United States
               Environmental Protection
               Agency
Robert S. Kerr Environmental
Research Laboratory
Ada, OK 74820
               Research and Development
EPA/600/SR-93/021   May 1993
EPA       Project  Summary
                Laboratory  Study  on  the  Use of
                Hot  Water to  Recover  Light Oily
                Wastes  from  Sands
               Eva L. Davis and Bob K. Lien
                 This laboratory research project in-
               vestigated the use of hot water to re-
               cover oily contaminants that are less
               dense than water, highly viscous  at
               ambient temperatures, and essentially
               nonvolatile. Displacement experiments
               were conducted at constant tempera-
               tures in the range from 10 to 50°C, and
               an increase of approximately 17 to 22
               percent in oil recovery was achieved.
               The major mechanism for the increased
               recovery appeared to be viscosity re-
               duction. Transient temperature dis-
               placement experiments were  also
               performed by placing the oil-saturated
               column in the incubator at 10°C and
               using water at 50°C to displace the oil.
               The oil recovery from these experi-
               ments was comparable to that found
               for a 40°C constant temperature water-
               flood. Capillary  pressure-saturation
               curves  and the  displacement experi-
               ments showed that the residual water
               saturation increases with temperature,
               while the residual oil  saturation de-
               creases with temperature. Comparison
               of the capillary  pressure for a given
               wetting phase saturation for  different
               fluid pairs and for different tempera-
               tures show that the ratio of interfacial
               or surface tensions cannot account for
               changes  in the capillary  pressure
               curves as the fluids and temperatures
               are changed.
                  This Project Summary was devel-
               oped by EPA's Robert S. Kerr Environ-
               mental  Research Laboratory, Ada, OK
               74820, to announce key findings of the
               research  project that  is fully docu-
               mented in a separate report of the same
               title (see Project Report ordering infor-
               mation at back)
Introduction
  Cases of soil and groundwater contami-
nation by organic liquids that are immis-
cible with water are numerous and involve
many  different types of organic liquids.
The properties of these fluids, such as
density, volatility, viscosity, and water solu-
bility, vary significantly, and therefore dif-
ferent remedial techniques will be required
in  dealing with these  different contami-
nants. For oils that are viscous and non-
volatile, enhanced recovery using hot water
has been demonstrated in the laboratory
by researchers in the petroleum industry,
and this technique has  been used at vari-
ous field sites.
  The purpose of this research project is
to  investigate the use  of moderately hot
water  for the displacement of oily con-
taminants from the subsurface. The ex-
pectation is that the heat source will be
waste heat from  an industrial process,
which will limit the injection temperature of
the water to approximately 50°C. A litera-
ture review was conducted into the effects
of  porous media and fluid properties on
the displacement of oil by water and the
effects of heat on the  displacement  pro-
cess. Laboratory experiments were con-
ducted to study the effects of heat on the
capillary pressure-saturation relations and
displacement process, and numerical simu-
lations were  run  in an attempt to model
the results.

Experimental Materials and
Methods
  The oil phase used for these experi-
ments was Inland 15 Vacuum Pump Fluid,
and distilled water was used for the dis-
placing fluid. The viscosity of the oil, its
density, and its surface  and interfacial ten-
                                                                Printed on Recycled Paper

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 sion  were measured over the range of
 temperatures  of  interest.  Two  different
 silica sands were  used for  the porous
 media. The first sand, referred to as 20/30
 sand, has a very uniform grain size distri-
 bution with all grains passing the #20 sieve
 but retained on the #30 sieve, making all
 grains in the range of 0.85 to 0.60 mm.
 The second sand was a mixture of three
 size ranges of sands, giving one third (by
 weight) of  the grains  in each of the size
 ranges of 0.85 to 0.50 mm, 0.50 to 0.25
 mm and 0.25  to 0.106 mm. This  sand is
 referred to as the mixed sand.
   Three types of experiments were per-
 formed.  Capillary pressure-saturation
 curves were determined for each of the
 sands for water-air and water-oil. The pres-
 sure-saturation relations were determined
 at the constant temperatures  of  10 and
 30°C. The  other two types of experiments
 were constant temperature displacement
 experiments in the range of  10 to 50°C
 and transient temperature displacements
 where the  oil-saturated column was held
 in an incubator at 10°C and water at 50°C
 was used to displace the oil. All displace-
 ment experiments were performed with
 one-dimensional stainless steel columns.
 The soil columns were initially fully satu-
 rated with water, which was displaced by
 oil. The oil was then displaced by water.
 The column effluent was collected in a
 fraction collector so that the fraction of oil
 in the effluent versus the amount of water
 injected could be determined.  The pres-
 sure at each end of the column was mea-
 sured throughout the displacements. The
 constant temperature  displacements pro-
 vided information on the flow properties of
 the sands and fluids at each of the tem-
 peratures, while the transient temperature
 experiments more closely  modelled the
 hot water displacement  that would occur
 in the field.

 Experimental Results and
 Discussion
  The capillary pressure-saturation curves
 for the water/air systems show that tem-
 perature  has a significant  effect  on the
 these curves.  The increase in  tempera-
 ture from 10 to 30°C caused a decrease
 of approximately 30 percent  in the dis-
 placement pressure for these curves and
 caused an  increase in the residual water
 saturation in the 20/30 sand. The residual
 saturation of the mixed sand was essen-
tially the same at each temperature. The
pressure-saturation curves  measured for
the water/oil systems  essentially did not
change over the temperature range of 10
to 30°C,  other than  changes  in the  re-
sidual water and oil saturations. Compari-
 son of the water/air to water/oil curves for
 each of the sands showed that the water/
 oil curves were significantly different from
 the  water/air curves. The  Brooks-Corey
 (1964) and  van  Genuchten (1980) equa-
 tions were fit to these curves, and using
 these equations the relative permeability
 to each phase as a function of saturation
 could be predicted.
  The constant temperature displacement
 experiments showed an increase in oil
 recovery of  about 17 to 22 percent as the
 temperature was  increased  from  10°C
 (which was  considered ambient tempera-
 ture) to 50°C. The greatest increases  in
 oil  recovery were found at  breakthrough,
 with increases as great as  30 to  50  per-
 cent. The mixed sand always showed a
 greater oil recovery than the 20/30 sand.
 The oil saturation remaining in the column
 after the injection of 10 pore volumes  of
 water was about 39 percent for the 20/30
 sand at 10°C,  and 30  percent at 50°C.
 For the mixed sand, the oil remaining af-
 ter  the injection of 10  pore  volumes  of
 water was  33  percent  at  10°C  and 23
 percent at 50°C. Thus, the increased tem-
 perature reduced the oil remaining in the
 column by 25 to 30 percent.
  These remaining oil saturations  are sig-
 nificantly  greater  than the residual oil
 saturations  found in the capillary pres-
 sure-saturation  curves. Considering the
 water to oil ratio  of the effluent at the
 end of the displacement experiments, an
 additional 16 to 20 pore volumes of wa-
 ter  would have  to be injected to  reduce
 the oil saturation in the columns to the
 true residual.
  Pressure  measurements  recorded dur-
 ing  these displacements showed that the
 maximum pressure during  the  displace-
 ment occurred at the time of water break-
 through, i.e., as the water reached the
 effluent end of the column. As the tem-
 perature increased, the pressures in the
 column  and the  pressure drop along the
 column decreased significantly.
  The transient temperature experiments
 were run to more closely model the  dis-
 placement  process that  would occur  in
 the  field. Water at 50°C was used to  dis-
 place oil at  10°C from the column, while
 the  system  was held in a constant tem-
 perature incubator. The temperature in the
 column was  monitored at 4 locations along
 the  column during the displacement. The
temperature at any location remained at
 10°C until the hot water front reached it,
then the temperature rose quite rapidly to
 its equilibrium temperature. At the influent
end of the column, the column reached at
maximum temperature of about 37 to 39°C,
and the equilibrium temperature along the
 column dropped off linearly along the col-
 umn to about 30°C close to the effluent.
 Undoubtedly,  the stainless steel column
 used for these experiments moved heat
 away  from  the  sand  faster  than  would
 occur  in a field  situation because  of the
 significantly higher thermal diffusivity  of
 stainless steel compared to that of silica
 sand.  Attempts to insulate the column  to
 reduce the heat loss increased  the tem-
 perature along  the  column by  approxi-
 mately  2°C  but  did not  appear  to
 significantly affect oil recovery.
   Despite the fact  that the heat essen-
 tially did not travel in front of the hot water
 front, the benefits of the increased tem-
 perature were realized in terms of  the oil
 recovery. The percent oil recovery  at the
 time of water breakthrough was not sig-
 nificantly increased, but the oil  recovery
 after water breakthrough was increased.
 The final oil saturation after the  injection
 of approximately 10 pore volumes  of wa-
 ter was similar  to  that achieved  in the
 40°C constant temperature water-floods.
   The pressure drop at the time of water
 breakthrough  for the transient tempera-
 ture displacement experiments was simi-
 lar to that measured in the 10°C  constant
 temperature  displacements. After  water
 breakthrough, the pressure drop along the
 column decreased quickly to a level com-
 parable to  a 40°C waterflood. Thus, the
 benefits of hot water in terms of the pres-
 sure required to  drive the displacement
 process was not realized until after water
 breakthrough.
   From the data of oil recovery versus
 volume of water injected for the constant
 temperature displacement experiments, the
 ratio of oil  permeability to  water perme-
 ability  can be calculated for the range of
 saturations in  the column between  water
 breakthrough and the end of the displace-
 ment by the  method  of Welge (1952).
 These  calculations showed that  the per-
 meability ratio at low water saturations  is
 shifted to higher values as the tempera-
 ture is  increased. As the water saturation
 is increased beyond about 0.4 to 0.5, the
 ratio of permeabilities  tend to merge to
 the same line. The relative permeability to
 oil and to water was also be calculated by
 the graphical technique  developed by
 Jones  and  Roszelle  (1978), which  is
 equivalent to the technique developed by
 Johnson et  al.  (1959).  The  relative
 permeabilities calculated by this method
 show  that  the relative permeability  to
 each  phase  tends to increase as the
temperature  increases, but the perme-
ability  ratios calculated from  these indi-
vidual  permeabilities do not change with
temperature. The permeability ratios cal-

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culated based on  the  method of Jones
and Roszelle (1978) are significantly lower
than the ratios calculated based on the
method of Welge (1952). It is not possible
to tell at this time  which technique gives
the more accurate  ratios.
Simulation of Constant Tempera-
ture Experiments
  Attempts  were made to simulate the
constant temperature displacements us-
ing the Buckley-Leverett (1941) equation
for two-phase flow. Using this equation,
the amount  of oil recovered from the col-
umn as a function  of the amount of water
injected can be calculated. Input needed
for the calculation  is the viscosity ratio of
the fluids and the  relative  permeability of
each fluid as a function of  saturation. The
permeability ratios  were calculated based
on the methods of Welge (1952) and Jones
and Roszelle (1978) and on the Brooks-
Corey (1964) and  van Genuchten (1980)
equations fit to the  capillary pressure-satu-
ration curves.  None of these permeability
ratios were able to  accurately simulate the
oil recovery history found in the displace-
ment experiments.  Some qualitative  infor-
mation, however, can still be gained from
these simulations.  Comparison of the re-
sults of the experiments with the simula-
tion  results when  permeability ratios
corresponding to a  10°C displacement are
used with the smaller viscosity ratios found
at higher temperatures shows that the in-
creased recovery at higher temperatures
found in the laboratory displacements are
greater than can be accounted for based
on the decrease in viscosity ratio alone.
Simulations  using the permeability ratios
determined at higher temperatures shows
that this increase in recovery is likely due
to shifts in  the  permeability ratios with
temperature.

Conclusions
  These experiments have shown that the
use of hot water will increase the recovery
of oils from sands over that which  can be
recovered using a waterflood at ambient
temperatures. The increase in oil recovery
found over the moderate  temperature
range studied here was approximately 17
to 22 percent. This reduced the residual
oil saturation remaining  in these  sands
after 10 pore volumes of water throughput
by approximately 25 to 30 percent. How-
ever,  even the residuals of 23 to 30 per-
cent of the pore  space  found in 50°C
constant temperature displacements would
probably require additional treatment.
  The wide range of contamination prob-
lems facing those involved in subsurface
restoration will  require  a  variety  of
remediation techniques in  order to deal
with the problems effectively and efficiently.
Thermal methods such as hot water dis-
placements  of oily  contaminants  is one
technique which should be useful in  the
recovery of an oily phase that is viscous
and  essentially nonvolatile. A major  ad-
vantage of hot water is that  it does  not
require the addition of new, potentially toxic
chemicals to the subsurface.

References
  Brooks, R. H.,  and A. T. Corey, Hydrau-
    lic Properties of Porous Medium,  Hy-
    drology Paper, #3,  Colorado State
    University,  Fort  Collins,  CO,  March
    1964.
  Johnson, E. F., D. P. Bossier, and Y. O.
    Nauman, Calculation of relative per-
    meability from  displacement  experi-
    ments, Trans. AIME, 216, 1959.
  Jones,  S.  C., and  W.  O. Roszelle,
    Graphical techniques for  determining
    relative permeability from displace-
    ment experiments, J. of  Pet. Tech ,
    30(5):807-817, 1978.
  van Genuchten, M. Th., A  closed-form
    equation for predicting the hydraulic
    conductivity  of unsaturated soils, Soil
    Sci. Soc. Am. J., 44:892-898,  1980.
  Welge,  H.  J.,  A simplified  method  for
    computing oil recovery by gas or wa-
    ter drive, Trans. AIME, 91-98, 1952.
                                                                   •&U.S. GOVERNMENT PRINTING OFFICE: 1993 - SSO-O67/SO130

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  Eva L Davis (also the Project Officer, see below) and Bob K. Lien are with Robert
    S. Kerr Environmental Research Laboratory, Ada, OK 74820
  The complete report, entitled "Laboratory Study on the Use of Hot Water to Recover
    Light Oily Wastes from Sands," (Order No. PB93-167906; Cost: $19.50; subject
    to change) will be available only from
          National Technical Information Service
          5285 Port Royal Road
          Springfield, VA 22161
          Telephone: 703-487-4650
  The EPA Project Officer can be contacted at
          Robert S. Kerr Environmental Research Laboratory,
          U.S. Environmental Protection Agency
          Ada, OK 74820
United States
Environmental Protection Agency
Center for Environmental Research Information
Cincinnati, OH 45268

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