 v-gradient 5000 0 1350 0.025 s
-1
0.001 s
-1
1450
1550
1650
1750
1850
T in K Dissolution time required for complete dissolution of sand grains in almost static and stirred soda-lime silica glass melts (forced convection with velocity gradient grad v) at different temperatures. Initial size Ao=100 mm.
Dissolution of sand and alumina grains in static and convective sodalime-silica glass melt at 1700 K, moving boundary effect taken into account (not on concentration profiles)
1.20E-04
1.00E-04
sand, grad v=0
sand, grad v=0.001 s

-1
sand, grad v= 0 steady state sand, -1 grad v=0.01 s alumina, -1 grad v=0.01 s
8.00E-05 radius in m
6.00E-05
4.00E-05
2.00E-05
0.00E+00 0 5000 10000
alumina, -1 grad v=0.001 s sand, steady state -1 grad v=0.001 s 15000 20000 25000
alumina, grad v = 0
30000
35000
time [s]
34
5. Fining Processes
35
Seeds after batch melting Coarse sand
Seeds after batch melting Fine sand
36
10 mm
Glass just after batch melting

- sample thickness 5 mm
to
8 mm
38
Bubbles & Seeds just after melting
Many small seeds and bubbles (Blisters) in glass melt

combustion space
(Mulfinger 1976 GTB)
heat transfer gas release
More than 100.000 per kg glass melt

thickness
temperature profile
reaction zone figure 1b glass melt layer glass level reaction zone
normal batch
Most bubble diameters: 0.05 -0.4 mm

glassmelt flow heat transferred figure 1c
In most glass melts (using carbonates):
bubbles in batch melting area: contain often mainly CO2

Large concentrations dissolved CO2 in melt During sand grain dissolution in melt: generation of fine CO2 seeds (Gispen)
from Glass Service
Fining
Objective of Fining:
Removal of bubbles and dissolved gases from the glass melt Rising velocity of bubble:
v ascension
= = R = g = c = Density of the glass melt [kg/m3] Viscosity of the melt [Pas] Bubble radius [m] Acceleration of gravity [m/s2] Factor (e.g. Stokes c = 2/9)
c g R =
40
Fining
Time to reach glass level at 1 meter [h]
Time to reach glass surface (1 meter)

250 1400 OC 200 1450 OC 150 100 1500 OC 50 0 0 100 200 300 400 500
41
1350 OC
Bubble diameter [m]

III. Fining gases and other dissolved gases diffuse strongly into bubble II. start of fining: gases diffuse into bubble
I. static bubble
Reaction in melt: release of fining gases Pgases melt > pt (pt is pressure in bubble)
Two fining steps
First step: primary fining High temperatures Bubble agglomeration and bubble size growth Dissolved gases diffuse from melt in to bubbles (like bubbles in soda drinks) Ascension to glass melt surface
Second step: Secondary fining/Refining (secondary fining) Dissolution of (small) remaining bubbles Only effective if bubble contains gases (CO2, O2, SO2+O2) that dissolve in cooling melts Glass melt should be lean in dissolved gases
43
Mechanism sulfate primary fining

Fining process in glass melt pSO2 pO21/2 aNa2O
pSO2 pO21/2
K=
K =
aNa2SO4
[SO3]
Increasing temperatures lead to increasing K-values extra oxygen gas & SO2 gas release: - oxygen & SO2 molecules diffuse into growing bubbles - bubble ascension increases (vascension~R2) - sulfate retention decreases
Fining (primary)
Fining agents added to the batch to enhance the rising velocity of bubbles Often used fining agent: Sodium sulphate Fining reaction: T > TFining onset Na2SO4 Na2O + SO2 (gas) +1/2 O2 (gas)
pSO2 pO2 K = [SO3 ]

'
Cm CO2
Stripping of CO2 and N2 from melt
CO2
SO2 O2
Cm N2
N2
Dilution of N2 & CO2 in bubble by fining gases
45
Multicomponent diffusion of gases in bubbles
d Shi Di 1 1 Rg T (Csi Cii) + (4R3 pt ) /(3Rg T) = 4R2 i R dt 2 pt Shi Di t 2
Shi = 1+ (1+ 2vR/Di )1/3
46
Fining/Refining: degassing & removal of bubbles

Mostly applied fining agents in glass industry: Na2SO4 & Sb2O5 Na2SO4 (m) SO2 (g) + 0.5 O2 (g) + Na2O (m) Sb2O5 (m) Sb2O3 (m) + O2 (g) Na2SO4 added in concentrations 0.1 1 wt. % to batches of: Soda lime glass for container, float and tableware E-borosilicate glass for fibres Na2SO4 partly decomposes during batch melting & releasing SO2 in early melting stages Dissociation temperature of Na2SO4 in melt: Between 1350 1480 C, depending on redox state Between 1100-1350 oC (reduced batches) Na2SO4+Na2S reactions forming SO2 and or S2 gas.
Fe2+/Fetotal
0.6 Sulfur retention (wt.%SO3) 0.5 0.4 0.3 0.2 0.1 0.0 -8
80
70
60
40
25
15
Sulfur only in Sulfur in form of S2form of SO42-, S2(probably also SO32-?)
Sulfur only in form of SO42-
1400 oC
1500 oC
-7 -6 -5 -4 -3 Log pO2 in the melt at 1400C (bar) -2 -1
-30
-20
-10
+10
+20
48
redox number
Mass Spectrometer
Synthetic gas
30 mm
49
High temperature test facility
50

1. Primary fining
Removal of bubbles by rising of bubbles to melt surface Bubble growth under influence of fining agents Stripping of dissolved gases by growing of gas bubbles (dilution)
Fining
51
Enhanced Sulfate Fining by Dissolved Water in Melt O2

N2 O2 SO2 CO2
H2O
H2O
In oxygen-fired glass furnace: peH2O = 0.25-0.40 bar Fining only if: peSO2 + peO2 > 0.70 - 0.75 bar In air-fired furnace: peH2O = 0.10-0.15 bar Fining only if : peSO2 + peO2 > 0.9 bar
52
Oxy-case SO2
O2
N2
CO2 O2 SO2
H2O Air case SO2
Evolution of fining gas: water lean & rich melts

Gas evolution during sulfate fining of soda lime glass melt - effect of water vapor level 60
Volume of gas in
50
water vapor pressure 0 bar 0.20 bar 0.60 bar
m /batch
40 30 20 10 0 1300
1400
1500
o
1600
Temperature in C
53
Stripping of dissolved gases from melt
54
Pressure in melt before and during fining & cooling

[S]initial= 0.3 mass% SO3 300 mgr water/kg [Fe2+]/ [Fetotal] = 20 %
Total internal pressure in melt bar
1.2 1.0 0.8 0.6 0.4 0.2 0.0 1200
1300
1400
o
1500
1600
Temperature in C
55
Partial pressure in float glass melt during heating

[S]initial = 0.3 mass% SO3 300 mgr water/kg [Fe2+]/ [Fetotal] = 20 %
Partial pressure in float glass melt in bar 1.E+00 1.E-01 H2 O 1.E-02 O2 1.E-03 CO2 1.E-04 N2 1.E-05 1250 1350 1450 Temperature in C
o
SO2
1550
56
O2
fining gas
mol/m3
CO2
mol/m3
Modeling dissolved gas distribution in glass melt tank


2. Secondary fining (refining)
Re-absorption of residual gases during controlled cooling Chemical solubility SO2 and O2 increases with decreasing temperature: gases will be re-absorbed during cooling. Physical solubility of dissolved gases increases slightly with decreasing temperature: these gases will also be reabsorbed during cooling
Refining
Fining at low pressure
- Same amount of gas needs large volume - Low partial pressures in bubble will stimulate gas diffusion from melt into bubble
59
6. Evaporation processes
60
Multi-component glasses
Different oxides Oxides in glass with high chemical activity or vapour pressure: React at glass melt surface with combustion gases Evaporate from glass melt surface Show depletion at surface layer INCONGRUENT EVAPORATION
61
Evaporation mechanisms
Direct evaporation of volatile glass components from the surface of the melt, e.g. volatilization of PbO from lead crystal melts; Evaporation of components by reactions in the melt itself, forming volatile compounds; generally such volatile compounds exhibit high activity coefficients and weak bonding with other glass melt species. An example: formation of alkali borates in alkali borosilicate melts, subsequently evaporation of alkali meta-borates/tetra-borates takes place, Na2O(melt) + B2O3 (melt) 2NaBO2 (melt) 2 NaBO2 (vapor) Evaporation by reactions of certain glass melt components with gas species at the surface of the melt. The evaporation rate & vapor pressure depends on the composition of the gas atmosphere above the melt. B2O3 (glass melt) + H2O Na2O (glass melt) + H2O (gas) Na2O(glass melt) + CO (gas) 2HBO2 (vapor) 2NaOH (vapor) 2Na (vapor) + CO2
62
Kinetics of evaporation
The volatilization rate is often determined by:
mass transport of the relevant species from the melt interior (bulk) to the surface; the vapor pressures of the volatile components at the surface of the melt, dependent on the glass composition, temperature and gas atmosphere; the mass transfer of evaporated species from the surface of the melt into the main gas stream above the melt.
Reactive evaporation
For reactive evaporation of a component j in the melt reacting with a gas k and forming gaseous species i with saturation pressure pi*, according to reaction: nj (melt) + mk (gas) Reaction equilibrium: pi*q qi (gas)
= K ajn pkm
The values of K (equilibrium constant, assuming chemical equilibrium at the glass melt surface) and aj (activity of component j in the molten glass at the surface) can be determined experimentally or by thermodynamic modeling
64
Static melt and static atmosphere above the melt (interface x = 0)

Diffusion in melt of reacting glass melt component j:
dCj/dt = Dm,jCj2/x2
at t = 0 at t > 0 at t > 0 - < x < 0 x x =0
Time dependency: Cjsurface(t).
Dm,j is the inter-diffusion coefficient of the volatile component j in the melt.
Cj = Cjbulk Cj = Cjbulk Cj = Cjsurface(t)
For the vapor i in a static gas phase with partial vapor pressure pi, the diffusion process in the gas phase can be described in a similar way:
(pi/RgT)/t = Dg,i 2(pi/RgT) /x2

Dg,i is the diffusion coefficient of the vapor I in the gas phase.
at t = 0 at t > 0 at t > 0
0<x< x x =0
pi = pi,gasbulk pi = pigasbulk pi = pi*(t)

65
4970 Na2 O concentration [mol.m ]

-3
4968 4966 4964 4962 4960 4958 4956 4954

0 0.01 0.02 0.03 0.04 0.05 0.06
DNa2O=3.3 10-11 m 2.s -1
5 sec. 50 sec. 250 sec.
distance from surface [mm]
Calculated time dependent- Na2O concentration profiles in static melt Situation: static conditions in semi-infinite gas phase with 0.55 bar vapor pressure and semi-infinite soda-lime-silica melt (13 wt% Na2O, 10 wt% CaO, 5 wt% MgO, 72 wt% SiO2). Dg,NaOH = 2.7 10-4 m2s-1 , Dm,Na2O = 3.3 10-11 m2s-1
Evaporation in gas flow above molten glass

pb,i main gas stream velocity, vg diffusion of gas i in gas boundary layer, Dgi
surface reaction: nj (melt)+ mk (gas) qi (gas) p*i glass melt surface C j-profile
Example: Na2O (m) + H2O(g) 2NaOH (g)
Transport of component j in the melt, Dm,j

67
Evaporation in gas flow

Average evaporation rate (over length Lg of gas flow above melt ) of component i (formed by reaction of glass compound j) into (turbulent) gas phase:
Qm,j =(ni/qi)Avg0.8g0.47gas-0.47Dg0.667Lg-0.2 Rg-1T-1BCj,x=0(t)
The proportionality parameter B depends on the furnace atmosphere composition and the chemical activity of the volatile component in the melt. For NaOH-evaporation, the B value depends on the water vapor pressure in the furnace atmosphere, B pH2O0.5
Mass transfer equations

Average evaporation rate (rate of loss of glass component j) over length Lg from leading edge: Qm,j = -Dm,j(Cj/x)x=0 = Cj,x=0(t) = (ni/qi) A vg0.8g 0.47gas-0.47Dg0.667Lg-0.2 Rg-1T-1 B Turbulent flow of gas
v = velocity, g refers to gas phase, Rg is universal gas constant, T in K, B ratio between vapour pressure i and surface concentration component j A = between 0.03 and 0.04 for turbulent gas flow (Re > 300000 or for disturbed flows)
69
Solution in flowing gas and static melt

For kd defined as /DmNa2O the solution for a single component j Evaporating from a static melt in flowing gas phase Assuming complete depletion at surface for t
MQm.j is the total evaporation mass loss per unit surface area between time 0 and
MQm.j = (Cj,0/kd){exp(kd2DmNa2O)erfc[kd(DmNa2O)0.5] -1 + 2kd(DmNa2O/)0.5} Cj,x=0(t) = Cj,0 exp(kd2DmNa2O)erfc[kd(DmNa2O)0.5]

Cj,0 = bulk concentration compound j at t=0
5500 Na2O concentration in 5000 melt [mol.m ]

-3
4500
stagnant gas
4000 3500 3000 0 0.5 1 1.5 2 2.5 distance from surface [mm]
Lg= 2 m, v= 2 m.s-1 Lg= 2 m, v = 5 m.s-1 Lg= 0.5 m, v= 2 m.s-1
Local concentration profile in soda-lime silica melt after 7200 seconds exposure time, calculated for NaOH-evaporation from static melt in static or flowing gas phases, (Lg= downstream distance from leading edge ). Temperature = 1500 oC, pH2O = 0.55 bar. Dm,Na2O = 3.3 10-11 m2s-1 Glass composition (mass %): SiO2 =72, Na2O =13, MgO = 5, CaO = 10
6000 Na2O-surface concentration parameter is temperature: 5000 4000 3000 2000 1000 0 0 5000 10000 15000 20000 time [s] 25000 30000 1723K 1773 K 1823 K 1873 K
Change in Na2O-surface concentration soda-lime-silica melt at different temperatures in flowing gas (5 ms-1), 1 meters downstream. pH2O in gas = 0.55 bar & Na2O in glass = 13 mass%. Dm,Na2O= 8 10-10 exp(-5655/T) in upper graph
[mol.m ]
-3
Experimental Set up to study (reactive) evaporation from molten glass

Thermocouples Platinum funnel Porous plate
Gases IN: Platinum coating (30 cm) N2, H2O, O2
Platinum boat
Platinu m gas samplin g probe
melt
73
Mass transfer in gas phase during transpiration evaporation test

Shtranspiration
0 .5 2 1 .5 = C1 + C 2 Re d Sc + C3 (Re d Sc ) 1 + 22 Sc 1 3
h g ,i =
Vessel with liquid of melt
Shtranspiration D g ,i d
Q g ,i =
hg ,i R T
pi (t ) * pi bulk
x=0
2.5E-03
2.0E-03 Water evaporation rate QH2O (moles s -1 m-2)
pi*(t) (e.g. p*NaOH or p*NaBO2) can be derived from evaporation (transpiration experiments) From measured Qg,i and Sherwood relations derived with model liquids
1.5E-03 Measurerments CFD model Empirical equation (2.19) 5.0E-04
1.0E-03
0.0E+00 0 100 200 Reynolds number Re (-) 300 400
74
1.E-06 SiO2:Na2O:CaO = 74:16:10 mol Modeled aNa2O (-) 1.E-07 Na2O.2SiO2 y = 0.9823x R2 = 0.9283 1.E-08
1.E-09 1.E-09
1.E-08
1.E-07
1.E-06
Measured aNa2O (-)
Na2O activity at glass melt surface determined by transpiration test
measuring p*NaOH: Na2O + H2O
2 NaOH
75
Derivation chemical activity of volatile glass component at surface of melt

K = exp(-G/RT) = p*NaOH2/aNa2O.pH2O From thermodynamic tables: G = GfNa2O+GfH2O- 2GfNaOH(g) p*NaOH is measured from QNaOH and pH2O is controlled aNa2O (surface) can be determined K is calculated by standard Gibbs free energy values of products & reactants of reaction
Non static melt & non static gas phase free convection by density gradients
Gas flow
Low Na2O
Mid Na2O
High Na2O
Float glass melt with Na2O concentration differences

6. Homogeneity of glass
Micro-mixing: transfer from high to low chemical activity by diffusion
Cm - 2 . D.t = A exp Co Lo 2
Macro-mixing: elongation of in-homogeneities exposed to velocity gradient in melt
C(x,t)
t=0 Cm (t) t = t1
dC d 2C = D 2 dt dx
Slow diffusion processes
t = t2 Co Lo
Macro-mixing
Reduction of diffusion distance, Lo
velocity v + dv
velocity v
y In the case, t dv/dy >> 1:
L=
L0 dv t dy
For macro-mixing in combination with diffusion (by approximation):
Cm 2 . D . t 3 .( dv / dy ) 2 = A .exp Co L2 0
A = proportionality factor dependent on the shape of the cord
Macro versus only Micro mixing

Small velocity gradients (> 0.01 m/s per m) enhance homogenisation process with factor 20 to 100 Velocity gradients by: Stirring Bubbling Temperature gradients free convection
80
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What does a number tell us without the proper unit?
81

Glass Fining

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Chemical & Physical Processes in Glass Melting Quality of glass melting process

Ruud Beerkens TNO Glass Group Eindhoven, The Netherlands

ICG EFONGA Spring School Montpellier 4-5 May 2009

ICG EFONGA Spring School Montpellier 4-5 May 2009

ICG EFONGA Spring School Montpellier 4-5 May 2009

flue gas chemistry

deposition and dust formation

1. Overview Chemistry & Physics of Glass Melting Processes

ICG EFONGA Spring School Montpellier 4-5 May 2009

Homogeneous molten glass

Parameters for processes in melting

How to assess: Temperatures and flows in glass melt ?

2. Tools: CFD Simulation Models Glass Furnaces

CFD Simulation Models example: local conservation of energy

increase sensible heat

local boosting or cooling

Energy equation, conservation law for energy in each volume element

Results of CFD simulation models

Redox and dissolved gases

Residence time distribution

Glass melt quality indices per trajectory

Application of CFD models

For optimum process settings

Time-transient (time dependent) for colour or pull change

Time-transient for process control (rMPC)

Batch Boosting electrodes

Example result CFD computation

ICG EFONGA Spring School Montpellier 4-5 May 2009

4 inch higher crown

ICG EFONGA Spring School Montpellier 4-5 May 2009

Glass melt path with lowest temperature index

ICG EFONGA Spring School Montpellier 4-5 May 2009

Sensors (short overview)

Pt / Ni-NiO // ZrO2 // pO2 (glass) / Pt

ICG EFONGA Spring School Montpellier 4-5 May 2009

ICG EFONGA Spring School Montpellier 4-5 May 2009

Return flow for batch heating Day hopper

Hot spot & evaporation

Spring zone & primary fining

ICG EFONGA Spring School Montpellier 4-5 May 2009

Scheme of melting process of batch blanket, charging velocity vg (m/s)

reaction zone figure 1b glass melt layer

ICG EFONGA Spring School Montpellier 4-5 May 2009

Detailed re-presentation of the batch melting process in glass furnace

Layer glassmelt Dissolution sand grains

melts loose batch

sand grains gas

melting reactions batch

carbonates (soda/lime) gas sand grains

melting reactions dissolution sand grains

glass melt 1400 c.

b. top of batch blanket

bottom side of batch blanket

ICG EFONGA Spring School Montpellier 4-5 May 2009

Example: Melting reactions of soda lime (dolomite) silica batch

High amount of heat required (550-850 oC)

Formation of primary melt phases (alkali rich carbonates), e.g.:

ICG EFONGA Spring School Montpellier 4-5 May 2009

Melting reactions of soda lime silica batch

MgO still present up to 1150 oC.

Dissolution reactions of SiO2, e.g. (coarse limestone)

Scheme of melting reactions of soda lime glass batch

800 1000 temperature in oC