SEPA
           United States
           Environmental Protection
           Agency
           Industrial Environmental Research EPA-600 7-78-097
           Laboratory         June T978
           Research Triangle Part, NC 27711
Effects of Interfacial
Properties on
Collection of Fine
Particles by
Wet Scrubbers

Interagency
Energy/Environment
R&D Program Report

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                                     EPA-600/7-78-097
                                              June 1978
Effects of Interfacial  Properties
 on  Collection of  Fine Particles
          by Wet Scrubbers
                       by

         G.J. Woffinden, G.R. Markowski, and D.S. Ensor

               Meteorology Research, Inc.
                    P.O. Box 637
               Altadena, California 91001
                Contract No. 68-02-2109
              Program Element No. EHE624A
              EPA Project Officer: D.L Harmon

          Industrial Environmental Research Laboratory
           Office of Energy, Minerals, and Industry
             Research Triangle Park, NC 27711
                    Prepared for

         U.S. ENVIRONMENTAL PROTECTION AGENCY
            Office of Research and Development
                Washington, DC 20460

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                              ABSTRACT

      Typical wet scrubber models were analyzed to determine the effects
of surface tension on particle removal efficiency.  Particle capture (re-
moval) is a two-step process:  (1) collision of a particle with a spray drop-
let and (Z) coalescence with the droplet.  A change in surface tension of the
scrubber water can influence both  steps.

      When the  surface tension of scrubber water is reduced,  spray droplets
will normally decrease in size.  The cumulative exposed droplet surface
area is therefore increased.  The  larger exposed collection surface can
improve  collision efficiency.   Too much reduction in droplet  size,  however,
can actually reduce collision  efficiency.  One effect of surface tension in
droplet-particle collisions is therefore to help optimize droplet size for
maximum particle  removal.

      The coalescence process after a particle collides with a scrubber
droplet has been described by the film thinning model.  The model assumes
that coalescence is controlled by the thinning rate of an air or vapor layer
trapped between an impacting particle  and droplet.  If the film thins and rup-
tures before the particle rebounds, coalescence occurs.  The thinning model
predicts  that a reduction in droplet surface tension allows deeper particle
penetration into the droplet.  The escaping vapor film therefore has a longer
more resistive  path,  resulting in longer thinning times, thus reduced
coalescence probability.  The film thinning model is an instructive starting
point  but it needs to be modified if disagreement with experimental results
is to be eliminated.

      When the  surface tension of a scrubber liquor is modified, collection
efficiency may be slightly improved or degraded depending  on the spray
droplet sizes and the sizes of particles being removed.
                                   111

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                              CONTENTS
                                                                  Page
Abstract                                                           iii
List of Figures                                                     v
Acknowledgments                                                  vii
List of Symbols                                                    viii
Sections
1.    Conclusions                                                   1
2.    Recommendations                                             2
3.    Introduction                                                   4
4.    Scrubber Models                                               5
5.    Application of Surface Tension Results to Scrubber Models      9
6.    Experimental Evaluations of Coalescence Theory               24
References                                                         48
Appendix - Surface Tension Effects on Particle Collection
           Efficiency                                             51
                                  IV

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                               FIGURES
Number                                                            Pa.g<

    1     Scrubber droplet size for maximum collection effi-
            ciency of particles 0. 5 to 20 pm diameter,  based
            on model (V = 80 m/sec. )                                10
    2     Scrubber droplet size for maximum collection
            efficiency,  based on model                               11
    3     Effect of surface tension on outlet particle concentra-
            tion for 20 pm particles,  typical of flyash                13
    4     Effect of surface tension on outlet particle concentra-
            tion for 0. 8 pm diameter  particles,  typical of
            laboratory aerosol                                       14
    5     Effect of surface tension on outlet particle concentra-
            tion for 0. 3 pm diameter  particles,  typical of
            cupola emission                                         15
    6     Models for surface deformation                           18
    7     Coalescence efficiency vs velocity of impact of 134p
            droplets impinging on 2. 2 mm drops: a) distilled
            water, a = 72 dyn cm  ; b) 0. 5% acetic acid solution,
            o = 70 dyn cm ; c) 5% acetic acid solution, o = 60
            dyn cm l.  Curve c) also  resulted for distilled water
            •when the drops were oppositely charged.  (List and
            Whelpdale, 1969)32                                       20
    8     Inverted bubble                                           21
    9     Film thinning model                                       22
   10     High speed cine microscope equipment used for ex-
            perimental evaluation of coalescence mechanisms         25
   11     Glass rod with simulated flyash particle mounted  on
            traversing mechanism                                   26
   12     Traversing mechanism for impacting particles into
            water droplets                                           27
   13     Coalescence of 1700 pm diameter glass particle with
            water droplet, 585 usec delay, 6 cm/sec                 30
   14     Coalescence of 1000 pm diameter glass particle with
            water droplet, 780 psec delay, 6 cm/sec                 31
   15     Coalescence of 725 pm diameter glass particle with
            water droplet, 468 psec delay, 6 cm/sec                 32
   16     Coalescence of 275 pm diameter glass particle with
            water droplet, 351 psec delay, 6 cm/sec                 33

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Number                                                           Pagi

   17     Coalescence of 100 i^m diameter glass particle with
           water droplet, 156|-isec delay,  6 cm/sec                 34
   18     10 Um diameter glass fiber impacting distilled water
           droplet.  Coalescence delay time <1 frame (i.e.,
           <39psec).                                              35
   19     Coalescence of 725 Um diameter glass particle with
           water droplet, 273 psec delay,  42  cm/sec                36
   20     Coalescence of 725 Urn diameter glass particle with
           water droplet, 234 kisec delay,  42  cm/sec                37
   21     Coalescence of 725 Hm diameter glass particle with
           water droplet, 273 usec delay,  42  cm/sec                38
   22     Coalescence of 725 pm diameter glass particle with
           water droplet, 234 psec delay,  42  cm/sec                39
   23     Coalescence of 100 \±m diameter glass particle with
           Freon TF, <39 usec  delay, 42 cm/sec                   40
   24     Coalescence of 100 p.m diameter glass particle with
           water/surfactant, <39 Psec delay, 42 cm/sec            41
   25     Coalescence of 100 Hm diameter glass particle with
           water droplet, 156 psec delay,  42  cm/sec                42
   26     Comparison of theoretical predictions and experimental
           measurements of coalescence delay time for water
           at 6 cm/sec impact velocity                             44
   27     Comparison of theoretical predictions and experimental
           measurements of coalescence delay time for water
           at 43 cm/sec  impact  velocity                            45
   28     Comparison of theoretical predictions and experimental
           measurements of coalescence delay time for Freon-
           TF at 43 cm/sec impact velocity                        46
   29     Comparison of theoretical predictions and experimental
           measurements of coalescence delay time for water
           droplets containing surfactant and  an impact velocity
           of 42 cm/sec                                            47
                                  VI

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                          LIST OF SYMBOLS
A      --   Area of contact between a particle  and a liquid droplet during
             collision
B      --   Correction factor in film thinning model
c      - -   Constant
Cn    --   Cunningham correction factor
       --   Drag coefficient
d      --   Diameter of liquid droplets
D      --   Actual particle diameter
D      --   Aerodynamic diameter of a particle
f      --   Constant that may include effects of surface tension,  particle
             growth, collection by means other than impaction, and other
             unknown parameters
F      --   Surface tension force
F(K, f) --   Function of inertial parameter, k,  and undefined factors, f
F      --   Resistive force exerted normal to  the surface on a particle
             during collision with a liquid droplet
k      --   Inertial parameter
K,     --   Constant
 A
K      --   Harmonic oscillator constant.   "Spring" constant in harmonic
             oscillator model of particle impact and bounce.
K      --   Inertial parameter based on throat velocity
P      --   Average penetration of a particle into a water  dronlet during
             collision
Q      --   Volumetric flow rate of liquid phase
 G
Q      --   Volumetric flow rate of gas phase
R      - -   Particle radius
S      --   Constant depending on the shape of the depression in a water
             droplet made by an impacting  particle
                                    vii

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t       --   Thinning time of air or vapor film trapped between a colliding
             particle and a  liquid droplet
v       --   Impact velocity
V       --   Critical impact velocity below which particle/droplet
             coalescence will not occur
V       --   Velocity of gas phase
 G
V       --   Critical impact velocity above which particle/droplet
             coalescence will not occur
x       --   Radius of particle/droplet contact area
y       --   Penetration depth of particles into a liquid droplet during
             collision
&           A variable that includes all terms from Equation 5  that are
             functions of droplet diameter
y       --   Constant depending on surface tension and particle  size
6       --   Thickness of vapor or air film at time of  rupture
6       --   Angle defining particle  contact surface area
A0       --   Mean free path of molecules in the vapor  film separating a
             particle  and a water droplet
\i       --   Viscosity of  gas
 G
p       --   Particle specific gravity
p       --   Density of liquid
a       --   Liquid  surface tension
a       --   Liquid-gas flow rate  parameter, Q   p
                                   Vlll

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                          ACKNOWLEDGMENTS
      The University of Washington,  under an MRI subcontract, performed
theoretical  studies on the effects of surface tension on coalescence. This
work was performed by Dr. John Berg and Scott Emory.

      Gratitude is expressed to Patrick A.  O'Donovan, Aerojet-General
Corporation,  for providing high speed photographic equipment used in these
studies.
                                   IX

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                              SECTION 1

                            CONCLUSIONS

1.   Particle collection in a wet scrubber requires impaction and coales-
    cence with a water droplet.  A change  in surface tension can affect
    both impaction and coalescence under  some conditions.

2.   Results of the theoretical study indicate that changes in surface tension
    of wet scrubber liquids can either improve or degrade particle impac-
    tion efficiency,  depending on particle size and scrubber operating condi-
    tions; however, changes  are expected  to be  small.

3.   Current models describing coalescence do not agree well with experi-
    mental  results so it is difficult to predict exact  effects of surface
    tension on coalescence.

4.   Theoretical results from this study can be used to imply relative
    effects  of surface tension on scrubber  performance,  however addi-
    tional experimental verification is needed.

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                            SECTION 2

                       RECOMMENDATIONS
1.   There is a large discrepancy between theoretical predictions based on
    the film thinning coalescence model and experimental results obtained.
    This discrepancy should be resolved by additional studies of the basic
    coalescence process.  The discrepancy could be due to one  of the
    following factors: assumptions in the film thinning model may be
    faulty, the film thinning mechanism may not be the controlling process,
    approximations used in the film thinning model may be too crude, or
    control of experimental conditions  may have been  inadequate.

2.   Additional laboratory experiments  will be required for theory modifi-
    cations.  These experiments  should include:

    •     Demonstration of the effects  of particle materials other than
          silica,  i.e., carbon and hydrocarbons.

    •     Extension of coalescence measurements to  smaller particles
          using higher optical magnifications and faster motion  picture
          cameras.  Present studies were limited to  coalescence delay
          time measurements in the order of 150u sec.  Small particles
          as in a wet scrubber appear to coalesce in much shorter times.
          A 10tan diameter particles, for example, might be expected to
          coalesce in ZOusec, while a  1pm particle might coalesce in
          approximately 4ysec.   Instrumentation with a lUsec resolution
          time,  such as  the Beckman and Whitley Model 189 framing
          camera, should be  used.

    •     Additional low surface tension liquids should be investigated
          in  order to verify that the observed "surface tension effects"
          are real,  and  not due to some other property of the specific
          liquids that were  used in this study.  The other liquids
          should  include (1) additional homogeneous compounds  and
          (2) water with other surfactants.

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•     Water droplets have been observed to float for long periods
      on a water surface under controlled conditions.  This phe-
      nomena cannot be adequately explained by the film thinning
      theory of coalescence. Additional studies,  both theoretical
      and experimental, should be conducted to show the cause of
      these  effects (e.g.,  surface tension, electronic polarizability,
      adsorbed monomolecular layers, or some  other undefined
      mechanism) and whether they can be applied to scrubber
      models to improve collection efficiency. Results of such a
      study  may also explain some of the differences observed
      between coalescence theory and experimental results.

Laboratory-scale scrubber experiments  should be  conducted to evalu-
ate theoretical scrubber performance predictions based on models
evolved under the present study. These experiments should show par-
ticle removal efficiency as a function of surface  tension, droplet size,
particle  size, and relative impact  velocity.

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                                SECTION 3

                             INTRODUCTION
      Wet scrubbers represent  one  of the  primary  methods  for  controlling
particulate  emissions  from large industrial operations.  Improvements in
collection efficiency can reduce the size and capacity of the  required con-
trol devices.  Because of the high cost for a large control device, relatively
small improvements can provide significant savings in original capital invest-
ment and in operating costs.

       The objective of this study was to conduct a theoretical  and  experi-
mental study to determine the effects of particle/liquid interfacial properties
on the  collection of fine particles by scrubbers and to apply results to  ana-
lytical scrubber models.

      The technical  approach included the following steps:

      •     Analysis of current wet scrubber models

      •     Theoretical analysis of surface  tension effects on
            particle collection efficiency

     •     Experimental testing of theoretical results

     •     Comparison of results with existing wet scrubber
            performance models

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                               SECTION 4

                           SCRUBBER MODELS


      The effect of surface tension is not explicit in most of the current wet
scrubber analytical models.  Penetration (one minus the collection efficiency)
in the Calvert model for  example, is given by Equation  1:
               P  =  exp -
 v  p  d
- ^  .       F (k, f)
where    P      =  average penetration

          Q      =  volumetric flow rate of gas phase

          Q      =  volumetric flow rate of liquid gas
            .L<
          V      =  velocity of gas  phase

          p       =  viscosity of gas

          p       =  density of liquid
            ±-i
          d       =  diameter of liquid drops
          F(k, f)  =  function of inertial parameter, k, and unknown
                    factors, f

      Surface tension,  as such, is not one of the parameters listed; how-
ever surface tension influences droplet breakup and, therefore, the resul-
tant droplet diameter,  d.  A reduction in droplet diameter improves col-
lection efficiency by increasing the number of droplets and therefore the
total exposed water surface area.  The interfacial surface properties may
also have a significant effect on the  "F" factor because it is primarily a col-
lection efficiency factor that included both collision and coalescence probabili-
ties.  It Is assumed that  surface tension does not have a direct effect on col-
lision probability (other than that due to droplet diameter), but that it
could have an effect on coalescence after impact.

      Only limited experimental studies on the effects of surfactants in scrub-
bers have been performed.  One is by Bughdadi.2  He concluded that addition of
surfactant (0. 1 percent Triton  CF-10) improved the collection •efficiency of
a venturi  scrubber,  especially  at low liquid-to-gas flow ratios.  He reported
that the overall collection efficiency improved from 99. 66 percent to 99. 93

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percent at 18^ water/28 m3 of gas  (4 gal/1000 ft3).  He attributed the im-
provement to easier penetration of the collected particulates into the scrub-
ber water droplets, thus providing more effective wetting.  He also observed
a reduction in spray droplet sizes  with surfactant additives.  (It is difficult
to explain the large change in penetration by collision processes alone. )

      It has been shown experimentally that spray droplet size is proportional
to the square root of the surface tension  for sufficiently  small liquid to
gas ratios:
                            d = ca*2                                 (2)

where    d    =  droplet diameter
          c    =  constant
          o    =  liquid surface tension

      The maximum surface tension of scrubber water is approximately
72 dynes/cm (pure water).  Additives and normal contaminants  in operat-
ing scrubbers will  typically reduce the surface tension to 50-60 dynes/cm.
If a surfactant is added, the surface tension can be further  reduced to 20-30
dynes/cm.  Therefore, the maximum possible reduction, from 72  to 20 dynes/
cm will reduce the spray droplet diameter by  only 50 percent at most.  In
actual practice, a maximum reduction of 20 percent is more realistic.  The
effect of droplet size reduction on  scrubber efficiency is not easily deter-
mined from the scrubber model, Equation  1.  The droplet size affects the
"F" factor which includes individual droplet collection efficiency and other
unknown factors.  Decreasing the size of droplets will increase the number
of droplets so that  droplet/particle collision efficiency •will be improved,
particularly for small particles.  There  is a practical limit, however, be-
cause when the droplets get small  enough they may not be removed from
the gas  stream by the  entrainment  separator.   The droplets in a scrubber
are usually very large (on the order of 50 to 200 um diameter) compared to
the particles being scrubbed (the most difficult particles to remove are
typically 0. 05 to 3. Opm diameter).  When there is a large difference in size
between the droplet and particle and the particle is in close proximity to
the liquid surface,  the droplet surface can be  considered as an infinite flat
plane.

4. 1   Effect of Drop Size on Collection

      Typically wet scrubber models have been described by Calvert, et al.1
These models assume that impaction on the droplets is the  only mechanism
active in controlling the collection  process.   This is  a good assumption if
the particles are greater than 5 microns aerodynamic diameter and may be
good for particles as small as one  micron aerodynamic diameter.

      Aerodynamic diameter  is defined as:

                                    6

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                         =  (PPCD)   D
1/2

                                  (3)
      where    D       actual particle diameter
               C       Cunningham Correction Factor,  a function of
                       D, and the mean free path
               p     =  particle  specific gravity

      The scrubber models assume that the droplets are formed at a velocity
much slower than the gas stream and the particles moving with the gas
stream are collected as they impact the droplets.  As the droplets are
accelerated by the gas  flow, the relative velocity decreases and they become
progressively  less efficient particle collectors.  The collection efficiency
typically approaches zero at the scrubber outlet.  The models also assume
that once a particle collides with a  droplet, it invariably sticks.  While
intuitively  reasonable,  much evidence suggests that this assumption may
need modification.

      Surface tension enters into droplet size since the droplets are typical-
ly produced by atomization of the scrubber liquor introduced into the rapidly
moving gas in  the scrubber throat.  The droplet  size has been historically
predicted by the Nukiyama and Tanasawa equation  , based on empirical
work:
                                                                    (4)
               d    =  drop diameter,  cm
               O    =  liquid  surface tension, dyne/cm
               V    =  gas velocity, cm/sec
               p    =  density of liquid,  g/cm
               U       viscocity of liquid, poise
           Q  /Q_   =  liquid  to gas ratio, dimensionless
            1^  \j
      This correlation indicates that the droplet size is proportional to the
square root of the surface tension for sufficiently small QL/QQ.  A number
of other  correlations have appeared in the literature showing a similar de-
pendence. 1>4
        *
      Droplet size enters directly into scrubber performance models.   Cal-
vert's model1 was selected as  representative because it appears to be  well
constructed and to agree reasonably well with experimental data.  For an
infinite throat length and zero  initial droplet velocity the model predicts
a penetration as indicated in Equation 5:

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  P - exp
where
                'DO
                                      K
                          PO
           K
DO
PO
drag coefficient
inertial parameter based on throat velocity

Q,   P,
                                                             (5)
                      QG  PG

         The assumption of infinite throat length is good for small particles
(less than 2 microns diameter) and/or small droplets  (less than 50 microns
diameter).  In any case, the general dependence on droplet size is adequate-
ly indicated.
                                    8

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                               SECTION  5

                 APPLICATION OF SURFACE TENSION
                   RESULTS TO SCRUBBER MODELS


      The effect of changing droplet diameter on scrubber collection effi-
ciency was calculated by combining all of the droplet size dependent terms
in the scrubber model, Equation 5, into a  single exponential factor, B.
      Results indicate that for any given particle size to be removed, there
is an optimum collection droplet size that will provide maximum collection
efficiency.  An example of the calculated results is shown graphically in
Figure  1.  The optimum droplet diameter is the point at which the collection
efficiency exponent is the  highest.  Because the exponent is negative, a
large absolute value  represents a low penetration of particles.

      The results given in Figure 1 assume an impact approach velocity
of 80 m/sec.   Calculations were also made for  other velocities.  The opti-
mum droplet diameters for velocities ranging from 5 to  80 m/sec are
plotted  as functions of particle  diameter in Figure 2.

      It can be seen from  the results in Figure  1 that a  change in liquid
droplet size may improve or degrade particle collection efficiency,  depend-
ing on the initial sizes  of the droplets and the particles  being scrubbed.  For
example, 1 Um diameter particles are removed most effectively by 40 ^m
diameter droplets.  If a scrubber produces lOOPm diameter droplets, its
collection efficiency  for 1  l-tm particles can be improved by reducing the
droplet size to 40i-im.  If the scrubber initially  produces 40Um diameter
droplets either a reduction or an increase in droplet sizes will decrease
the collection efficiency of 1pm diameter particles.

      Generally, the penetration for large particles will be increased and
that for small particles will be decreased when droplet  sizes are reduced.
The overall penetration will likely decrease since nearly all large particles
will be  collected in any case.  If the scrubber is operating at near the
optimum efficiency over most of the size  distribution, changing the surface

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10.000
1.000          100           10

    DROPLET DIAMETER (pn)
 Figure 1.  Scrubber droplet size for maximum collection
            efficiency of particles 0. 5 to 20 um diameter,
            based on model (V =  80 m/sec.)
                           10

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  10,000
   1.000
I

as,
W

w
E-
U

0.
O

o

S
D


H
0.
O
    100
     10
                          y////
                          w
                                                  80 rn/sec.

                                                  40 m/sec.

                                                  20 m/sec.

                                                  10 m/sec.

                                                   5 m/sec.
        0. 1
                          1                 10

                       PARTICLE DIAMETER (fan)
100
   Figure 2.   Scrubber droplet size for maximum collection

               efficiency, based on model.
                                11

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tension is not likely to have much influence (if the coalescence properties
remain unchanged) since the peaks in Figure 1  are fairly broad.

      Table 1 shows the change in penetration for three different drop
sizes assuming a reduction of the surface tension by a factor of 2,  (the
maximum likely due to addition of surfactant).

      In this case the  drop  size was assumed proportional to the square
root of surface  tension and independent of the liquid to gas ratio.  The
initial drop sizes without surfactant are arbitrary. This  table indicates
the maximum change in penetration that could be expected due to surface
tension variation.  Actual changes  in real scrubbers should be smaller.


     TABLE 1.  PREDICTED CHANGE IN SCRUBBER PENETRATION
                DUE TO  ADDITION OF SURFACTANT

            throat velocity         =    8000 cm/sec
            particle size           =    1 Pm (aerodynamic diameter)
            penetration fraction
              without  surfactant     =    .02

 Drop Size       Drop Size
 Without          With             B            B           Fractional
Surfactant        Surfactant      Without        With         Penetration
  (Um)             (Pm)        Surfactant    Surfactant     w/Surfactant

   205             144           2.10          2.44            .011

   144             102           2.44          2.70            .013

    51             36           2.93          2.89            .021


      Note that penetration  is reduced by nearly a factor of 2 in the first
two cases but increased slightly in the last.   These calculations also indi-
cate that if demisting  is not a problem,  a spraying device which produces
smaller droplets than  those indicated by Equation 4 could result in de-
creased penetration.   Equation 4 predicts a drop size of about 125 microns.

      Figures 3, 4, and 5 show changes in relative outlet concentration
versus  size and surface tension for typical scrubber parameters. The
inlet size distributions are  log normal with geometric mean diameters
and standard deviations which  correspond to typical fly ash, lab aerosol,
and cupola aerosol respectively.  The distributions are normalized so
that the peak value is  1000 and the  area under the curves  represents
the total relative amount  escaping the scrubber.  The drop sizes were
                                   12

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                                                       INLFT  AEROSOL DISTRI PUT I ON

                                              d(j (Geometric Mean Diameter)      =

                                              a_ (Geometric Standard Deviation) =

                                                 (Liquid/Gas  Flow Ratio)        «


                                                 (Pas Velocity)
                                                 (Surface Tension):
                                  3

                               1/700


                               4000 cm/sec
	 35 dynes/cm
0.1                            l.n                             ln.n

                            AERODYNAMIC DIAMETER, microns

       Figure 3.  Effect of surface tension  on outlet particle concentration
                  for 20 pm particles, typical of flyash.
                                          j
                                       inn.o

                                       78-011

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   500 i-
   400  -
UJ 300  -
o
o
   ?oo  -
   100  -
      r .1
                                                             INLFT AEROSOL  01 STPr PUTTON
                                          dg  (Geometric Mean  Diameter)
                                          
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Ul
              1000

               900
           •-•  800
               ?nn
               60P
               500
               400
               300
               ?00
           ac.
               100
                     J  I  I 1 I
                  0.0'
         INLET AEROSOL DISTRIBUTION

df,  (Geometric Mean Diameter)      =
o  (Geometric Standard Deviation) =

^i_ (Liquid/Gas Flow Ratio)
0.
V  (Gas Velocity)
o,  (Surface  Tension):
                                                                    70
                                                             ---- 35 dynes/cm
  0.3 ftm
    2

1/700

 4000 cm/sec
                                           I    ill
                                                                          J	I	I  l  l  I  i
                                    o.?  o. TO. /in.',       i.n       ,>,o    i.o ".n r, ,r
                                      AERODYNAMIC  DIAMETER,  microns
                                 ir. 0
                   Figure 5.  Effect of surface tension on outlet particle  concentration for
                               0. 3 pm diameter particles, typical of cupola emissions.

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calculated using Equation 4 and are 173 and 143 microns for surface ten-
sions of 70 and 35 dyne/cm, respectively.  The drop size does not decrease
by the square root of two as in Table 1 because of the presence of the surface
tension in the denominator of the second term in Equation 4.  The outlet
concentrations decrease about 15 percent between 0. 5 and 1. 5 microns,  a
relatively small change in comparison to Table 1.  The smaller change in
penetration is due mainly to the smaller change in drop size.  The re-
sults in Figures 3 to  5 are also typical of larger liquid to gas ratios and
higher velocities.  Note that the development of nozzles which produce
smaller droplets have the potential of considerable  improvement in scrubber
performance.

Coalescence Effects

      It has been observed that when two droplets or a  particle and a drop-
let collide they sometimes bounce apart (Jayaratne5, Schotland8,  Lobl ,
Levin8).  The most widely cited theory predicting whether coalescence
will  occur is the film thinning model.

      The model assumes that as a particle collides with a water droplet,
a thin layer of air or  vapor is trapped between the particle and the deformed
surface of the droplet.  This air layer  prevents immediate coalescence.
The  layer thins under the compression forces produced during the collision
process; however, thinning is opposed  by the layer's viscous forces. If
the layer thins sufficiently before the colliding particle rebounds,  the layer
ruptures and coalescence occurs.

      One serious  problem is that the calculations based on this model,
give  results that are inconsistent with those observed by experiment.  Sec-
ondly, due to the crude assumptions made in order to carry out the calcu-
lations, it is not currently possible to determine whether the inaccurate
results are due to simplifying assumptions or because  the thinning layer
phenomenon is not actually the dominating process in coalescence.

      The thinning layer  model calculations are presented and discussed in
detail in Appendix A.   The salient feature  of the way these calculations are
performed is that the impact process is reduced to  that of a simple harmonic
oscillator with a "spring" constant given by Equation 7.
                                  16

-------
 where     R   =  particle radius
           c   =  droplet surface tension
           Pp  =  particle density
           S   =  a constant which depends only on the shape of
                  the depression assumed to be made by the
                  impacting particle.

      For the model used by Lang9 and Emory10 S = 1.  Jayaratne's more
 rounded depression is  more realistic and gives an S = (1.6).  The two
 shapes are shown in Figure 6.

      Viscous forces acting in the liquid may also be considered.  Emory10
 indicates that they are several orders of magnitude less than the calculated
 surface tension forces, however, and they may be neglected for practical
 purposes.  Emory10 and  Arbel11 also indicate that electric double layer
 forces  are smaller than  the surface tension forces and can be neglected.

      Coalescence is assumed  to occur if the layer thins to a rupture thick-
 ness 6 before rebounding.  6  is assumed constant.  A condition for
coalescence may be derived and the result is shown in Equation 8,
              BV<    S-(?                                      (8)
               =  particle radius
           B   =  an approximate correction factor used if 6 is less than the
                  mean free path,  X0; B = 0. 71 (6/Xo)[2 -  0. 71 (6/\o)]
           V   =  Impact velocity normal to the surface
           S   =  constant depending on the shape of the depression
                  in a water droplet made by an impacting particle

       Note that Equation 8 predicts that given a sufficiently small velocity,
coalescence will always occur.  However, above a certain velocity,  V    ,
 depending upon R, the particle radius, coalescence will not occur.

       V    is obtained by dividing Equation 8 by R2 B:
        max             7          ^

         '  v     = |  s  — V   *2                                  <9>
            maX    3      u R2B
                           G
       The rupture thickness may be estimated from theoretical or experi-
 mental determinations.  The fact that coalescence is impeded by increasing
 impact velocity seems intuitively incorrect and experiments confirm this
                                    17

-------
                 Model 1
           Lang 9,  Emory10
                  Model 2
                 Jayaratne6
Figure 6.   Models for surface deformation
                   18

-------
intuition:  Below a certain velocity, Vc,  coalescence does not occur and
above  Vc it does (Schotland6, Jayaratne5, List52).  In addition, the time for
a colliding drop to rebound is strongly dependent on impact velocity as
shown by Jayaratne  .  The film thinning model described above predicts a
rebound time independent of velocity (since  the period of a simple harmonic
oscillator is independent of its initial velocity).  Lastly,  the rupture thick-
ness 6 is in fact an arbitrary factor.  Emory10 suggests 50 A  while
Jayaratne suggests 1000 A.  This difference makes a factor of 400 differ-
ence in Equations 8 and  9.

      The idea that a particle traps an air layer which impedes coalescence
seems accurate intuitively,  so the question  remaining is what is wrong with
current thinning layer models.   The answer to this question is currently
unresolved; however, the problems fall into three areas (or  possibly a com-
bination of the  three).

1.    Film thinning  may not be the dominant process.  Significant evidence
      exists to suggest this possibility.  The most compelling results were
      obtained  by List12.  Figure 7 shows coalescence efficiency for small
      droplets  impacting upon a water surface.   The addition of small and
      moderate amounts of acetic acid increases the coalescence at low
      velocities.  These results suggest that surface forces are dominant
      and that, at least for low velocities, film thinning may  not be a con-
      trolling factor.  The thinning layer model depends  only upon liquid
      density and square root of the surface tension of the liquid and these
      factors vary only a relatively small amount in Figure 7.  Note that
      for a 5 percent acetic  solution,  coalescence occurred at all impact
      velocities.

      If smaller water droplets fall onto a clean water surface from low
      heights,  they float along the surface for a considerable length of
      time13, much longer than appears accountable by the film thinning
      model.   Small amounts of detergent can greatly increase the life of
      these floating  globules.  Again, surface forces appear responsible.
      It is  impossible to achieve the same effect with mercury drops on a
      clean mercury surface;  however,  a small amount  of oil (di octyl
      phalate in this case) will  stabilize  small surface drops  of mercury
      indefinitely (personal observation). Lastly,  it is posrible to create
      an -"inverted bubble" in water14.  If water is carefully dropped into a
      dish of soapy water, a drop may submerge itself surrounded by a
      thin layer of air.  These  "inverted" bubbles are stable  until they
      drift upward and break against the surface.  If a slightly more dense
      liquid drop is  used it may sink and thus last for a  considerable length
      of time.
                                   19

-------
                 €>©•
                               VCLOOTT (ntl")
Figure 7.  Coalescence efficiency vs velocity of impact of
           134H droplets impinging on 2.2 mm drops: a) dis-
           tilled water, a=7? dyn cm"1; b) 0.5% acetic acid
           solution, o=70 dyn cm 1; c) 5% acetic acid
                                 -i
           solution, o= 60 dyn cm  . Curve c) also resulted
           for distilled water when the drops were oppositely
           charged.  (List and Whelpdale, 1969)te
                             20

-------
An inverted bubble is shown in Figure 8.  Again it appears that surface
forces and surface layers are the dominant mechanism in preventing
coalescence.  Unfortunately, all of the above effects have been observed
with fairly large liquid drops.  There is no direct evidence to  shov.
•whether these phenomena occur between the solid and  liquid  particles
in a  scrubber; however,  since solid particles are likely to have an
adsorbed water  film (or other adsorbed films) it seems that  surface
effects similar to these may occur.  Also, it is interesting from a
practical viewpoint, that a compound such as acetic acid appears to
greatly increase coalescence.
                                          AIR
                         SUBMERGED
                         WATER
                         DROPLET
AIR  FILM
                                                    77-3'. 1
                 Figure 8.   Inverted bubble
                             21

-------
2.    The assumptions used to calculate the film thinning model predictions
      may have been too crude.  The Reynolds formula16 is used to calcu-
      late the time, t,  for the trapped air layer to thin to a rupture thick-
      ness,  6.
                                      2
                        t    T  U_ -4:	-T                           (10)
      where
         &   =  area of contact
         FJ^J  =  force acting on particle normal to surface
         U Q  =  absolute viscosity of air
         6   =  film rupture thickness

Figure 9 illustrates the important dimensions  in the film thinning
model.
                   Figure 9.  Film thinning model
                                                             77-361/1
      Equation 10 is valid when ymax <0. 5 R,  which will include most cases
      of interest; however, it is also assumed in order to calculate the
      thinning time, t,  that the ratio of F to A2 is constant.  This is simply
                                                          .10
not the case,  in fact, for the models of Lang9, Emory1", and
Jayaratne6, the ratio of F to A is a constant:

                F  = yA,
                                                                        11)
                                   22

-------
      vhere y is a constant depending only on the surface tension and particle
      radius.  Thus the ratio A2/F must be proportional to A which changes
      from 0 to  Amax (and back to zero if the particle rebounds).  Before the
      particle forms a  trapped layer, the area A,  is zero and the thinning
      time.  Equation 10,  also becomes zero since AS/F is  zero.  Thus,  the
      model actually appears to predict that the thinning layer collapses
      before penetration begins.   This conclusion does agree with the data
      shown in Figure 4 for the 5 percent acid solution.  The problem in
      Equation 10 is that  the change of A with respect to F  during the col-
      lision process has been neglected.

3.     Important factors may have been ignored in calculating thinning time.
      All the calculations discussed above assume that the  major forces  act-
      ing to decelerate the particle result from surface tension.  Inertial
      forces and the droplet internal pressure are neglected.  In actuality
      it is these very forces that are  responsible for stopping the particle;
      the surface tension acts to transmit these forces (to the thinning layer).
      The surface tension also plays a role in absorbing energy from the
      incoming particles since the  surface stretches.  It is likely that the
      coalescence described by Equation 8 is  inaccurate because these
      forces are neglected.  Unfortunately, it is difficult to include inertial
      effects since  the  entire process such as the forces  acting on the
      particle through the thinning layer, the  thickness of the thinning layer,
      the flow fields in the droplet, and the form of the depression (not just
      its relative dimensions) change with time and  velocity, and are inter-
      related.   The  set of differential equations describing the  process and
      the method of solution are complicated and would require extensive
      calculations for solution.   It is  difficult to simplify the processes so that
      meaningful estimates can be made.  Yet, it appears essential that  this
      type of calculation be performed if the film thinning model is to be
      properly evaluated.  The  results could easily  show that the thinning
      layer  plays a minor part in preventing coalescence.

      Another phenomenon which is normally  neglected is the stability of
      the thinning layer.  While it does appear likely that a higher surface
      tension causes the layer to thin more rapidly, increased  surface
      tension will also  make the layer more stable.   Lang9 has  given the
      stability a preliminary treatment but a more detailed study is  needed.
      In particular,  it seems intuitively  likely that the layer will break
      down once the thickness at some point approaches the local mean free
      path.  Also, the inertial forces involved in collision are quite  large
      and these  too act to decrease stability.
                                   23

-------
                                SECTION 6

        EXPERIMENTAL EVALUATIONS OF COALESCENCE THEORY
      Simple  laboratory experiments were devised to measure  film thin-
ning times and the effects of surface energy on the thinning times.  These
experiments were  planned to  evaluate, at least qualitatively,  the film thin-
ning theory.

      The impact and coalescence process  for  a water  droplet and a  glass
sphere (representing a fly ash particle)was observed with a high speed motion
picture camera looking  through a microscope.   The water droplets were
approximately 1000 to  3000 um diameter and were suspended  on the end of
a microliter syringe needle.  The glass spheres were made by drawing a
glass rod  into a fine fiber and forming a ball on the tip end. The particles
ranged from 1 0 to 3500um diameter. The  suspending  rods were as small as
lOum diameter.  Rods  10 nm  diameter without a sphere on the end were
also used to simulate 10 um diameter particles.

      The experimental setup  is shown in Figures 10  and 11 .   The support-
ing syringe and  glass rod were mounted on three-dimentional micromanipula-
tors so that they could be moved independently within the field-of-view of
the camera. The glass  particle was caused to impact the water droplet  by
rapidly advancing the horizontal traverse mechanism of the particle support,
Figure 12. Radioactive  polonium strips were mounted near the  particles
and droplets to eliminate electrostatic charges. Radiation from the polonium
ionizes  the air so that surface charges bleed off.   Experiments without the
polonium tended to  give more variable film thinning time measurements.
The camera used was a  Beckman and Whitley Dynafax, operating at a top
speed of 26, 000 frames per second, with individual frame exposure times
of 2. 5 y,sec. The camera is a continuous writing rotating  drum camera with
224 frames.

      The camera speed was measured to within ±5 percent.   A measure-
ment uncertainty of ±1/2 frame at each end of the thinning time measure-
ments introduces an additional potential error of ±39  ^i sec. A thinning
time of  1,000 ysec,  therefore, has  a random experimental variation of
approximately ±10 percent while a thinning time of 100 y, sec, has a random
variation of approximately ±50 percent.

                                    24

-------
'-n
                                                                                   Syringe
                                                                                   Droplet
                                                                                   Support
       Xenon
       Flash
       Lamp
    ic 1®
Support
                                                                                                  77-084
      Figure  10. High speed cine microscope equipment used for experimental evaluation of
                 coalescence mechanisms.

-------
                                                               77-083
Figure 11. Glass rod with simulated flyash particle mounted on
           traversing mechanism.

                               26

-------
Figure 12. Traversing mechanism for impacting particles into water droplets.
                                                                               77-114

-------
       Coalescence  delay times were measured as functions of particle size,
impact velocity,  and droplet surface tension.  Film  thinning time was taken
as the coalescence delay time; i.e.,  the time from  first contact until a liquid
meniscus was first discernable.  For example, in Figure 13 first contact
occurred on frame 9 and coalescence occurred on frame 24. The delay is
therefore equivalent to 1 5 frames at 39 H sec/frame, for a total delay time
of 585 yisec.  The time per frame is determined from the camera "speed; at
26, 000 frames per second the time between frames is 39 jisec.  The camera
speed was held constant at 26, 000 frames/sec for most of the experiments.
A summary of experimental variables is given in Table 2.
                    TABLE 2.  EXPERIMENTAL, VARIABLES

            Particle Size Range:          10 to  3500 ^m diameter
            Droplet Diameter:             2 mm,  nominal
            Droplet Surface Tension:      72 (Distilled Water), 30 (1%
                                          Triton X-l 00 in Water),  17.3
                                          (Freon TF) dynes/cm.
            Impact Velocity:              5 to 1 00 cm/sec.
      Typical high speed motion pictures produced during the test pro-
gram are included  in Figures 13 through 25.  Table 3 summarizes variables
that are illustrated.  The cases shown in the figures were selected to show:

      1.    The decrease in coalescence time resulting from a decrease
           in particle size (Figures 13  - 18 )

      2.    The minimal change in coalescence delay time resulting  from
           a change in impact velocity (compare Figures 13 -  18 at  6 cm/
           sec impact velocity with Figures 19 - 25 at 42 cm/sec).

      3.    The effect of surface tension in reducing coalescence delay
           times (Figures  23 - 25).
                                    28

-------
            TABLE 3.  EXPERIMENTAL VARIABLES ILLUSTRATED EN FIGURES 13-25
IN)

Figure
No.
13
14
15
16
17
18
19
20
21
22
23
24

25
Particle
Diameter
(Hm)
1700
1000
725
275
100
10
275
275
275
275
100
100

100
Impact
Velocity
(cm/sec)
6
6
6
6
6
42
42
42
42
42
42
42

42

Droplet
Composition
Dist. Water
Dist. Water
Dist. Water
Dist. Water
Dist. Water
Dist. Water
Dist. Water
Dist. Water
Dist. Water
Dist. Water
Freon TF
1% X-100 in
Dist. Water
Dist. Water
Surface
Tension
(Dynes/cm)
72
72
72
72
72
72
72
72
72
72
17.3
30

72
                                                                           Remarks

                                                                   No. 13-17 show the effect
                                                                    of changing particle size.
No.  19-25 are replicate ex-
  periments to demonstrate
  reproducibility.

Homogeneous low surface
  tension droplets.
Surfactant, low surface
  tension water droplets
Distilled water for compari-
  son with Figure 24.

-------
Figure 13.  Coalescence of 1700 Um diameter glass
            particle with water droplet, 585 Usec
            delay,  6 cm/sec.
                          30

-------
Figure 14.
Coalescence of 1000 pm diameter glass
particle with water droplet,  780 psec
delay, 6 cm/sec.
                31

-------
                                                  c
                                                       77-120
Figure 15.  Coalescence of 725 Um diameter glass particle
            with water droplet,  468 t^sec delay, 6 cm/sec.

                          32

-------
Figure 16.  Coalescence of 275 Um diameter glass
            particle with water droplet,  351 Usec
            delay, 6 cm/sec.

                       33
                                                   77-121

-------


Figure 17.  Coalescence of 100 pm diameter glass
            particle with water droplet,  156 psec
            delay,  6 cm/sec.

                        34
                                                   77-122

-------
                             m~'
                             W
                             •        i
^^^•takl^^^^iMi^l  ^^B
              MM
              i^L^—^     J  Hi         ;
HB»lMIM«.^Mrf  ••
              I	i m         .  L.
  ^Bt_—.^^fci^*"*^^^^^"^*  ^^^^^B
                            ^^^^1   ^^^^^^^^  ^^
                                             77-350
    Figure 18. 10 pm diameter glass fiber impacting distilled
             water droplet.  Coalescence delay time <1 frame
             (i. e. , <39 Psec).

                        35

-------
                                                          77-351
Figure  19.
Coalescence of 725 urn diameter glass particle
with water droplet, 273 usec delay,  42 cm/sec.

                   36

-------
BBIr	^H     ^_^___^_—
                                                            77-345
 Figure 20.  Coalescence of 725 Um diameter glass particle with
            water droplet, 234 Msec delay, 42 cm/sec.
                              37

-------
                                                           77-342
Figure 21.  Coalescence of 725pm diameter glass particle with
            water droplet, 273 psec delay,  42 cm/sec.

                               38

-------
                                                         77-347
Figure 22 -   Coalescence of 725 Hm diameter glass particle with
            water droplet, 234 psec delay, 4Z cm/sec.


                              39

-------
                                                             77-348
Figure 23.  Coalescence of 100 pm diameter glass particle with
            Freon TF, < 39 psec delay, 42 cm/sec.

                              40

-------
                                                             77-081
Figure 24.  Coalescence of 100 pm diameter glass particle with
            water/surfactant, < 39 psec delay,  42 cm/sec.
                              41

-------
Figure 25.  Coalescence of 100 Urn diameter glass particle with
            water droplet, 156 psec delay,  42 cm/sec.
                                                              77-076
                               42

-------
      Delay time measurements for water droplets with an impact velocity
of 6 cm/sec are plotted as a function of particle diameter in Figure 26 for
comparison with theoretical predictions from the film thinning model of
Emory  .

      The experimental results are consistent and reasonably reproducible;
however,  they differ from the theoretical predictions by as  much as 2
orders of magnitude for larger  droplets.  For the large particle experi-
ments,  the particles were nearly the same size as the water droplets.  An
error could, therefore, be introduced by the false assumption that the drop-
let was large  compared to the solid particle.  Some of the random experi-
mental variation could  also be due to uncontrolled parameters including
ambient temperature,  relative humidity, water purity,  and  particle cleanli-
ness.  No special control of these factors was made; however, because of
the limited ranges of variations they are not expected to have large  effects.
Ambient temperatures  ranged from 19 to 22° C (67 - 12° F).  Relative
humidity ranged from 40 to 50 percent.

      Figure 27 shows  the results obtained when the velocity was increased
to 43 cm/sec.  The dotted lines showing the range of scatter for the 6 cm/
sec velocity data are included for comparison.   It appears that delay times
are slightly shorter at  the higher velocity,  especially for  small particles.

      The high velocity results  were repeated using droplets of Freon-TF
instead of water.  The  Freon represents a homogeneous liquid with  a low
surface tension, approximately 17.3 dynes/cm, (compared  to 72 dynes/cm
for pure water).  A homogeneous liquid was selected in order to minimize
the effect of the polarized  Helmholtz double layer  that is expected to be
present at the  surface of water  droplets containing a  surfactant.  The short
range molecular dipole forces in  the double layer  could have an effect on
coalescence that is separate from the surface tension effect by itself.

      Results of the Freon coalescence  measurements are given in Figure
28.  It appears that the range of random variation in  the measurements
is wider than  for the water droplet coalescence measurements. None of the
Freon-TF delay times  were longer than for water but some were consider-
ably shorter.   Therefore,  if there is an effect on a delay time due to the re-
duced surface  tension of Freon-TF, the effect appears to  reduce the delay
time.

      Results of experiments using surfactants in water are given in Figure
29.  There is insufficient data available to draw conclusions at this time,
however,  it appears that if there  is an effect on coalescence delay time due
to addition of a surfactant,  the delay is  shorter.
                                   43

-------
a
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Q
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"2 io"3 10
                  COALESCENCE DELAY TIME, second
Figure 26.  Comparison of theoretical predictions and experi-
            mental measurements of coalescence delay time
            for water at 6 cm/ sec impact velocity.
                         44

-------
     10,000
    Jj  1,000
    o

    u
a
H
w
S

Q
w

o
H
«

2
•_«
o
o
            XII  l\.
              SJ\ I
              ^
                     rV!-
                           \\
                             \
                                           43 cm/>cc
                                  ! i^
                                ^v

                                       Vv
                             i	v

                                         ^   \
                                         V  1  \
I I
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                                           .
                                      \
                                               SM9

                                                   \
                                1  •  !
        loLU
                    COALESCENCE DELAY TIME, second
Figure 27.  Comparison of theoretical predictions and

            experimental measurements of coalescence

            delay time for water at 43 cm/ sec impact

            velocity.
                        45

-------
   10.000
  •  1,000
 u
 H
 W
 5


 Q
 U

 O
 P
 05
      100
        10 •                    10""                   10"4

                   COALESCENCE DELAY TIME, second

Figure 28.  Comparison of theoretical predictions and experi-

            mental measurements of coalescence delay time

            for Freon-TF at 43 cm/sec impact velocity.
                          46

-------
  10,000
c
o
u
U
H
U
2

5
Q

W

O
M
H
ct
1.000
     100
                  COALESCENCE DELAY TIME, second
  Figure 29.  Comparison of theoretical predictions and experi-
              mental measurements of coalescence delay time for
              water droplets containing surfactant and an impact
              velocity of 42 cm/sec.
                           47

-------
                            REFERENCES

1.    Calvert, S. , Yung,  S.,  Barbarika,  H. , Venturi Scrubber Performance
      Model.  Air Pollution Technology, Inc.,  Final Report to U. S.  En-
      vironmental Protection Agency,  Research Triangle Park, North
      Carolina,  1976.  196 pp.

2.    Bughdadi,  S. M. , Effect of Surfactants on Venturi Scrubber Particle
      Collection Efficiency,  M. S. Thesis.  Department of Thermal and
      Environmental Engineering, Southern Illinois University of Carbon-
      dale,  1973.

3.    Nuykiyama,  S. ,  and Tanasawa, Y. ,  Trans.  Soc. Mech.  Eng. (Japan)
      4,  86,  138 (1938); 5, 62, 68 (1939); 6,  II-7  11-15 (1939); 6,  11-18
      (1940).

4.    Wolfe, H.  E. ,  and Andersen, W. H. , Kinetics,  Mechanism,  and
      Resultant Droplet Sizes  of the Aerodynamic  Breakup of Liquid Drops.
      Aerojet-General Corporation Report No. 0395-04 (18) SP,  1964.

5.    Jayaratne, O.  W., and Mason,  B. J.,  The Coalescence  and Bouncing
      of Water Drops at an Air/Water Interface.   Proc. Roy.  Soc. , A(280):
      545,  1964.

6.    Schotland, R. M.,  Experimental Measurements Relating to the
      Coalescence of Water Drops with Water Surfaces. Disc. Faraday
      Soc.,  (30): 72,  I960.

7.    Lobl,  E. L. personal communication,  1976.

8.    Levin, Z. , Neiburger, M.,  and Rodriguez,  L. , Experimental
      Evaluation of Collection and Coalescence Effects in Cloud Drops.
      J. Atmos. Sci., 30(1): 944-946, 1973.

9.    Lang, S. B., and Wilke, C. R., A Hydrodynamic Mechanism for
      the Coalescence of Liquid Drops.  University of California, Berkeley,
      California, 1971. 23 pp.
                                  48

-------
10.   Emory,  S. ,  and Berg, J. ,  The Effect of Liquid Surface Tension on
      Solid Particle-Liquid Droplet Coalescence.  University of Washington,
      Task Report to U. S.  Environmental Protection Agency,  Contract
      No. 68-02-2109.  May,  1977.

11.   Arbel,  N. , and Levin, Z. , The Coalescence of Water Drops, I. A
      Theoretical Model of Approaching Drops, and II.  The  Coalescence
      Problem and  Coalescence Efficiency.  Department of Geophysics and
      Planetary Sciences,  Tel Aviv University, Rarnat Aviv,  Israel,  1977.
      I.  25 pp. II.   25 pp.

12.   List, R. , and Whelpdale, D.  M., A Preliminary Investigation of
      Factors Affecting the Coalescence of Colliding Water Drops.  J. Atmos.
      Sci., (26): 305,  1969.

13.   Stong, C. L. , Water Droplets That Float on Water,  and Lissajous
      Figures Made with a Pendulum.  Scientific American,  August,  1973.
      pp. 104-109.

14.   Stong, C. L. , Curious Bubbles in Which a Gas  Encloses a Liquid
      Instead of the  Other  Way Around. Scientific American, April, 1974.
      pp. 116-121.

15.   Reynolds, O. ,  Phil. Trans.  Roy. Soc., A(177):157 1886.
                                   49

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                       APPENDIX
SURFACE TENSION EFFECTS ON PARTICLE COLLECTION  EFFICIENCY
                            By




                   Scott F.  Emory  and


                      John  C.  Berg


           Department of Chemical  Engineering
                University  of  Washington
                   Seattle,  WA  98195
                           51

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                                ABSTRACT
     Modifications in existing theory concerning the collection on non-




wet table or partially non-wettable particles in wet scrubbers are presented.



In particular, the requirement for the thinning and rupture of a gas film



between particle and liquid is included.  Results suggest that decreasing



the liquid surface tension may decrease the probability of particle capture.
                                    52

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Introduction




     The commonly used models for the wet scrubbing of particulates  from




gases assume that collision of the solid particles with the surface of the



scrubbing liquid always results in the capture of the particles (loldshmid &




Calvert, 1963).  Such a view seems to be supported indirectly by tie gen-




eral success of predictions based on that assumption, of overall collection




efficiency of scrubbers removing a wide variety of particulates.




Nonetheless, the formal possibility of collision efficiencies less than




100% was acknowledged by Fuchs (1964), and seemingly valid reasons Were




advanced for supposing that all collisions should not necessarily result




in attachment.  In particular it was believed that non-wettable particles




might simply be reflected if they did not penetrate the liquid to suffi-




cient depth to allow total envelopment.  Pemberton (1960) developed predic-




tions of collection efficiencies for totally non-vettable particles (contact




angle = 180°) based on the above envelopment criterion, and McDonald  (1963)




later extended the model to cases of partial non-wettability (90°"  <




contact angle < 180°).  The Pemberton-McDonald model implied that for given




solid particles  the capture fraction, and hence the collection efficiency,




should increase if the surface tension of the collecting liquid is reduced.




The use of surface active agents might thus be advantageous in improving




collection efficiency, and indeed some reported results suggest that this




is the case (Hesketh, 1974; Rabel, 1965).  Such increases in overall col-




lection efficiency might also be explained, however, by a greater degree




of atomization of the collecting liquid.  Other results (Taubman &




Nikitina, 1956,1957; Drees, 1966; Goldshmid & Calvert, 1963) suggest, more-




over, that just the opposite occurs, i.e., collection efficiency falls when
                                    53

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Che liquid surface tension is reduced.  Still other reports (Weber, 1968, 1969]



claim no effect at all.  In an attempt to resolve some of the above apparent



contradictions, and in particular to assess the findings of adverse effects



of surfactant, the present work re-examines the assumptions and development



of the Pemberton-McDonald theory.



Improved Model



     Two significant shortcomings of the Pemberton-McDonald theory are that:



          1) No allowance for the thinning of the vapor film between the



          solid particle and liquid surface is made i.e., the film is assumed



          to rupture immediately upon "impact", and



          2) Rebounding particles, i.e, particles without sufficient kinetic



          energy to produce total envelopment are thought to escape even



          though coalescence has been assumed.




A more plausible sequence leading to particle capture is as follows.



Initially at least, a particle deforms the liquid surface inward while nested



in a thinning but unruptured vapor film.  Short of complete envelopment, the



particle is caught if coalescence, i.e., vapor film rupture, occurs before



the particle comes to rest and rebounds.  After coalescence, wettable



particles would reside in the droplet interior and non-wettable particles,



rather than escaping, would be retained in the liquid surface by surface




tension forces acting as dictated by small receding contact angles.  This



new view is strongly supported by the work of Weber (1968, 1969) who observed



experimentally that reduction In particle wettability did affect the loca-



tion of the captured particle but did not prevent capture itself, which



occurred every time actual contact was observed between liquid and particle.



Thus an appropriate criterion for capture, in contrast to that of complete
                                    54

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envelopment, is that the vapor film thinning proceed fast enough for
coalescence to occur during the particle penetration/rebound cycle.  All
particles except those corresponding to the limit of total non-wetting
should be equally capable of capture regardless of their specific wettability,
provided only that the particle/liquid interaction time is greater than the
time required for the vapor film thinning.  Predicted trends in capture
efficiency with fluid properties and system parameters should thus reflect
the trends predicted for the ratio of interaction time to film thinning
time, R.  Large values of this ratio assure capture while values much less
than unity indicate no capture.  Present knowledge of the details of the
film thinning process in particular is not adequate to permit quantitative
evaluation of the above ratio, but qualitative predictions of its trends
with such parameters as liquid surface tension, particle size and particle
velocity (relative to the liquid) should be possible if other factors are
assumed to remain unchanged.
     The objective of the computations which follow is the prediction of
such qualitative trends, and while the models used for calculating both the
particle/liquid interaction time and the film thinning time are highly
simplified, we believe them to reflect the important features of both
processes.
     An. approximate solution for the pa-ticle/liquid interaction time can
be obtained.by considering the vapor and liquid phases separately and
assuming the liquid surface at any instant to have the easily-described
shape shown in Figure 1.  The particle is thus modelled as a smooth sphere
nested in a vapor filB of uniform thickness.  The liquid surface is initially
flat, a good assumption since the collecting droplets are usually more than
a thousand times larger than the particles.  We assume further that the
total force resisting deformation of the liquid surface is the sum of a
                                    55

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 surface  tension  and  a viscous contribution so that  the equation of motion



 for  the  particle becomes:
with initial conditions (t - 0) :  Z - -R and dZ/dt = V .  Inertial effects



in the liquid are thus neglected.  Neither Brownian motion nor slip between



the particle surface and the gas are considered so that the present treatment



is restricted to particle sizes larger than approximately 0.5 urn.



    Referring to Figure 1, we write for the surface tension force



resisting particle entry:



             F  - 2iroR sin20                                        (20)
              o


The viscous resistance to deformation will be a form drag only, ignoring



the viscosity of the thinning film in the computation of particle/liquid



interaction time.  We assume provisionally that the drag experienced by the



vapor-enveloped penetrating particle can be approximated as the appropriate



portion of the drag on a completely submerged bubble moving with the same



velocity through an infinite medium in pseudo-steady creeping flow.  For



this case, the pressure profile is (Levich, 1962):




           p, • -v — j  cos 8,                                       (3)





from which




           F^ -  | iruRV [(|)3 + 1]   ,                              (4)




It is found that for all reasonable values of the system parameters, F  is



at least three orders of magnitude less than ?Q.  It thus appears  to



contribute negligibly to the total force resisting particle entry, and



refinements in the computation of its value are unwarrented.
                                      56

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     The rate of thinning of a spherical film of vapor (air) has been


given by Lang (1962) in the form:
                      _
            dt        4                      »
                  24»R%alrP<9)



where P(0) - cos(ir-G) - 1 - 4 In [cos(^)]-  The compressive force, F,


in Equation (5) is equal at any instant to the total force resisting penetra-


tion, viz., FO + F  ~ F    An estimate of the time for thinning to rupture


can be obtained by assuming that the rupture thickness, H, is very much


smaller than the initial thickness and that the compressive force is constant


with time and equal  to the average penetration resistive force.  We can then


write for the thinning time •
             t - -       P(6) -     .                           (6)

                    F
                     o
In order to obtain numerical estimates of t, we assume further that rupture


occurs at a film thickness of 5oX [Ewers and Sutherland (1952) predict that


molecular fluctuations will guarantee rupture at this film thickness . ] and


that the angle 6 used in the calculation corresponds to the point of maximum


penetration depth.


Results and Discussion


     Solutions of Equation (1) were obtained using the Runge-Kutta method, and


results for several values of particle size, velocity, and liquid surface


tension are shown in Table 1 and Figures 2 & 3.  Table 1 shows the maximum


predicted extent of liquid surface indentation prior to either capture or


rebound, and it is seen that such deformation is typically very shallow.


Such a picture is at variance with the deep penetration capture models of
                                   57

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Pemberton and McDonald for non-vetted particles but In agreement with




numerous published photographs of the particle/liquid interaction (e.g.,



Woffinden, et al., 1977).  Trends in capture probability with surface tension a



particle size are most clearly seen in Figure 2 & 3.   Decreasing surface



tension is seen to have a small negative effect on particle capture.  As



surface tension is lowered, the penetration depth increases, enlarging the



area of the thinning film.  The resulting increase in thinning time is



greater than that in the interaction time, providing a possible explanation



for an observed negative effect on collection efficiency of adding  surfac-



tant to the liquid.




     The computations also predict that small particles are more readily




collected than larger ones, but this result reflects the fact that the



particles have been taken as smooth spheres.  For most particulates, this



assumption is not valid.  Particles will usually be rough, and asperities



on the particle surface will produce local thin spots in the vapor film



leading to film collapse at much shorter times than predicted on the basis



of a uniform film.  The minimum size of asperities on a particle surface



would probably be a more characteristic size parameter than the particle



diameter.




     Finally, increased impact velocity is also seen to decrease the capture



probability.  This is explained, as is the surface tension effect, by the



increase in-penetration depth leading to longer film thinning time.




Acknowledgement



     This work was supported by funds from the Environmental Protection



Agency administered as a subcontract of Meteorology  Research,  Inc.,



Altadena, California.  The authors are indebted to Dr. L.E. Sparks of EPA and



to Mr. G.J. Woffinden and Dr. D.S. Ensor of MRI for helpful discussions.





                                     58

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Nomenclature





D  B particle diameter, urn



F  - compression force on vapor film, dynes



F  - viscous force resisting particle penetration, dynes



FQ - liquid surface force resisting particle penetration, dynes



F  « F   averaged over the particle/droplet interaction time



H  » vapor film rupture thickness, cm



M  = particle mass, g



P(0) «  dimensionless function  of 0, defined in text



R  « particle radius, cm



R  « ratio of interaction time to  film  thinning  time



V  = relative velocity between particle and collecting drop,  cm/sec



V  = "impact" velocity  (V at  time  zero), cm/sec
 o


Z  «  particle  penetration, cm (cf. Figure 1)



0  = angular measure of particle penetration



h  = vapor film thickness,  cm



p  = pressure,  dynes/cm



r  B radial  coordinate



t  = time, sec



z  « axial coordinate



6  = angular  coordinate



V  - liquid viscosity, poise



o   » liquid  surface  tension,  dynes/cm
                                     59

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Literature Cited

Drees, W., Staub-Reinhalt. Luft. ^6, 31 (1966).

Ewers, W.E., Sutherland, K.L., Aust. J. Sci. Res.. Series A. 5^ 697 (1952).

Fuchs, N.A., The Mechanics of Aerosols, pp. 338-352, MacMillan, New York, 1964,

Goldshmid, Y., Calvert, S., A.I.Ch.E. J.. £, 352 (1963).

Hesketh, H.E., J. Air Poll. Control Assoc.. 24. 939 (1974).

Lang, S.B., A Hydrodynamic Mechanism for the Coalescence of Liquid Drops,
    Univ. of California  Lawrence Radiation Lab. Report No. UCRL-10097,
    Berkeley, 1962.

Levich, V.G., Physiochemical Hydrodynamics, p. 395, Prentice-Hall,
    Englewood Cliffs, 1962.

McDonald, J.E., J. Geophysical Res.. £8, 4993 (1963).

Pemberton, C.S., Int. J. Air Poll.. _3, 168 (1960).

Rabel, G., Neuhaus, H., Vettebrodt, K., Staub-Reinhalt. Luft. 25, 4 (1965).

Taubman, A., Nikitina, S., Akad. Nauk SSSR. 110. 816 (1956).

Taubman, A., Nikitina, S., Akad. Nauk SSSR. 116. 113 (1957).

Weber, E., Staub-Reinhalt. Luft. 28, 37 (1968).

Weber, E., Staub-Reinhalt. Luft. J9, 12 (1969).

Woffinden, G., Ensor, D., Markowski, G., Sparks, L., "Interfacial Surface
    Effects on Particle Colection," Second Fine Particle Scrubber Symposium,
    New Orleans, May, 1977.
                                      60

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Captions to Figures






Figure 1.       Coordinate system for particle penetration.




Figure 2.       Ratio of interaction time to film thinning time, R, as a




                function of liquid surface tension with particle diameter as




                parameter (for an "impact" velocity of 7.6 cm/sec).




Figure 2.       Ratio of interaction time to film thinning time, R, as a




                function of "impact" velocity with particle diameter as




                parameter (for a liquid surface tension of 72.A dynes/cm).
                                      61

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                               TABLE 1
"Impact"
Velocity
(cm/sec)
7.6
it
it
it
tt
tt
35
64
Liquid
Surface Tension
(dynes /cm)
72.4
60
50
40
30
20
72.4
it
Penetration Depth/Particle Radius
8.2 x 10~3
9.0 x 10~3
9.8 x 10"3
1.1 x 10"2
1.3 x 10~2
1.6 x 10~2
3.8 x 10"2
6.9 x 10"2
Dimensionless penetration depths (penetration depth/particle radius) for



a 0.5 urn particle.  (Impact velocities of 7.6 and 64 cm/sec are the



terminal falling velocities in air of 50 and 200 um water drops, respectively.)

-------
vapor
liquid
                 Fluid advances toward
                 particle with velocity, V.
    FIGURE  1
         63

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 100.0
LJ
j| 10.0

0
=!   1.0
O

1  0.1
LU
  0.01
                                        D=0.5
D=1.0jjm

         20      30     40     50     60     7O

              LIQUID SURFACE TENSION (dynes/cm)
                         FIGURE 2
                           64

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 100.0
LJ
o 10.0
UJ
    1.O
o:
u
0.1
  0.01^—l
          10
                                       = O.5jum
             20      30     40      50


              IMPACT VELOCITY  (cm/sec)
60
                         FIGURE 3
                         65

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                                TECHNICAL REPORT DATA
                          (Please read Inunctions on the reverse before completing)
        NO.
  EPA- 600/7-78-097
                           2.
                                                       3. RECIPIENT'S ACCESSION NO.
J TITLE AND SUBTITLE
 Effects of Interfacial Properties on Collection of
  Fine Particles by Wet Scrubbers
                                 5. REPORT DATE
                                  June  1978
                                 6. PERFORMING ORGANIZATION CODE
 7 AUTHORIS)
 G. J.Woffinden, G.R. Markowski, andD.S.Ensor
                                 8. PERFORMING ORGANIZATION REPORT NO

                                  MU 77 FR-1503
9 PERFORMING ORGANIZATION NAME AND ADDRESS
Meteorology Research, Inc.
P.O. Box 637
Altadena, California  91001
                                                       10. PROGRAM ELEMENT NO.
                                 E HE 62 4 A
                                 11. CONTRACT'GRANT NO.

                                 68-02-2109
 12. SPONSORING AGENCY NAME AND ADDRESS
 EPA, Office of Research and Development
 Industrial Environmental Research Laboratory
 Research Triangle Park, NC 27711
                                 13. TYPE OF REPORT AND
                                 Final; 6/75-12/77
                                                                        PERIOD COVERED
                                 14. SPONSORING AGENCY CODE
                                  EPA/600/13
 is. SUPPLEMENTARY NOTES JERL-RTP project officer is D.L.
 541-2925.
                               Harmon, Mail Drop 61, 919/
 16. ABSTRACT
          The report gives results of an analysis of typical wet scrubber models to
determine the effects of surface tension on particle removal efficiency.  Particle
capture  (removal) is a two-step process: collision of a particle with a spray droplet,
and coalescence with the droplet. A change in surface tension of the scrubber water
can influence both steps. The coalescence process (after a particle collides with a
scrubber droplet) has been described by a film-thinning model that assumes that
coalescence is controlled by the thinning rate of an air or vapor layer trapped be-
tween an impacting particle and droplet. If the film thins and ruptures before the
particle rebounds, coalescence occurs.  The thinning model predicts that a reduction
in droplet surface tension allows deeper particle penetration into the droplet. The
escaping vapor film therefore has a longer more resistive path, resulting in longer
thinning times,  thus reduced coalescence  probability. When the surface tension of a
scrubber liquid is modified, collection efficiency may be slightly improved or de-
graded depending on the spray droplet sizes and the sizes of particles being removed.
                             KEY WORDS AND DOCUMENT ANALYSIS
                DESCRIPTORS
                                          b.IDENTIFIERS/OPEN ENDED TERMS
                                             c. COSATI Field/Group
Air Pollution
Dust
Scrubbers
Gas Scrubbing
Mathematical Models
Interfacial Tension
Efficiency
Coalescing
Air Pollution Control
Stationary Sources
Particulate
Removal Efficiency
13B
11G
07 A, 131
13H
12A
07D
14B
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