EPA-600/2-76-017
March 1976
Environmental Protection Technology Series
                                     RENOVATION  OF
        INDUSTRIAL INORGANIC WASTEWATER  BY
  EVAPORATION WITH INTERFACE ENHANCEMENT
                               Industrial Environmental Research Laboratory
                                    Office of Research and Development
                                   U.S. Environmental Protection Agency
                                          Cincinnati, Ohio  45268

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                RESEARCH REPORTING SERIES

Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have  been grouped  into five series. These five broad
categories were established to facilitate further development and application of
environmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The five series are:

     1.    Environmental Health Effects Research
     2.    Environmental Protection Technology
     3.    Ecological Research
     4.    Environmental Monitoring
     5.    Socioeconomic Environmental Studies

This report  has been  assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series. This series describes research performed to develop and
demonstrate  instrumentation, equipment, and methodology to repair or prevent
environmental degradation from point and non-point sources of pollution. This
work provides the new  or improved technology required for the control and
treatment of pollution sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.

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                                           EPA-600/2-76-017
                                           March 1976
     RENOVATION OF INDUSTRIAL INORGANIC WASTEWATER

       BY EVAPORATION WITH INTERFACE ENHANCEMENT
                          by
                    Hugo H. Sephton
            Sea Water Conversion Laboratory
               University of California
              Richmond, California
                 Project  Number  R-802753
                     Project  Officer

                   Richard B.  Tabakin
          Industrial  Pollution Control  Division
Industrial  Environmental  Research  Laboratory  (Cincinnati)
                Edison,  New Jersey 08817
      INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
           OFFICE OF RESEARCH AND DEVELOPMENT
          U.S.  ENVIRONMENTAL PROTECTION AGENCY
                CINCINNATI, OHIO  45268

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                           DISCLAIMER
     This report has been  reviewed  by  the  Industrial  Environmental
Research Laboratory, U.S.  Environmental  Protection Agency, and
approved for publication.   Approval  does not  signify  that  the con-
tents necessarily reflect  the views  and  policies of the  U.S. En-
vironmental  Protection Agency, nor  does  mention of trade names or
commercial products constitute endorsement  or recommendation for
use.
                                  i i

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                          FOREWORD

     The multi-media  character of pollution resulting from
the extraction, processing, conversion, and utilization of
energy and mineral resources, and from industrial processing
and manufacturing, requires an approach which recognizes
the complex impact of these operations on our environment.

     The Industrial Environmental Research Laboratory,
Cincinnati, utilizes  a multidisciplinary approach in the
development and demonstration of technologies to effectively
deal with the pollution associated with these operations.
The Laboratory assesses the environmental and socio-economic
impact of industrial  and  energy-related activities and identifies
and evaluates control alternatives.

     This report evaluates a novel method of increasing the
efficiency of an evaporative process to recycle three types of
industrial waste waters;  power plant cooling tower blowdown,
industrial steam generation blowdown, and an acidic mine
drainage type of wastewater.  The method, known as interface
enhancement, involves the addition of a surfactant to the
wastewater stream prior to passing the stream through a vertical
tube evaporator.  For all three waste streams a considerable
increase in heat transfer performance was observed.   It was
concluded that substantial capitol and operating cost savings
could be realized by modifying existing evaporation systems to
accommodate the interface enhancement technique.

     This project was one of several projects undertaken by
IERL-C to demonstrate new approaches to increasing the reuse
of industrial wastewater,  a source of much water pollution
throughout the country.   This  report will be especially interesting
to those individuals involved  in the design or operation of
industrial systems which use large amounts of water for cooling
purposes, and to individuals involved in industrial  waste water
research.
                               David G.  Stephan
                                   Director
            Industrial Environmental Research Laboratory.Cincinnati
                                i i i

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                                   ABSTRACT

     A  novel method of vertical  tube evaporation  (VTE) to  improve heat
 transfer  performance was applied  to the concentration of three types of  in-
 dustrial  wastewaters.  This method, interface enhancement, relies upon the
 addition  of a few parts per million of a selected surfactant to the waste-
 water feed followed by imposed two-phase foamy  liquid-vapor flow over the
 heat transfer surfaces.  Applied  to the concentration of power plant cooling
 tower blowdown and boiler blowdown, interface-enhanced VTE provided an
 approximate 120 percent increase  in the usual VTE heat transfer performance,
 using a 5,000 gpd pilot plant having double-fluted aluminum-brass distillation
 tubes,  under process conditions that are realistic for large industrial plants.
 Acidic  mine drainage water, concentrated by double-fluted titanium evaporator
 tubes provided about a 60 percent heat transfer performance enhancement.
 Beneficial side effects of the surfactant additive were to inhibit the crystal-
 lization  of solutes, permitting concentration of the wastewaters to smaller
 volumes.  This work indicates feasibility and improved economics for renova-
 tion-recycle of each of the three types of wastewater examined.
     Industrial feasibility demonstration projects for each of the three waste-
water types examined are recommended.   A method and flow diagram for the de-
 salination-recycle of power plant cooling tower blowdown by interface-
enhanced VTE integrated with a typical  power plant coolant cycle and utiliz-
 ing waste heat from that cycle, is described and recommended.
     This report was submitted in fulfillment of grant number R802753 under
partial  sponsorship by the Environmental  Protection Agency.  Work was com-
pleted as of May 31, 1975.
*U.S. Patent No. 3,846,254, November 5, 1971*
                                      i v

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                               CONTENTS






                                                               Page



ABSTRACT                                                        jv




LIST OF FIGURES                                                 vi




ACKNOWLEDGMENTS                                                vjf






SECTIONS




  I   CONCLUSIONS                                                 1




 II   RECOMMENDATIONS                                             3




III   INTERFACE-ENHANCED VERTICAL TUBE EVAPORATION                5




        INTRODUCTION                                             5




        BACKGROUND                                               7




        PROJECT PLAN                                            10




        UPFLOW VTE PILOT PLANT FACILITY USED FOR THIS STUDY     12




        UPFLOW VTE PYREX GLASS EVAPORATOR                       20




        DISTILLATION TUBES USED IN THE VTE PILOT PLANT          23




        EXPERIMENTAL WORK                                       25




          1)   Investigation of Cooling Tower Slowdown           25




          2)   Industrial Steam Generator Slowdown Concentration 36




          3)  Acidic Mine Drainage Concentration                k6




        DISCUSSION                                              53




        REFERENCES                                              58

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                                    FIGURES


Number                    Title                                        Page

  1      SIMPLIFIED FLOW DIAGRAM FOR UPFLOW VTE PILOT PLANT              13

  2     UPFLOW VERTICAL TUBE EVAPORATION PILOT PLANT                    14

  3     STEAM SIDE FLOW PATTERN                                         16

  4     TYPICAL TWO-PHASE FLOW THROUGH VTE ORIFICE PLATE                19

  5     FOAMY ANNULAR FLOW FROM DISTILLATION TUBES                      21

  6     PYREX TUBE CRYSTALLIZING EVAPORATOR                             22

  7     AXIALLY AND SPIRALLY DOUBLE-FLUTED DUTILLATION TUBES            24

  8     ENHANCEMENT OF HEAT TRANSFER PERFORMANCE IN VTE                 27
          OF MOHAVE COOLING TOWER SLOWDOWN

  9     HEAT TRANSFER PERFORMANCE OF MOHAVE COOLING TOWER BLOWDOWN      28

 10     CONCENTRATION OF MOHAVE POWER PLANT COOLANT BLOWDOWN            30
          BY INTERFACE-ENHANCED VERTICAL TUBE EVAPORATION AT 130°F

 11      RENOVATION AND RECYCLE OF POWER PLANT COOLING TOWER BLOWDOWN    31

 12     UPFLOW VTE PERFORMANCE WITH BOILER BLOWDOWN                     38

 13      INTERFACE ENHANCEMENT RESPONSE WITH BOILER BLOWDOWN             40

 ]k     INTERFACE-ENHANCED UPFLOW VTE PERFORMANCE WITH BOILER           *»1
          BLOWDOWN

 15      10-FOLD CONCENTRATION OF BOILER BLOWDOWN                        1*3

 16      INTERFACE ENHANCEMENT RESPONSE WITH COPPER TUBES                1»9

 17      INTERFACE ENHANCEMENT RESPONSE WITH ALUMINUM-BRASS AND          51
          TITANIUM TUBES
                                     VI

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                              ACKNOWLEDGMENTS




     This work was supported by a research grant from the Environmental




Protection Agency and,  in part,  by the University of California.   The author




gratefully acknowledges the technical  assistance of Mr.  Carl  L.  Freel, and




the helpful interest of Mr. Richard B. Tabakin of the EPA. Assistance in




providing wastewater samples for the test program was received from the




Bechtel Power Corporation and several  other industrial entities.  Thanks




to Margaret Knight for typing the manuscript.
                                      VI I

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                           SECTION I:   CONCLUSIONS



     The following conclusions were drawn from or confirmed by  the work




reported here:




     1)  The  interface-enhanced mode of operating a  vertical  tube evaporator




(VTE) is technically feasible for the  concentration-recycle of  each of the




three types of industrial  wastewaters  examined;  the  main  beneficial effects




to be anticipated are substantial capital and/or operating cost savings.




Evaporator heat transfer performance enhancements  ranging from  60 to  150




percent were demonstrated under process conditions  that are  realistic for



industrial operation.




     2)  Side effects of the interface-enhancement  agent  examined provided




additional advantages; these side effects are an inhibition  of  the onset




of crystal formation during the gradual concentration of  wastewater and  the




dispersant effect of the surfactant additive.




     3)  In the case of the concentration-renovation of Mohave  Power  Plant




cooling tower blowdown, a tenfold evaporation was  readily obtained  after  the




addition of 10 ppm of a selected surfactant,  at heat transfer performance




rates about double those obtained without the additive.   These  results




indicate that cooling tower blowdown can be most economically desalted for




recycle by integrating a VTE loop within the temperature  span available  in




the coolant cycle of a large power plant, as shown in the flow diagram of




Figure 1 1.




     4)  Several  alternative methods of cooling tower blowdown  renovation-




recycle can benefit significantly from the adoption of the  interface-enhanced




mode of operating an evaporator.  These  include concentration of blowdown




by vapor compression VTE, by multiple effect VTE with upflow or downflow of




the feed, and by low temperature VTE utilizing waste heat for evaporation.




                                       1

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     5)   In the case of examining an industrial  boiler blowdown the applica-




tion of  interface-enhanced VTE provided substantial  benefits;  the evaporator




heat transfer performance was more than double its conventional performance,




and a concentration factor of 20 was readily obtainable without significant




precipitation of solutes occurring.




     6)  The renovation-recycle of industrial  boiler blowdown  by either  the




single effect vapor compression VTE  method or by a multiple effect VTE  is




feasible and appears economically acceptable with the interface-enhanced




mode of operation.




     7)  In the case of the acidic mine drainage type of wastewater examined




it was apparent that the addition of a surfactant before its concentration




by upflow VTE provides the benefits  of retaining particulates  in suspension,




inhibiting the crystallization of solutes, and of increasing the evaporator




heat transfer performance substantially.   Because of the highly corrosive




nature of this type of effluent, titanium tubes  and stainless  steel equip-




ment are  indicated to be advisable;  copper-based alloys were indicated  as




unsuitable.  The heat transfer performance of titanium distillation tubes




was  increased by about 60 percent by the addition to the feed of about  10



ppm of a selected surfactant.

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                        SECTION II:  RECOMMENDATIONS




     The following recommendations are submitted, based on the work performed




under this project:




     1)  In order to demonstrate the advantages of this approach for industrial




wastewater renovation-recycle to the satisfaction of all interests, a mobile




pilot plant facility should be designed in cooperation with an architect-




engineering firm knowledgeable in the power plant field.  Subsequent field dem-




onstration tests should be jointly sponsored by several interested utilities and




carried out in collaboration with such interests, to provide a means for the




rapid evaluation and possible adoption of these procedures by industry.



     2)  Regarding industrial boiler blowdown renovation, it is recommended




that a demonstration project be undertaken by a large  industrial complex, for




instance a petroleum refinery.  The objective of such a project would be to




design, construct and field test a vapor compression VTE plant of a size and




scope that will satisfy industry and the EPA about the application, cost and




benefits of the interface-enhanced mode of VTE operation for industrial




wastewater recycle.




     3)  In regard to the concentration and recycle of highly corrosive



effluents, such as acid mine drainage and plating plant effluents,  it  is




recommended that further definitive test data be obtained by means of a




relatively small (about 3 to 5,000 gpd) mobile vapor compression VTE, con-




structed of titanium and stainless steel, and tested on three typical waste-



waters.




     k)  The beneficial interface-enhanced heat transfer effects have now




been well demonstrated on several  types of aqueous media.  However, the effects




of surfactant additives on evaporation under crystallizing or precipitation

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VTE conditions have not been adequately defined.   It is recommended that




further study be carried out in this area in the interest of wastewater




renovation-recycle.




     5)  The side effects of the surfactant additives that have been identified




appear to be beneficial.  These are the dispersant effect, the inhibition of




solute cyrstal1ization during concentration, and the inhibition of erosion and




corrosion.  These side effects should be more precisely defined, especially the




longterm benefits and disadvantages, including the useful  lifetime of the sur-




factant additives during continuous recycle and the fate of their thermal



degradation products.

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                                 SECTION I!I




                  INTERFACE-ENHANCED VERTICAL TUBE EVAPORATION



 INTRODUCTION




     The objective of this project was to obtain heat  transfer performance




data on the application of a novel evaporative procedure for wastewater  reno-




vation by pilot plant tests with several industrial  wastewaters.   These  data




would provide a basis for evaluating the process feasibility, and  the  cost




reductions available in the possible future  industrial  application of  this




procedure.




     The novel distillation method, "Interface Enhancement Applied to  the




Evaporation of Liquids,"  (1) relies upon the addition of a few parts per




million (ppm) of a selected surfactant to the liquid to be evaporated,




followed by imposing foamy two-phase, vapor-liquid flow over the heat  transfer




surfaces.   This mode of flow provides a k- to 6-fold increase in the brineside




or evaporation-side coefficient, which  in turn provides an evaporator  per-




formance enhancement or overall heat transfer coefficient increase of  50 to




200 percent, for multieffect vertical tube evaporation  (VTE) performed under




otherwise conventional process conditions ( 1 ).  The degree of enhancement




depends on the process conditions applied, such as whether the upflow or




downflow VTE mode is used, the type of distillation tube  installed, and the




evaporation temperature and the temperature difference  applied as well as the




type and concentration of surfactant additive used  (2,  3, b, 5).   In the case




of upflow VTE, the application of  interface enhancement has a very significant




further effect of improving the upflow  tubeside hydrodynamic stability.  This




follows from  the  improved foamy mode of  flow, whereby the liquid holdup in




the distillation  tube  is  reduced  by about a factor of 5.  Stated differently,




the liquid residence  time  is  substantially  reduced; this means that  the

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hydrostatic pressure drop, contributing a parasitic loss, is much reduced.



The net result is that the tubeside hydrodynamic pressure gradient is sub-




stantially lowered, usually by a factor ranging from 3 to 6.  Consequently,




the upflow process stability is significantly improved;   this in turn permits




stable upflow VTE operation at reduced effect-to-effect  temperature differences,




in the interest of saving heat, or fuel (6, 7).  It also permits relatively




high heat transfer performance at low evaporation temperatures and under




relatively low temperature differences (AT); such as used in vapor compression




VTE.



     Another distinct advantage of the interface-enhanced mode of VTE operation,




especially meaningful for wastewater renovation, is that the surfactant addi-




tive tends to suppress crystallization of solutes,  disperses particulates




present in the distilland to prevent their deposition on heat transfer surfaces,




and that  it can provide some erosion-corrosion protection by the formation  of




a surfactant layer adsorbed to the heat transfer surface and other surfaces  (8).




     The planned scope of work included pilot plant tests with three typical




industrial wastewaters; test data were to be obtained under typical upflow




VTE process conditions including data with the interface-enhanced mode of




operation.  The wastewaters tested were power plant cooling tower blowdown,




industrial steam generator (boiler) blowdown and an acidic mine drainage type.




     The pilot plant used was available from the author's earlier OSW-sponsored




projects on the development of enhanced heat transfer for VTE of seawater.




Some modifications were made for the tests reported here.  In addition a small




Pyrex glass-tubed upflow VTE was constructed to determine the effect of sur-




factant additives on solute crystallization during  the gradual concentration




of these wastewaters.

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BACKGROUND




     The interface-enhanced mode of upflow VTE  had  been  fairly well defined




in previous work in this laboratory, at  least for seawater  conversion under




typical multieffect process conditions  (1, 2, 3, ^,  5).   Several  reports




have also appeared on work done elsewhere, confirming  the effectiveness of




this enhancement procedure for downflow  VTE (9) and for  horizontal  tube




multieffect evaporation (HTME) (10).




     Approximately four years of development work by pilot  plant  testing  in




this laboratory preceeded the present work.  During this development period,




the interface enhancement effects were defined  for  a series of  special  and




commercial grade full-sized distillation tubes  of both smooth-walled,  and




various fluted-wall configurations.  The process conditions applied included




all the most significant parameters imposed in  the  individual  effects  of  a




real,  industrial installation.  Heat transfer performance enhancement  effects




had been demonstrated to be consistently obtained with a series of about




twelve different surfactants and with both freshwater and seawater feeds




under all of the usual  range of upflow VTE process  conditions (3, 5,  6).




The magnitude of this enhancement effect varied in  a consistent manner,




depending upon the type of distillation  tube,  the type and concentration  of




surfactant used and the process conditions applied  within the usual multi-




effect VTE range.  Thus it was known that  the  most effective upflow VTE




performance enhancement effects were obtained when the feed entering the




distillation tubes  was caused to  flash or partially vaporize into a two-




phase  liquid-vapor flow, for  instance, by  passing a preheated feed through




a  suitable nozzle or  orifice  (3).   In this manner evaporation of the liquid




is assured to occur along  the entire length of the distillation  tube.

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      The most significant  interface  enhancement  effects  have  been shown  to be



 the following (3,  5):




      1)   The imposed  foamy  mode  of vapor-liquid  flow over  the heat  transfer




 surfaces provides  for  thin-film, wiped-film evaporation.   This  results from




 the continuous  renewal  of  the  liquid  film  laid down onto this surface from




 liquid phase carried  interstitially  to  the vapor bubbles as a network of




 foam swept  over  this  surface by  the  vapor phase  flow.  This thin-film evapora-




 tion mechanism applies  to  both upflow and downflow of  the  feed.  It  is im-




 portant,  for high  interface enhancement, that the foamy  layer be maintained




 throughout  the  length of the distillation tubes.  This requires initiation




 of  foamy flow as or before  the feed  enters these tubes,  for instance, by




 flashdown at an orifice; continuation of the foamy layer flow depends on an




 adequate rate of evaporation, yet a  not excessive rate of  vapor flow which




 tends to break the foam up.  These parameters determine  the diameter and




 length of distillation  tube of a particular metal and flute profile best




 suited a  given evaporation  temperature and AT applied.




      2)   The second enhancement effect applies to the upflow  VTE mode only.




 It  has been  shown that  the  residence  time of the liquid  phase (feed) is sub-




 stantially  reduced as a result of the imposed foamy vapor-liquid flow through




 the  tubes.   Stated in other words,  the  liquid hold-up  is reduced, and this




 follows  from the more rapid passage of the liquid phase  through the tubes as




 a result  of  the foamy consistency.   As a consequence of  this  reduced liquid




 hold-up,   the  hydrostatic pressure drop axially through the distillation tubes




 is substantially reduced.   This in turn provides for the 3- to  10-fold hydro-




 dynamic tubeside pressure drop reductions.   These actual  two-phase pressure




 drops are constituted of a hydrostatic element, and a hydrodynamic element




which include  accelerational and frictional  pressure drop elements. Since the




                                      8

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downflow VTE has a very low hydrodynamic pressure drop  and  no  hydrostatic




pressure drop element, the pressure drop reduction effect of  interface  en-




hancement does not apply to this mode of VTE.   This explains,  in  part,  why




interface enhancement is about 50 percent less effective in downflow VTE




applications.  Another reason is that stable,foamy two-phase flow is much




more readily maintained in upflow VTE than in the downflow  mode,  and at




much lower surfactant concentrations.



     One of the main additional advantages of interface-enhanced  upflow VTE




over the downflow application follows from the fact that the former operation




does not require effect-to-effect feed  transfer or recirculation pumps.  This




provides a significant capital cost saving and more significant operation-




maintenance  (0 £• M) cost savings.  A  recent cost comparison study performed




by Kaiser Engineers  (11) concluded that  the capital cost savings provided by




interface-enhanced upflow  VTE over the  conventional downflow mode amount to




at least 25 percent and that 0 5- M cost savings would  be about 30 percent.




     The most  significant  single effect of  interface enhancement  is  to improve




the upflow  VTE tubeside stability; this permits  stable operation  even  at




relatively  low AT-values.  As  a  consequence,  one  can  increase  the number of




effects permissible within the  available temperature span of  120  to  250 F




usually  available  for a multieffect  VTE plant.   As a direct  result  of  the




 increased number of  effects,the gain ratio, or economy ratio,  is  increased




by up  to 50 percent  In the interest  of  saving steam or fuel.   Another  result




 is that  design flexibility is  improved, allowing improved  optimization of




capital  versus energy costs  (k)-




     Apart  from process  development  knowledge and experience, a  5,000 gallon per




day  (gpd) upflow VTE pilot plant was available  in this laboratory from previous




projects sponsored by the Office of  Saline Water  (OSW), for use in the present study.




                                         9

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 PROJECT PLAN




      a)  An initial  phase of about  three  months was  planned during which time



 the available equipment and facilities were  to be  reconditioned and  improved,




 in preparation for the main phase of  the  work.  Some preliminary exploratory




 work would also be done during  this phase.   Equipment and facilities made




 available for this project from California State and OSW sources were  inventoried




 at about $75,000.




      b)  The main  phase of this study included definitive tests, with  the  5,000




 gpd pilot plant, on  typical  wastewaters evaporated under realistic upflow  VTE




 multieffect process  conditions,  both  without and with surfactant additives  to




 these feeds.   It was anticipated that at  least three typical  industrial waste-




 waters would be examined.   These waters would be selected in  collaboration with




 EPA staff,  or as suggested by EPA,  to ensure relevance of the  test data.




      The main benefits  to  be expected from this project were:




      a)   A substantial  reduction in the cost of renovating  industrial wastewaters




 by VTE,  which produces  a  high quality distilled water for beneficial use.  The




 dispersing  effects of surfactant additives, to prevent fouling and scaling of




 heat  transfer surfaces, were to  be evaluated.  This  should permit evaporation




 to increased  solute  concentrations, and the evaporation of wastewaters that




 contain  particulate  and colloidal matter.  Disposal  of these  relatively small




 residual  concentrates would  be  at reduced cost;




      b)  A  broadened  scope  for applying evaporation  processes  in the renova-




 tion  of  industrial wastewaters,  to advance the state of the art of pollution




abatement.  A  reeent  study by Kaiser  Engineers ( 6 )  concluded that capital




cost  savings of about 25 percent and  annual cost savings of about 33 percent




are obtainable on a  12.5 MGD downflow VTE/MSF plant  if an upflow VTE/MSF process




with  interface enhancement  is adopted instead of the downflow mode.

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      c)  Advancement of our understanding of the mechanisms responsible for




 the  substantial  increase  in heat and mass transfer  rates, obtained by the




 interface  enhancement method of evaporation to be applied in this work.




      Additional  benefits  anticipated included training of students while




 working  toward  their MS or PhD degrees.  Well-trained personnel should provide




 a  valuable service  to the public,  in the environmental and public utility




 fields.  The proposed project would also be of benefit to the University of




 California,  by  providing  opportunities  and facilities for furthering the




 educational  process, generating  innovations and  advancing the state of the art




 in the field of wastewater  renovation.




      The legal  requirements for  industrial compliance with water quality




 standards  place  a  high priority on  the rapid development of suitable  tech-




 nology for purification of wastewater.   The  interface enhancement method  for




 VTE operation of this proposal appeared to provide  a very promising  tool  for




 complying  with  these  requirements  in some  instances.  Its development, and




 introduction into this  field  seemed well justified.




 Surfactant Additive Recovery-Recycle




      A method of recovery from concentrated  brine and  recycle  of  95~97 percent




 of the surfactant,  added  as a heat transfer  enhancement  agent  in  the VTE,  has




been developed through  the pilot  plant  stage   '   .  This  procedure,  foam




fractionation, provides  simultaneous  benefits  such as removing  (and  allowing




recovery) of metal ions  of interest as  well  as  particulates,  notably ferric




hydroxide from the VTE  blowdown  concentrate.   The foam  fractionation procedure




is  economically  attractive.
                                       11

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UPFLOW VTE PILOT PLANT FACILITY USED FOR THIS STUDY




     A versatile single effect, 5,000 U.S. gpd, 18-tube VTE pilot plant was




 designed and constructed  primarily  with  OSW  support  under  earlier   research




 and development projects  for  application of  interface  enhancement  to seawater




 desalting (k).  This  pilot plant was  also utilized  in this  EPA-sponsored




 work,and is  represented  in the simplified flow diagram of  Figure  1  and  shown




 photographed in Figure 2.  This  facility, comprising a reboiler  loop, an




 18-tube VTE  loop  and a heat reject  loop,  could impose  all  the significant




 process  conditions,  relevant  to  any one  of the effects in  a  typical multi-




 effect  VTE plant,  upon the 18-tube  VTE  loop.   This loop was  constructed from




 nonferrous materials compatible  with wastewater.  The  tubes  used  for these




 tests were double-fluted  aluminum-brass  (Yorkshire Imperial  Metals  Ltd.) of




 0.042-inch wall thickness, 2-inch OD x  10-foot heated  length, in an oxidized-




 annealed condition.  The  industrial  wastewater tested  was  recirculated  through




 the VTE  loop.   The interface-enhanced data were obtained after the  further




 addition of  a  selected surfactant to the  feed  in 5 to  50 ppm concentration.




 The VTE  loop was  washed with  fresh  water  and charged a fresh batch  of wastewater




 before  each  test  series.




      In  operation,  the desired steam-side temperature  (Ts) was preset on an




 automatic controller actuating a motorized steam valve to  admit boiler  steam



(at^Spsig) to  the  tubes of the U-tube heat exchanger in the  reboiler loop,




 shown on the far  right of Figure 1.  Fresh water was evaporated on  the  shell-




 side of  this heat  exchanger while in upflow, two-phase flow.  This  two-phase




 stream was injected tangentially into the large-domed  vapor  release vessel




 on  the upper right of  Figure  1.  The residual  liquid phase was recirculated




while the vapor produced was  conveyed to  the VTE loop  to serve as heating




 steam for the  18-tube  bundle.  To determine the total  heat flux  (Oj of  the




                                       12

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   COOLANT
   RECYCLE
COOLANT
 HEAT REJECT LOOP
                                     UPFLOW VTE EFFECT
           REBOILER LOOP
          SIMPLIFIED FLOW DIAGRAM FOR UPFLOW VTE PILOT PLANT
FIGURE I

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             Hlk-JB
UPFLOW VERTICAL TUBE EVAPORATION PILOT PLANT
FIGURE 2

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18-tube bundle the condensates off the steam-sides of these tubes  were



collected and their rates of flow measured,  individually for ^ selected  tubes




and, collectively for the remaining 15 tubes.   These measurements  showed




that variations in flux for individual tubes were within 2 percent.   A




measured fraction of the total steam flow was vented from the 18-tube bundle



and condensed, to remove noncondensables and to assure positive flow across




the steam-sides of the tube bundle.  All these steam-side condensates were




maintained under vacuum and returned to the reboiler loop with which it



comprised a closed cycle.




     Having the steam-side temperature  (Ts)  controlled at a level  present on




the automatic controller, the desired temperature difference (AT)  across the




walls of the  18-tube bundle depended upon the total heat flux (Qj  and the




duty of the heat reject loop shown on the left of Figure 1.  In order to




maintain this duty at a steady rate, a  large volume of relatively hot water




coolant was recirculated under moderate pressure  (40 psig) through the heat




reject loop at about 1,000 gallons per minute, and cold water was constantly




injected into this coolant with the simultaneous  rejection of hot water from




it.  The AT for the VTE loop was  in this way controlled at any desired level




(±0.1 F), after the steam-side temperature, Ts, became stabilized at its




selected, preset level (±0.1°F).




     Wastewater feed was admitted  into  the VTE loop under vacuum, and recir-




culated at about 100 F until deaeration was completed under evacuation.   The




steam-sides of the tubes were  in  a dark-brown, ox idized-annealed and fully




stabilized condition after  intermittent operation for about 2 years without




any reconditioning.  The 18-tube  bundle and steam-side  flow  pattern  are  shown




in Figure 3.  providing positive flow  across the  entire  bundle  and a  measured




vent rate (3~10%) collected along the entire  length of  the tube bundle.





                                      15

-------
               STEAM SIDE   FLOW  PATTERN

Distillation tubes were  spaced 0.5-inch on a triangular pattern,  with dummy
tubes  (shaded) and baffles to ensure continuous steamside flow from the
plenum to the vent tube  along the entire bundle length.  The vent tube had
0.125-inch holes drilled at 6-inch intervals along its entire length for
adequate vent collection.
                                                    FIGURE 3
                                   16

-------
     Under typical  operating conditions,  the  temperature of  the deaerated




feed was adjusted to correspond with the  steam-side  temperature  (±1  F) by




passing it through  a steam-heated exchanger,  controlled by an  automatic steam




control valve, and  was then dumped into a standing  leg.  From  this  standing




leg the feed flowed through the feed distributor  into  the  inlet ends of the




18-tube bundle, under force of gravity and in response to  the  inter-effect




temperature difference.  Upon passing through the orifice  plate,  the feed




flashed down to provide a two-phase vapor-brine system for evaporative flow




up the tubes.  Two-phase flow up the tubes was maintained  by the  vapor released




from the brine; continuous evaporation of the brine was  supported by heat




passing through the tube wall from the steam  condensing  on the steam-sides




of the tubes.  The  hydrodynamic pressure  drop through  the  tubes,  measured  in




a direct manner by  means of sight glasses communicating  with the tube  inlet




ends (post-orifice) and with the vapor release vessel, provided a continuous




indication of the hydrodynamic oscillations and of  the upflow stability  in




the distillation tubes.  The pressure drop across the orifice plate, and  the




hydrostatic pressure of the feed before passing through the orifice plate,




were also measured  with manometers.  Outflow of brine from the tubes was  usually




in the form of an annular layer on the tube inner wall,  while the vapor  phase




flowing up in the center of the tube was  relatively free of liquid.  A dis-




continuous, gushing mode of outflow was usually observed,  with the annular




brine  layer emerging  in spurts,but with the vapor core flow appearing to be




continuous.  Entrainment separation from the vapor produced was readily




accomplished with an  impingement plate and a mesh demister positioned about




20 inches above the tube outlet ends,  in the vapor release vessel shown in the




top center of Figure  1.  Primary separation at the tube outlet ends was aided




by having the tubes extended above  the upper  tube sheet, and  by having slots




                                      17

-------
or holes in this part of the  tube.   The vapor produced was condensed in the




heat reject loop and returned to the brine loop.




     Temperature measurements were made with platinum-resistance probes pro-




viding a direct, digital display of steam-side temperature (Ts), of feed tem-




perature below the orifice plate (Tf), of final  brine temperature (Tb)  immedi-




ately after passing through the vapor release vessel, and of the temperature




difference (AT = Ts - Tb).  These data were checked by measuring the vapor




pressures on the steam-side (Ps) and the brine-side (Pv) with an absolute




manometer and correcting for boiling point elevation, and by mercury-filled




thermometers installed  in direct contact with the flowing fluids.




     Upflow VTE heat transfer data were obtained under steady-state operating




conditions, first without any addition of surfactant to wastewater feed, and




then with specific concentrations of a selected surfactant added to this feed.




Data without surfactant additives compared well  with those obtained earlier in




an OSW sponsored test series with this pilot plant.  The interface-enhanced




data were obtained with the same process conditions, after the addition of a




selected surfactant (Neodol-25-3A, or Neodol 25-3S, Shell Chemical Company)




to the wastewaterfeed.  Surfactant addition was observed to bring about a




significant change in the mode of two-phase flow, characterized by foaming




at the inlet and outlet ends of the tubes and by a substantial reduction in




the tube pressure drop, AP.  These typical modes of flow through the orifice




plate,  spaced about three inches from the tube inlet ends,are shown in Figure




k.  Without a foaming agent additive the feed flashed down at the orifices




into a  continuous liquid layer, with the vapor and feed liquid passing through




this liquid layer into  the tube inlet ends.  After the addition of surfactant




the feed flow was radically changed.  Flashdown at the orifice plate produced




foamy jets passing through a vapor-filled space into the tubes.  This mode




                                       18

-------
                    a.  Without Foaming Agent Added to Feed,
      b.   With  Foaming  Agent  Added,  and Orifices in Line with Tube Ends.



          c.  With Foaming Agent, and Orifices Offset from Tube Ends.





TYPICAL TWO-PHASE FLOW THROUGH VTE ORIFICE PLATE                   FIGURE




                                       19

-------
 of  flow is  associated with a substantial reduction in the hydrodynamic pres-



 sure  drop  (AP)  through  the distillation tubes, by a factor of 3 to 10 compared




 to  the  typical  AP without surfactant additives.  Rotating the orifice plate




 to  cause  impingement of some of the foamy jets against the tube sheet filled




 this  entire space with  foam and produced a further increase in performance.




 This  is of  significance because one can thereby ensure wetting of the tube




 inlet section with foam by means of secondary orifices placed interstitially




 of  the  regular  orifices that are lined up with the tubes.




      The mode of foamy  two-phase flow from the tube outlet ends after the




 addition of surfactant, is shown in Figure 5.  The residual  liquid, carried




 through the tubes by the vapor phase core flow, is ejected as a foamy annulus




 in  contact  with the tube inner wall; this liquid or foam phase flow is dis-




 continuous  or gushing randomly from the 18 tubes.








 UPFLOW  VTE  PYREX GLASS EVAPORATOR




     An all-glass Pyrex-tubed evaporator, shown in Figure 6, was constructed




 with  the objective of obtaining data and information on the solute-crystallization



 behavior of wastewaters.  This equipment comprised a pair of Pyrex tube upflow




 VTE tubes of 1-inch x 5-foot dimensions having steam jackets, and being




 tangentially connected to a 5-liter spherical cyclone vapor-liquid separator.




 The top of  the cyclone separator was connected via a 2-inch vapor discharge




 to an efficient vacuum-operated condenser connected to a distillate reservoir




which permitted periodic removal of the distillate without interrupting the




 vacuum-evaporation process.   The base of the cyclone separator vessel  was




 connected to a 2-inch diameter standpipe for recirculation.   The distil land




was recycled back to the distillation tubes via 1/8-inch orifices provided




 in the form of Pyrex glass valves fused to the inlet ends of these tubes.




                                       20

-------
tsi
                           FOAMY ANNULAR FLOW FROM DISTILLATION  TUBES
FIGURE 5

-------
PYREX TUBE CRYSTALLIZING EVAPORATOR
FIGURE 6
                           22

-------
The minimal liquid holdup in this apparatus  was  bout  800  ml,  and  its




capacity was about k liters when full.  Provision was  made for  the  continuous




addition of feed during evaporation, thus providing concentration  of waste-




water feed by any desired factor.  This permitted close observation of  the




modes of two-phase flow with and without the addition of  a surfactant to  the




feed, and of the concentration levels at which percipitates were  formed.




     Operation of this evaporator under vacuum conditions was  provided  by a




rotary oil vacuum pump protected by a final  condenser.  Typical evaporation




temperatures were in the range of 90 to 110  F depending upon the  solute content




of the distil land, and the cooling water temperature.  The AT applied was




such as to provide a heat flux through the walls of the distillation  tubes




about equal to that of aluminum-brass tubes  of the same dimensions used at




a conventional AT of about 10°F.








DISTILLATION TUBES USED  IN THE VTE PILOT PLANT




     The VTE heat transfer tubes used  in this study were all of the double-




fluted or enhanced type, having their walls  formed into axial  or spiralled




grooves or flutes.  This provides complementary flutes on both the inside




and outside  (brineside and steamside) surfaces of the tubes.  This type of




wall modification provides an approximately 5-fold increase in the steamside




coefficient at an additional cost of about 30 percent added to the cost of




the smooth tube from which the double-fluted  tube  is  formed (9  )•  Such




tube profiles are shown  in Figure 7.
                                      23

-------
r-o
2-INCH 00  DOUBLE-FLUTED
ALUMINUM-BRASS
.0^2-INCH  WALL
                                                                    2-INC;; SPIRALLY FLUTED
                                                                    ALUMINUM-BRASS
                                                                        -INCH WALL
                3-INCH OD DOUBLE-FLUTED
                ALUMINUM-BRASS
                    -INCH WALL
                                                 2-INCH OD SPIRALLY
                                                 FLUTED TITANIUM
                                                 .020-INCH WALL
                      AXIALLY AND  SPIRALLY  DOUBLE-FLUTED DISTILLATION TUBES
                                                  FIGURE  7

-------
EXPERIMENTAL WORK




I)   Investigation of Cooling Tower Slowdown




     Background.   The adoption of evaporative  cooling  for  steam  power plants




to reduce their environmental  impact  by limiting  undesirable  effluents projects




the need for an economically acceptable method of renovating  cooling tower




blowdown.  Vertical  tube evaporation  to further concentrate the  blowdown  to




the concentration limits permitted by its  solute  content,  followed  by crystal-




1izing-evaporation to a slurried salt residue, relies  on well-defined and




acceptable technology (12).   If these evaporation procedures  are performed




at relatively low temperatures, one can utilize heat rejected from  the power




plant as the driving force for evaporation;  low temperature evaporation  in-




creases the acceptable concentration  limits  of calcium and magnesium salts  in




the blowdown brine and reduces corrosion and fouling problems of equipment.




While heat of evaporation is essentially free at  these low temperatures




(around 120 F) the evaporator performance is rather low,  requiring  a relatively




large heat transfer surface area and  increased capital costs.  Methods  of in-




creasing the evaporator heat transfer performance, thereby reducing the capital




cost, provides an even more substantial overall cost reduction on this  low




temperature evaporation than in the case where the cost of fuel  has to  be in-




cluded.  Interface enhancement (1, 2, 3, *0  offers a novel and promising method




of increasing the performance of vertical  tube evaporation (VTE) at quite low




added cost, while it concurrently reduces the potential for  scaling, fouling




and corrosion of the evaporator.




     VTE performance data.  A  large batch of cooling tower blowdown (1,500




gallons) was collected from the Mohave Power Plant with the assistance  of the




Bechtel Power Corporation in November  1973, and  trucked to the VTE pilot plant




facility for these  tests.   It  had a pH of 8.k and contained close  to 10,000




                                       25

-------
ppm of total dissolved solids.  This blowdown was slightly turbid,  and was  used



as such without clarification.




     The heat transfer enhancement effect and the tubeside pressure drop re-




duction effect responsive to the gradual addition of a surfactant to the




blowdown brine during upflow VTE under typical steady state process conditions




are shown in Figure 8.  The evaporator performance (U) at 210 F was approxi-




mately doubled by the addition of 5 ppm of Neodol-25-3A (Shell  Chemical  Company)




while the pressure drop (AP) was simultaneously reduced from about  30 to 7-5




inches of water.   Further additions of surfactant up to 25 ppm produced a




gradual further heat transfer enhancement to 3,000 Btu per hr-ft -  F.  The




most effective surfactant concentration was about 10 ppm, which provided a




120 percent enhancement of the overall heat transfer coefficient.  The tube-




side pressure drop was also at a minimal value of 5~inches of water with 10 ppm




of additive.




     The overall  heat transfer performance through the available evaporation




temperature range of 120 to 220°F under typical  multi-effect upflow VTE con-




ditions,  obtained without, and with 10 ppm of Neodol  additive to the blowdown




brine feed are shown in Figure 9-   It is apparent that, in the case without




surfactant addition, the performance was maximal  at 180 F; this indicates




that some fouling or scaling occurred at the higher brine temperatures even




with the pH of the brine adjusted to 6.8.  On the other hand, a substantial




increase in performance was obtained at these process conditions after the




addition of 10 ppm of a surfactant.  Interface enhancement was somewhat less




effective in the  120 to 1^0°F range at this low a surfactant concentration.




This should be improved by using a somewhat higher surfactant concentration




and by using 3-inch diameter tubes (5).
                                      26

-------
                          ENHANCEMENT OF HEAT TRANSFER PERFORMANCE
                          IN  VTE  OF HOHAVE COOLING TOWER SLOWDOWN

                          Effect  of gradual  addition of surfactant
                          to  the  feed on the overal1 heat transfer
                          coefficient,  U, and the pressure drop,  AP,
                          at  an upflow VTE temperature of 210°F,
                          AT  = 8°F, using 2.5 year-old bundle of
                          18  aluminum-brass  tubes of the double-
                          fluted  type.   Feed pH 6.8.
     3000
3
4_l
CO
O
U
I/)
i
LU
I
     2000
     1000
                                        I
             I
                     30
                                                                                         (M
                                                                                     20
                                                                                        _c
                                                                                        u
                                                                                        a.
                                                                                        <
                                                                                        a.
                                                                                        O
                                                                                        CC
                                                                                        a
                         cc
                         a.
                                                                                        O
                                                                                        cc
                                                                                        O
                                                                                        X
                                                                                     10
                            5            10           15

                              SURFACTANT ADDITIVE CONC.,  ppm
20
 25

FIGURE 8
                                             27

-------
                                T
                3000
            3
            4-1
            CD
                2000
            O
            O
CD
HEAT TRANSFER PERFORMANCE OF
MOHAVE COOLING TOWER SLOWDOWN
Overall heat transfer coefficient,
U, without and with surfactant addition
at 10 ppm, through the evaporation
temperature range 120 - 220°F, AT range
16.5 - 7-5°F, during upflow vertical  tube
                             evaporation  at  pH
                             18  aluminum-brass
                             fluted  type.
                  &. 8, us i ng a
                  tubes of the
bundle of
double-
                1000
                                                                                           U WITH 10 ppm ADDITIVE
                                                                                           U WITHOUT ADDITIVE
                                120
                            160
                                                                    180
                    200
                                220
                                                        EVAPORATION TEMPERATURE,
                                                                                                            FIGURE 9

-------
     Figure 10 shows the upflow VTE performance  (U)  during  the concentration




of cooling tower blowdown by interface-enhanced  evaporation at 130  F,  in




comparison with conventional evaporation (broken line).   Also shown are per-




formance data calculated after deducting the  AT  loss due  to apparent  boiling




point rise as observed.   The steamside temperature was  held at \k2  F  and  the




condenser flux was held  at steady state for these data.   Some precipitate




formation was observed at brine concentrations of 2 percent and  higher.   A




slight increase in performance was observed as  the brine  concentration in-




creased from 1 to 1.67 percent, in spite of the  increased solute content  of




the brine.  This is attributable to the simultaneous concentration  of the




surfactant in the brine, which increases the  evaporation  coefficient  as




indicated by Figure 8, and as also reported in  earlier  work (8).  The decline




in performance at brine concentrations beyond the onset of crystallization




is attributable to the loss of surfactant from  solution due to  its  adsorption




on the crystal or precipitate surfaces.  This rationale requires confirmation




in further work planned.




     A relatively inexpensive and effective method of stripping  surfactant




additives from blowdown brines, by foam fractionation,  has been  developed in




this Laboratory, and demonstrated on a pilot plant scale  (13).   This  procedure




also clarifies the brine concentrate and facilitates its  further concentration




in a crystallizing evaporator to produce useful  salts,  such as  sodium sulfate,




and a final slurried concentrate for ponding or disposal.  The  foamate fraction




containing the surfactant concentrate can be recycled after its  clarification.




     Discuss ion.  The use of surfactant additives in blowdown concentration




by VTE utilizing waste heat available  in a power plant cooling  cycle provides




significant improvements  in process flexibility and economy i 11). Figure 11 shows




a possible method of  integrating this coolant renovation-recycle system  into




                                       29

-------
                          CONCENTRATION OF MOHAVE POWER PLANT COOLANT SLOWDOWN
                        BY INTERFACE-ENHANCED VERTICAL TUBE EVAPORATION AT 130°F

-------
                                                                                  COOLANT
                                                                                  MAKE-UP
                                                 BARO-
                                                 METRIC
                                                 CONDEN-
                                                 SER
                                                                                   COOLANT
                                                                                   MAKE-UP
     DISTILLATE             SOLIDS SLOWDOWN
RENOVATION AND RECYCLE OF POWER PLANT COOLING TOWER SLOWDOWN
FIGURE  11

-------
 the  flow diagram of an existing power plant.  The upper half of Figure 11




 represents an existing power plant coolant cycle; the lower half shows the




 renovation loop added on via k valves, permitting shutdown of this loop and




 reversion to the original cycle of operation, if desired.  The power plant




 could be reverted to the original mode of operation at any time within the




 time required to close valves 1, 2, 3 and k, and opening valve 5 to resume




 the usual discharge of blowdown, for instance to a reservoir for later




 renovation.  Since about 5 percent of the total  turbine exhaust steam is




 utilized in the evaporator loop (via valve 2) a small forced-draft cooling




 tower is added to this loop to make up for the reduced demand on the power




 plant cooling tower.  The condensate of this exhaust turbine steam is returned




 from the first effect (VTE-1) to the boiler via valve 1.  A portion of the




 hot coolant is diverted to the evaporation loop, as blowdown, via valve 3-




 The vapor produced in VTE-1 serves as heating steam for the VTE-11 and the




 forced circulation crystallizing evaporator (FC-VTE), and these condensates




 are available (DISTILLATE) for a beneficial  use such as boiler feed makeup




 or potable fresh water or for return to the main coolant loop.  Vapors pro-




 duced in the VTE-11  and FC-VTE are returned to the main coolant loop as




 condensates from the barometric condenser via valve 4; dilution of the coolant




with condensates reduces coolant makeup and pretreatment requirements.  The




coolant makeup for the barometric condenser and small cooling tower need




not be softened since it is continuously diluted with this distilled water,




and becomes part of the main coolant loop.  Another option is to divert the




DISTILLATE (from VTE-11  and FC-VTE) to serve as coolant makeup for the small




cooling tower,  in which event this coolant will  be distilled water entirely;




this provides a source of cooled distilled water (as  blowdown) for the above




beneficial  uses.   It is  apparent that the rate of producing such cooled




                                      32

-------
distillate will  depend on the rate of  turbine  exhaust  steam flow through




valve 2, and it  can be substantially  increased by  partial  replacement of




main cycle condenser capacity with additional  heat duty  in the VTE's, baro-




metric condenser and small  cooling tower.




     In addition, the further adoption of  this proposed  means of evaporative




cooling, to partially replace cooling  condensers  in future power plants, can




provide the significant beneficial result  of producing more distilled water




than that required to maintain scale-free  operation of a cooling tower.  This




additional, pure distilled water product could in  part be diverted  for  another




beneficial use,  for instance, for boiler feed  makeup and to  reduce  the  salinity




of a domestic or municipal  water supply.  In relation to the  proposed  Palo  Verde




power plant, where secondary or tertiary treated  municipal effluents are to be




used for power plant cooling, the adoption of  this proposed  coolant recycle




scheme could provide some pure, distilled  water,  for instance for  the  dilution




of Colorado River water to reduce its  salinity.  This technology will  also




provide increased flexibility in coolant pretreatment; for instance, the need




for softening may be reduced, thereby reducing chemical  costs as well  as final




saline wastes.  Since the coolant is stripped  of volatile constituents by




repeated passage through the cooling towers, the subsequent evaporation of




the blowdown should produce pure distilled water of potable quality.




     Conclusions.   It is clear from the above data and observations that the




interface-enhanced mode of VTE operation can provide a substantial   increase




in the heat transfer performance during blowdown evaporation, especially at




blowdown concentrations below the crystallization or precipitation  limit.




This limiting concentration  is  increased by the presence  of the surfactant




additive, probably by  interfering with  the  rate of crystal growth  through




adsorption of the additive on newly formed  crystal surfaces.




                                        33

-------
     The benefits of  increased heat transfer performance are mainly as




 follows:




     (a)   it permits  the use of an increased number of effects in the multi-




 effect VIE plant while maintaining the per-effect distillate production at a




 lower per-effect AT than in conventional VTE operation (k).   This permits a




 proportionate increase in the gain ratio, in the interest of substantial  steam




 or  fuel savings.  This aspect of interface enhancement also improves design




 flexibility, permitting an improved design optimization with reference to




 capital versus operating costs.




     (b)  Slowdown brine concentration with waste heat accentuates the sig-




 nificance of interface enhancement for reducing capital costs.  This applies




 to  both upflow and downflow VTE operation.  It also permits  the production




of  distilled water by allowing the inclusion of a two-effect downflow VTE




within the waste heat temperature span available in a power plant cooling




cycle,  as shown in Figure 11.




     (c)  Interface enhancement can be applied to vapor compression VTE




operation for cooling tower blowdown renovation to reduce the required heat




 transfer surface in such an installation.




     (d)  Operation and maintenance costs of blowdown evaporators should  be




 reduced by the use of surfactant additives because of the particulate dis-




persant effects of surfactant; this should reduce fouling and corrosion of




heat transfer surfaces.

-------
     Solute precipitation data.   Observations made in earlier work,  and  data




obtained with the Pyrex tube evaporator indicated that the dispersant  effect




of the surfactant additive delays the onset of crystallization.   This  side




effect is quite beneficial; it can reduce the capacity requirements  of the




relatively expensive crystallizing evaporator to be used subsequently.




     In a typical run, 16 liters of Mohave blowdown was evaporated at  130 F




to a residual volume of 1.8 liters (in 1.5 hours), at which concentration




a crystalline precipitate was first observed.  This concentrated residue




was withdrawn and separated into a 50 ml  fraction containing a muddy sedi-




ment and a clear supernatant fraction (1.75 liters) from which further




crystallization occurred over the next 48 hours.   In a follow-on run with




surfactant addition at 8 ppm to the feed, 20  liters of Mohave blowdown having




0.3 ml of Neodol-25-3-S (Shell Chemical Co.) added was similarly evaporated




at 130 F to a residual volume of  1.66 liters  (12-fold concentration) when




a crystalline precipitate was first observed.  This  residual concentrate was




separated into a 25 ml fraction containing a muddy precipitate and a  clear




fraction (1.63 liters) from which further crystallization occurred over  the




next two days.   It was apparent from  these tests  that  the addition of a




surfactant depresses  the crystallization of solutes  during evaporation of




Mohave coolant blowdown.
                                      35

-------
2)   Industrial Steam Generator Slowdown Concentration




     Large  industrial boilers produce a considerable volume of concentrated




blowdown, depending upon the quality of the feed water used.   The blowdown




from steam  generators serving a large refinery can reach 500,000 gallons per




day on the  basis of using treated tapwater as boiler feed.   The proportion




of blowdown to feed is determined by the scaling potential  of the pre-treated




feed and the need to keep boiler heat transfer surfaces free of corrosion,




fouling and scaling in the interest of high heat transfer performance and




fuel economy.  The concentration in the blowdown of the naturally occurring




salts, as well as of boiler feed additives such as antiscaling compounds and




corrosion inhibitors could render it unsuitable for discharge to, for instance,




a municipal  effluent treatment plant.




     It was  the objective of this series of tests to determine the feasibility




of using the interface-enhanced method of VTE operation to reduce industrial




boiler blowdown to a very small volume while simultaneously pro^cing distilled




water of pure quality suitable for a beneficial use.




     The use of surfactant additives as evaporator heat transfer performance




enhancement  agents had been demonstrated and was anticipated to also be




effective for boiler blowdown.  A second beneficial effect of these additives




previously observed is to inhibit the format ion of scale and to act as a




dispersant  for particulate matter in suspension.




     Three series of tests were carried out with the blowdown obtained from




a large industrial steam generation plant.  These test series were;




     (a)   Typical  upflow VTE heat transfer performance data using the 5,000




gpd pilot plant tubed with 2-inch OD x 10-foot long double-fluted aluminum-




brass tubes.

-------
     (b)   Test data on the upflow VTE heat  transfer enhancement  response




and the pressure drop reduction effect responsive to the  gradual  addition




of a selected surfactant to boiler blowdown feed  evaporated  at 210  F.




     (c)   Interface-enhanced upflow VTE performance data  through  the  range




of typical effect-to-effect process conditions,  comparable to the data  shown




under  (a).




     (d)   Heat transfer performance and solute precipitation behavior during




the gradual  10-fold concentration of boiler blowdown having  10 ppm  of a




selected surfactant added.




     (e)   Solute precipitation behavior during the gradual 20-fold  concentra-




tion of boiler blowdown having 10 ppm surfactant added, examined during




evaporation in the Pyrex glass upflow VTE.
      (a)  Typical upflow VTE data:  Figure 12 shows the overall heat transfer




coefficient and tubeside pressure drop data obtained with boiler blowdown




(adjusted to pH 6 by the addition of sulfuric acid) under the usual multi-




effect evaporation temperature, temperature difference (AT) and feed flow




conditions.  Data are shown for double-fluted aluminum-brass and copper tubes




of 2-inch OD x 10-foot heated  length.  These data are consistent with earlier




tests on freshwater and seawater obtained  in this laboratory




and elsewhere  (  3 ).  The heat transfer performance with 2-inch tubes is




generally low  in the 120 to l60°F range where the tubeside pressure drop  is




relatively high and the upflow stability  low.  These tubes perform satis-




factorily in the 160 to 2kO°F  range; 3-inch diameter tubes would be preferable




for the  lower  range.
                                       37

-------
            3000
        o

       CM
            2500
VjJ
03
        ^  2000
        LJ
o
o

ac
UJ
            1500
            1000
             500
                                  	1	j	!	1	1	

                                     UPFLOW VTE PERFORMANCE WITH 301LER SLOWDOWN


                                   Overall  heat transfer coefficient U, through the evaporation
                                   temperature range 120 to 240°F under typical multieffect process
                                   conditions; tube bundle pressure drop.
                           B
                           A
                                                      Plot A:   Heat transfer performance of Al-Br tubes
                                                      Plot 3:   Heat transfer performance of Copper t'.ibe
                                                      Plot C:   B'jndle tubeside pressure drop
                                                               60
                                                                                                            50
                                                                                                                         O

                                                                                                                         l/l
                                                                                                                         Q.
                                                                                                                         O
                                                                                                                         ce
                                                                                                                         o
                                                                                                             30
                                                                                                             20
                                                                                                                         10
                                                                                                                         UJ
                                                                                                                         CO
                                                                                                                      10
                             120
                                 140
160         180

   EVAPORATION TEMP.
                                                                              200
220
                                                                                                      240
                                                                                                           FIGURE  12

-------
     (b)  The upflow VTE interface enhancement response with  boiler  blow-

down at an evaporation temperature of 210 F responsive to the gradual  addi-

tion of Neodol 25-3A (Shell  Chemical  Co.) is shown in Figure  13.   Data were

plotted for the overall heat transfer coefficient of the 14-tube  bundle  of

double-fluted aluminum-brass tubes and for a double-fluted copper tube,  as

well as the tube bundle pressure drop.  These data were again consistent

with earlier reports (2,3,^), confirming the dramatic pressure drop reduction

effect and the substantial  performance enhancement by the addition of a  sur-

factant and the imposed foamy two-phase flow of the feed over the heat

transfer surfaces.  For instance, the 14-tube bundle performance  was increased

by  117 percent after the addition of 10 ppm of surfactant, while  the pressure

drop was concurrently reduced by a factor of 11 from kO to 3.5 inches of

water.  The comparable response of the copper tube was even better at 149

percent enhancement, consistent with earlier data (3). Further additions of

surfactant provided further increases in performance and a slight increase

in  the tubeside pressure drop; the beneficial maximum surfactant  concentration

was about 30 ppm.
     (c)  Figure Htshows the interface-enhanced upflow VTE heat transfer

performance through the usual multieffect evaporation temperature range of
          o
120 to 2kQ F.  These data, in comparison with the data discussed under (a)

above (Figure  12 ), indicate the advantage obtainable by the use of surfactant

additives in blowdown evaporation.  The distillate productivity rate is about

doubled while  the tubeside pressure drop is substantially reduced to ensure

stable operation of the multieffect upflow VTE.
                                      39

-------
  I            I            I            I            I


 INTERFACE ENHANCEMENT RESPONSE  WITH  BOILER  BLOWDOWN


 Variations in U  and  AP responsive  to the  gradual

 addition of  a surfactant
                                                 o  A
                Plot A:   Heat  transfer performance, AI-Brtub«

                Plot B:   Heat  transfer performance, Copper tub<

                Plot C:   Tube  bundle  pressure  drop
                                                               30
                                                                   u.
                                                                   o
                                                      20
                                                                   i
                                                                   UJ
                                                                   CC
                                                         UJ
                                                         ca
                                                         a.
                                                                   LU
                                                                   CO
                                                                10
10
  20
30
50
SURFACTANT ADDITIVE CONC.  ppm

              ko
                                                    FIGURE  13

-------
     3000
     2500
3
*J
00
     2000
£    1500

1

§
     1000
2
Ul
              	1	1	1	T
                            INTERFACE-ENHANCED UPFLOW  VTE  PERFORMANCE WITH  BOILER  SLOWDOWN

               Heat  transfer performance  and  tubeslde  pressure
               drop  through the evaporation  temperature  range
               120-240°F after the addition of  10 ppm  of
               a surfactant to the feed.
                                                                                                           60
                                                                                                           50
                                                                                                               o
                                                                                                               in
                                                                                                               Q.
                                                                                                               o
                                                                                                           30
                                        Plot  A:   Heat transfer  performance,  Al-Br tubes
                                        Plot  B:   Heat transfer  performance,  Copper tube
                                        Plot  C:   Tube bundle pressure drop
                                                                                                            20
      500
                                                                                                            10
                      120
                                             160         180         200
                                                EVAPORATION TEMP.  °F
                                                                                 220
                                                                                                 FIGURE 1**

-------
      (d)  A  large volume  (800 gallons) of industrial boiler blowdown was




subjected to a gradual concentration by a factor of 10 while in recirculated




flow  through the VTE pilot plant, to determine the effects of solute concen-




tration on the heat transfer performance.  The pH of the blowdown was




adjusted from 12 (as received) to 5-5 by the addition of sulfuric acid (80 ml)




and 10 ppm of Neodol-25-3A (Shell Chemical Co.) was added for this test series.




Deaeration of the feed was affected by recirculating it through the VTE pilot




plant under vacuum.  The steamside temperature of the VTE tube bundle was




maintained at 220 F and the initial AT applied was  10 F.  The condenser flux




was held constant during the entire run, resulting  in a gradual decrease in




the AT to 7 F responsive to the  increase in boiling point as the solute con-




tent  increased.  Heat transfer performance data are plotted for the 14-tube




bundle of 2-inch OD double-fluted aluminum-brass tubes and for a similar




copper distillation tube as a function of the residual  feed volume in Figure




15 .  It is interesting to note  that the gradual increase in solute concen-




tration did not have a negative effect on the overall  heat transfer coefficient




in this case.  This is the result of the simultaneous concentration of sur-




factant in the residual feed and of the fact that the solubility limit of




solutes was not reached during this 10-fold concentration of the blowdown.




In fact a gradual increase in evaporator heat transfer performance




to about 25 percent was obtained during the course of this blowdown concentra-




tion by a factor of 10.  Also of interest was the fact that no excessive




foaming was experienced.  The final solute content  of 'this 10-fold concentrate




was about 16,500 ppm (or 1.65%)  including 100 ppm of the added surfactant.

-------
     3000
     2500  ~
 I
CO

o
-   2000
o
o
u.
in
i
1500
     1000
UJ
o
      500
         800
                     700
        10-FOLD CONCENTRATION OF BOILER SLOWDOWN

Heat transfer performance during the gradual  concentration
of boiler blowdown after the addition of 10 ppm of a surfactant.
                                 Plot A:
                                 Plot B:
                 Heat transfer performance,  Al-Br tubes
                 Heat transfer performance,  Copper tubes
                                                         _L
                                                                                 _L
                                                                                        _L_L
                            600         500         400         300         200

                              RESIDUAL  FEED VOLUME,  GALLONS  IN RECIRCULATION
                                                                                             100  80

                                                                                                FIGURE  15

-------
      (d)   In a final experiment 40 liters of boiler blowdown with 10  ppm of




surfactant added was concentrated in the Pyrex glass VTE of Figure 6.




This  concentration proceeded by a factor of 20,  to a residue of 2 liters,




without any significant precipitation of salts being observed.   This  residue




was dark colored from suspended particulates,  all  of which were readily




maintained in suspension by the presence of the  surfactant additive.
     Discussion.   From the data plotted in Figure 13 it is  apparent  that  the




addition of about 10 ppm of surfactant to boiler blowdown evaporated  at  210  F




in an upflow VTE using double-fluted aluminum-brass  tubes provides  an




approximate 120 percent increase in the evaporator performance,  and an 11-fold




reduction in the tubeside pressure drop.  These data indicate that  interface




enhancement should provide substantial cost reductions  in the concentration




of such wastewaters.   With appropriate evaporator design options,  these  cost




reductions can be either in terms of capital  cost or operation-maintenance




costs.




     It is clear, from a comparison of the data plotted in Figures  12 and




Nt,  that the interface-enhanced mode of evaporation provides an approximate




doubling of the upflow VTE heat transfer performance.   Stated in different




terms,  one can increase the rate of concentration of boiler  blowdown  by




about 100 percent by the addition of about 10 ppm of surfactant  to  it followed




by imposing the foamy mode of two-phase flow through the upflow  distillation tube




under otherwise conventional  process conditions.




     The 10-fold concentration of boiler blowdown at 210 F without  loss  in




heat transfer performance after the addition of 10 ppm  of surfactant  is  con-




sidered very promising.  These would essentially be the ideal VTE  process

-------
conditions for an evaporator utilizing vapor recompression  as  the means



of supplying the process heat requirements.   Vapor compression (VC)  is




probably the least costly method of concentrating boiler  blowdown.   Concen-




tration by a factor of 20 to 25 should be readily achievable  by  VC-VTE




with an interface-enhanced performance of about 2,000 Btu per  hr-ft  -  F.




Several alternative types of compressors, both electrically driven




mechanical, or steam-jet types, are commercially available. The  main ad-




vantage provided by interface enhancement is in this instance taken  in terms




of a capital cost reduction;  the heat transfer surface area  or  number of



distillation tubes used can be reduced by half.




     The alternative approach of using an interface-enhanced  multiple effect




VTE provides the basis for saving heat or fuel costs.  In this case  the main




advantage can be taken in terms of an improved economy ratio, by increasing




the number of effects normally permissible, by about 50 percent.  Economy




ratios of up to 18 pounds of distillate product per pound of  heating steam




are possible (6).  Intermediate choices are of course possible, thus allow-




ing flexibility for optimizing overall costs by balancing  the elements of




capital and operation-maintenance costs.




     The beneficial side-effects of surfactant additives were also significant




though not precisely  defined  in this case.  The dispersant properties of the




additive had an apparent beneficial effect of  retaining particulates in sus-




pension during the 10-and 20-fold concentrations of boiler blowdown.  The heat




transfer surfaces remained clean during  these  operations.

-------
 3)  Acidic Mine Drainage Concentration
     Drainage and seepage from active and abandoned mines and from slagpiles
 associated with such mines can present effluents that are environmentally harm-
 ful.  These effluents are usually high in acidity due to atmospheric oxidation
 of sulfur compounds producing sulfuric acid in solution.  Acidity levels in the
 pH-range of 2 to 4 have been reported.  In addition such effluents also contain
 other undesirable solutes such as salts of iron, copper and zinc.  Depending upon
 the length of atmospheric exposure, iron compounds can be present as ferrous
 sulfate which is gradually oxidized to ferric sulfate.  The drainage water ex-
 amined in this study originated from a pyrites slag pile.  Two types of this
 effluent were examined:  the first was collected directly from the slagpile
 before significant exposure to air oxidation and was high in ferrous content;
 the second type was high in ferric content, substantially fully oxidized by
 prolonged exposure to air and partial  solar evaporation-concentration.  The
 highly corrosive nature of these effluents presented a major operating problem.
 The VTE pilot was in part constructed of copper-based alloys and stainless
 steel, and subject to corrosive attack, especially at higher temperatures.
     The experimental procedures applied can be summarized as follows:
     (a)   The solute behavior of these drainage waters was examined by gradual
 concentration in the pyrex glass VTE,  to the point of precipitation of ferrous
or ferric sulfate, both without and with a surfactant additive.
     (b)   Heat transfer performance data were obtained in the VTE pilot plant
within the evaporation temperature range of 120 to 200°F.  Data were obtained
with copper,  aluminum-brass and titanium tubes of the fluted type.
     (c)   The highly corrosive nature of this wastewater dictated limited use of
the VTE pilot plant for its examination.  Solid precipitation studies were there-
fore conducted with the pyrex tube exaporator.  This wastewater is comparable to
electroplating rinsewater,  at least in terms of its metal ion content and cor-
 rosiveness.   Therefore, pilot plant tests with electroplating rinsewater were
also avoided.

-------
     (a.l.)   The fresh ferrous-containing  drainage water  had a TDS of about




5^,000 and a pH of 3.3. Other constituents were  about  100 ppm of copper




sulfate and about 150 ppm of zinc sulfate.  Six  liters  of this were evaporated




in the glass-tubed evaporator of Figure 6, at 40 C  (104 F).  to a residual




volume of 2.0 liters, at which point a whitish crystalline precipitate started




to form, at 3-fold concentration.




     Eight liters of this drainage water containing  5  ppm of added Neodol-25~3A




(Shell Chemical Co.) were evaporated in the glass-tubed evaporator at 90-105  F,




to the onset of crystallization which occurred at a  residual volume  of 2.2




liters.  Further crystallization occurred upon standing in this  3-6-fold




concentrate.




     Comment:   It was apparent that the addition of  a surfactant to  this




water  (a) facilitated  its evaporation by upflow VTE, and also inhibited  or




retarded the onset of crystallization, but did not necessarily influence




the final solute concentration  level  in the  presence of crystalline precipitates.




      (a. 2.)  The oxidized,  ferric containing drainage water had a TDS of




about  66,000 and a pH of about 2.0.  Other constituents were about 120 ppm




•>f copper and  180 ppm  of zinc sulfates.




      Eight  liters of  this water  were  evaporated  at about  100 F  in the glass-




tubed  evaporator  to  the  appearance of  crystalline material  in the concentrate.




From  this k.4-fold  concentrate  (1.80  liters), further  crystallization occurred




upon  standing.




      Eight  liters of this water containing 5 ppm of surfactant additive




 (Neodol-25-3A)  were  concentrated at  about 90 F  in the  glass-tubed evaporator




 to  initial  crystal  formation,  and then drained.  This  6-fold concentrate




 (1.35 liters)  was  set aside to deposit additional crystalline material.

-------
      Comment:   It was apparent  that  the addition of 5 ppm of a surfactant




 retarded  crystallization and also  improved upflow VTE stability and efficiency.




      On a basis of  these results it  was decided that definitive heat transfer




 performance  tests with  the pilot plant were justifiable.
      (b.l.)  Heat  transfer performance data obtained were limited by the




corrosive  nature of  this acidic water.  Two pilot plant runs were conducted




with  the 5,000 gpd VTE shown  in Figure 1, using separate 80 gallon samples




of  the  fresh, ferrous-sulfate high drainage water only.




      First  run:  The pilot plant was tubed with 18 spiral-corrugated copper




tubes of 2-inch OD x 10-foot  length x 0.30-inch wall thickness (Yorkshire




Imperial Metals, Ltd.) for this test.




      Eighty gallons of drainage water were deaerated in the pilot plant by




recirculation under vacuum (29.5-inch Hg).  VTE heat transfer performance




data were  then taken as described earlier at evaporation temperatures of




140°, 160° and 180°F using typical multi-effect process conditions with feed




flows of one gallon per minute per tube.   Neodol 25-3A was then added to the




feed at 10 ppm concentration, and heat transfer performance data were again




taken at evaporation temperatures of 180, 160, 140 and 118 F.  These data




are shown  in Figure 16 attached.




     Comment:  It was clear from the data in Figure 16 that interface enhance-




ment provided an approximate 71 percent heat transfer performance enhancement




at 180 F with 10 ppm of Neodol-25-3A additive.  The two-phase pressure drop




(AP) through the tubes was simultaneously reduced from about 39 to 8 inches




of water,  to improve the upflow stability and increase distillate production




proportionately.

-------
                             INTERFACE ENHANCEMENT RESPONSE WITH COPPER TUBES
      o

     CM
       •fci
      
-------
      There was an apparent reduction in the enhancement effect of Neodol




 with time of the test, but this was not conclusive and it was decided to




 defer to a second test.




      Second run:  For the second run, four of the 18 distillation tubes in




 the bundle were replaced with a double-fluted aluminum-brass tube (Yorkshire),




 a spiral-corrugated titanium tube  (ORNL), and two double-fluted titanium




 tubes (Timet-Grobb).




      Eighty gallons of fresh slagpile effluent were deaerated in the pilot




 plant at 29.5 inch Hg, after which its pH was 3-1.  Heat transfer performance




 data were then taken at evaporation temperatures of 125, 150, 180 and 200 F




 as before.  At 200°F Neodol-25-3A was added to the feed to the 10 ppm level,




 and the performance data were repeated.  The process conditions were then




 held at steady state, at 200 F evaporation temperature, for 2 hours, re-




 peating data-taking at 30 minute intervals without observing any significant




 reduction in the performance, thus showing that the surfactant additive is




 not significantly degraded by these process conditions.




     Heat transfer performance data are shown in Figure 17.   The aluminum-




brass tubes responded best to Neodol addition; the overall heat transfer




coefficient (U)  increased by 100 percent, from 1302 to 2718 Btu per hr-ft -°F.




at 200 F.  The titanium tubes showed an interface enhancement response of 63




percent.   The tube bundle pressure drop was reduced from 40 to 9.5 inches of




water by the addition of the surfactant, comparable with the first run, and



the spiral-corrugated copper tubes also responded similarly to the first run




in heat  transfer performance, as shown in Figure 16.




     Comment:   The heat transfer performance enhancement effect by Neodol




addition ranges  from about 60 to about 100 percent at an evaporation tempera-




ture of  200 F,  depending upon the type of distillation tubes used.  Aluminum-




                                       50

-------
      o
     CM
	1	1	r
 INTERFACE ENHANCEMENT RESPONSE WITH ALUMINUM-BRASS AND TITANIUM TUBES

 Overall  heat transfer coefficients (U)  responsive to 10 ppm Neodol
 addition to acidic wastewater feed at 200°F, with double-fluted
 aluminum-brass  and titanium tubes in the 18-tube upflow VTE pilot plant.
      -C
      I.
      o.
          2000
wi
      o
      O
          1000
      <
      QC
                                                        Plot  A
                                                        Plot  B
                                                        Plot  C
                                                 U vs Evap. Temp., Double-fluted Aluminum-brass tube
                                                 U vs Evap. Temp., Double-fluted Titanium tube
                                                 U vs Evap. Temp., Spiral-corrugated Titanium tube

                                                 	I	I	
               120
                                       140
                                             160

                                       EVAPORATION TEMPERATURE,
                                                                                        180
                                                                                                                200
                                                                                                                    FIGURE  17

-------
brass (double-fluted) performed best, but titanium tubeswi 1 1 be the better




choice because of corrosion-fouling problems.   The double-fluted titanium




tubes showed a performance enhancement of 63 percent with  10 ppm Neodol.




The 4-fold pressure drop reduction by surfactant addition  permitted stable




upflow VTE operation at AT levels of 6-7 F,  within the range of vapor com-




pression operation.  Neodol  has sufficient thermal stability at these process




conditions for use as an interface enhancing agent.   Considerable deposition




of what appeared to be porous copper was observed at the distillation tube




outlet ends.  Metal surfaces were generally  fouled by brownish deposits




requiring repeated washing with dilute acid  feed at  pH.  to remove.

-------
DISCUSSION




     Several methods of wastewater concentration are available,  for  the




purpose of providing recycle water having a relatively  low solute  content




and a concentrated wastewater residue for disposal.   The selection of what




method to use is of course dominated by their comparative economics  and  by  the




technical feasibility as it depends on the chemical  properties  of  the waste-




water.  Combinations of the available concentration  procedures  should also




be considered ,in the interest of overall  cost reductions.  The  most  significant




solute concentration methods are by evaporation, of  which several  alternative




procedures are applicable: by reverse osmosis (RO),  by electo dialysis  (ED),




by ion exchange (IE) and by precipitation techniques.  Included in evaporation




technologies are vertical  tube evaporation (VTE) either with upflow or  downflow




of the feed, multistage flash evaporation (MSF)  and  crystallizing evaporation (CE).




     The determination of the comparative economics  of these concentration




methods are quite complex and beyond the scope of the present study.  However,




recent studies conducted at the Bechtel Corporation  provide a comparative




cost evaluation at  least for the case of cooling tower concentration-recycle;




their conclusions provide a cost basis for ranking VTE with respect to  other




feasible alternative methods.  The present study provides a basis for com-




paring the cost of  interface-enhanced VTE with  that  of the conventional  VTE




used  in the Bechtel studies.  Recent design comparison studies performed by




Kaiser Engineers provide a capital cost comparison of  interface-enhanced VTE




with conventional VTE and MSF plants of  large size  for sea water  desalination.




     The above studies by Awerbuch and Rogers (12) on  the desalination of




cooling tower blowdown for a large  (2,200 MWE)  power plant using  cold lime




soda softened river water for cooling, were  reported  in  the  recent  EPA-AIChE




sponsored Watereuse conference.   A 20-fold concentrated  blowdown




                                        53

-------
was considered for further concentration to a solid residue, utilizing a

total of fourteen alternative procedures, and the comparative costs (capital,

operating and total) were determined.  Their process combinations considered,

and the costs computed can be summarized as follows:

                                                	Costs In $M	
Concentration Method                            Cap!tal    Operating   Total

 1.  Crystallizing evaporation                     15.7      25-7      41.4

 2.  MSF preconcentration at 230°F maximum          9.1       20.3      29.4
     feed temp.; Crystallizing evaporation

 3.  MSF preconcentration as in 2; Vapor           15.8      21.2      37.0
     compression evaporation with
     crystal slurry recycle feed

 4.  MSF preconcentration' at 19°F maximum           7.2      17.8      25.1
     feed temp;
     Crystallizing evaporation

 5-  MSF preconcentration as in 4;                 10.9      19.4      30.3
     Vapor compression evaporation with
     crystal slurry recycle feed

 6.  Ion exchange;                                  8.8      17.8      26.6
     Reverse osmos is;
     Crystallizing evaporation

 7.  Ion exchange;                                 21.8      23.4      45.1
     Reverse osmosis;
     Vapor compression evaporation with
     crystal slurry recycle feed

 8.  Ion exchange;                                  5.2      12.1      17.2
     Reverse osmosis;
     MSF with 230 F max. temp.;
     Crystallizing evaporation

 9.  As in case 8 except using a                    7.4      12.6      20.0
     vapor compression evaporator with
     crystal slurry recycle feed

10.  Ion exchange;  Reverse osmosis;                 6.0      13.9      '9-9
     MSF with 190°F max. temp.;
     Crystallizing evaporator

11.  As in  case 10 except using a Vapor            8.3       14.7      23.0
     compression evaporator with crystal
     slurry recycle feed

                                      54

-------
                                                        Costs  In  $M
Concentration Method continued

12.  Hot-coolant heated upflow VTE
     for preconcentration;  Crystallizing
     evaporator heated by hot coolant

13.  Turbine exhaust heated upflow VTE
     for preconcentration;  Crystallizing
     evaporator similarly heated

14.  Downflow VTE preconcentrator and
     crystallizing evaporators replacing
     one power plant condenser, both
     heated with turbine exhaust steam
Capital    Operating   Total

    8.3       11.6      19.9
    7.7
    6.1
9.9
3.6
17.6
 9.7
     The least expensive method of blowdown concentration-recycle thus requires

replacement of one of three typical power plant condensers with a VTE for pre-

concentration followed by a VTE for crystal 1izing-evaporation, both heated by

turbine exhaust steam.  This method, however, wi 1 1  probably require demonstration

before it wi11 be considered acceptable by the power industry since it requires

a change in the established coolant cycle.  Alternative method 13 appears the

most acceptable from the power plant operators point of view since it requires

only an addition to conventional coolant cycles. The last three and most

promising of the fourteen alternative methods can be further improved, and

their cost figures can be reduced by applying  interface enhanced evaporation

in the blowdown concentration by VTE.  The emphasis in the above Bechtel

study was to obtain comparative cost figures; the absolute costs may need

adjustment.

     Another alternative method of blowdown concentration recycle was recently

proposed by the author  (ll) based on data  from this study, using turbine
^Private communication with the authors.
                                      55

-------
exhaust steam for preconcentration by interface-enhanced  VTE,  followed  by



conventional crystallizing evaporation.   The main advantage of this  method




is that it permits the use of two evaporation effects  within the temperature




span available within a conventional  power plant coolant  cycle.   This pro-




vides a basis for either producing distilled water for a  beneficial  purpose,




such as for boiler feed or potable use,  or to dilute the  coolant in  the main




power plant coolant cycle.  Since the heat transfer performance  is  in this




case about double that of case 13 above, those cost figures would apply




fairly closely here and the distillate produced would  be  the gain, approxi-




mately.  Alternatively one could use the single-effect approach  of case 13




and reduce the VTE heat transfer surface by a factor close to 50 percent.




The capital cost advantage of the reduction in distillation tube requirements




and the ability to use upflow VTE instead of downflow VTE provide a  capital




cost saving of about 25 percent for a large seawater desalting plant, accord-




ing to a study by Kaiser Engineers (  6  ).  In a recent design comparison




study of the interface-enhanced upflow VTE with  conventional  MSF for sea-




water desalination by Kaiser Engineers ( 5 ) it was shown that the heat




transfer surface requirement of this VTE is only about half that of  MSF and



the evaporator vessel size is reduced by about 40 percent.




      In order to arrive at realistic  capital and operating cost  figures for



the use of  interface-enhanced VTE  in  the  concentration of cooling tower blow-




down by waste heat, one would have to perform a detailed design  study which




was outside the scope of  this work.   However  it  is apparent that a flow dia-




gram such as in Figure  11 should be both  acceptable to power plant operation




and more economical than  the other alternatives considered. In  the case of




the most economical of  the fourteen above proposed methods the  use of  interface




enhancement will undoubtedly reduce this  cost further by a significant amount.




                                      56

-------
     The recommended procedure for cooling tower  blowdown  concentration,




based on this study, is  the one based  on  the  flow diagram  of  Figure  11.




This approach was presented at the Second National Conference on Complete




Watereuse by the author in a paper titled "Recycle of Power Plant Cooling




Tower Blowdown by Vertical Tube Evaporation with  Interface Enhancement,




Utilizing Waste Heat."




     This procedure combines  the advantages of minimal interference with the




normal  power plant  operation  and good economy, and it provides distilled




water for boiler feed makeup  or another beneficial use.  This recommended




procedure can be added on  to  a pre-existing power plant or can be designed




into a  new plant.   Normal  operation of a  pre-existing power plant can be




resorted  to  at any  time, within the approximately 30 seconds  required to




close k valves through which  the added-on loop interfaces with the power




plant coolant cycle.  The  only difference between the normal, pre-existing




operation and the added-on, combined  operation is that the demand on the




original  cooling tower  is  reduced  by  about 5 percent; this  is a  beneficial




effect, especially  during  hot weather conditions.
                                      57

-------
 REFERENCES
 1)  "Interface Enhancement Applied to Evaporation of Liquids," Hugo H. Sephton,
     U.S. Patent No. 3,846,254, November 1974.

 2)  "Vertical Tube Evaporation Utilizing Vortex Flow and Interface Enhancement,"
     Hugo H. Sephton, U.S. Department of the Interior, Office of Saline Water,
     Research and Development Report No. 574, May 1970.

 3)  "Interface Enhancement for Vertical Tube Evaporators:  A Novel Way of
     Substantially Augmenting Heat and Mass Transfer," Hugo H. Sephton,
     Presented at the American Society of Mechanical Engineers Heat Transfer
     Conference, Tulsa, Oklahoma, August 1971, ASME Publication 71-HT-38.

 4)  "Upflow Vertical Tube Evaporation of Seawater with Interface Enhancement:
     Process Development by Pilot Plant Testing," Hugo H. Sephton, Desali nation.
     Vol. 16, No.  1, pp. 1-13, February 1975.

 5)  "Desalination by Upflow Vertical  Tube Evaporation with Interface Enhancement,"
     Hugo H. Sephton, Proceedings, International Desalting and Environmental
     Association Conference, Ponce, Puerto Rico, April 1975-

 6)  "Interface Enhancement for Vertical Tube Evaporation of Seawater," Hugo
     H. Sephton, Proceedings of the 4th International  Symposium on Fresh Water
     from the Sea," Vol. 1, pp. 471-480, September 1973.

 7)  "Upflow Vertical Tube Evaporation with Interface Enhancement:  Pressure
     Drop Reduction and Heat Transfer Enhancement by the Addition of a Surfactant,"
     Howard L. Fong, C. Judson King and Hugo H.  Sephton,  Desalination, Vol. 16,
     No. 1, pp 15-38, February 1975.

 8)  "Effects of Alkyl  Amine Surfactants on Mass Transfer Controlled Corrosion
     Reactions," G. Kar, I. Cornet and D. W. Fuerstenau,  J. Electrochem. Soc.
     119, 33-39 (1972).

 9)  "Performance Characteristics of Advanced Tubes for Long Tube Vertical
     Evaporators," L. A. Alexander and H. W. Hoffman,  Office of Saline Water,
     Research Development Progress Report No. 644, January 1971, p. 68.

10)  "Some Factors Affecting Heat Transfer Coefficients in the Horizontal
     Tube Multiple Effect (HTME)  Distillation Process," R. B.  Cox, Proceedings
     of Third International Symposium on Fresh Water from the Sea, 1 (1970) 247-263.

11)  "Recycle of Power  Plant Cooling Tower Slowdown by Vertical Tube Evaporation
     with Interface Enhancement," Hugo H. Sephton, Presented at EPA-AIChE Second
     National  Conference on Complete WateReuse,  Chicago,  Illinois, May 4-8, 1975.

12)  Desalination  of Cooling Tower Slowdown," L. Awerbuch and A. N. Rogers,
     Presented at  EPA-AIChE Second National  Conference on Complete WateReuse,
     Chicago,  Illinois, May 4-8,  1975.
                                         53

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                                  TECHNICAL REPORT DATA
                           (Please read Instructions on the reverse before completing)
1. REPORT NO.
  EPA-6QO/2-76-017
                             2.
                                                          3. RECIPIENT'S ACCESSION-NO'.
4. TITLE AND SUBTITLE
  Renovation of Industrial Inorganic Wastewater by
  Evaporation with  Interface Enhancement
                                            5. REPORT DATE
                                             March 19T& (Issuing Date)
                                            6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
      Hugo H.
Sephton
                                                          8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
  Sea Water Conversion Laboratory
  University  of California
  1301 South  U6 Street
  Richmond, California  9U80U
                                            10. PROGRAM ELEMENT NO.
                                              1BBQ36;ROAP 21 AZQjTask 019
                                            11. CS»KM«SCT/GRANT NO.
                                                  R-802753
12. SPONSORING AGENCY NAME AND ADDRESS
   Industrial Environmental  Research Laboratory
  Office of Research and Development
  U.S. Environmental Protection Agency
  Cincinnati,  Ohio   1+5268
                                            13. TYPE OF REPORT AND PERIOD COVERED
                                            14. SPONSORING AGENCY CODE

                                                   EPA-ORD
15. SUPPLEMENTARY NOTES
16. ABSTRACT           •                                ,   ,.
       A  novel method of vertical tube evaporation (VTE) to improve heat  transfer
  performance  was applied to the concentration of three types of industrial waste-
  waters.  This method, interface enhancement, relies upon the addition of a few
  parts per million of a selected surfactant to the wastewater feed followed by
  imposed two-phase foamy liquid-vapor flow over the heat transfer surfaces.  Applied
  to the  concentration of power plant cooling tower blowdown and boiler blovdown,
  interface-enhanced VTE provided an approximate 120 percent increase  in  the usual
  VTE heat transfer performance, using a  5,000 gpd pilot plant having  double-fluted
  aluminum-brass distillation tubes, under  process coaditions that are realistic for
  large industrial plants.  Acidic mine drainage water, concentrated by double-fluted
  titanium evaporator tubes provided about  a 60 percent heat transfer  performance
  enhancement.  Beneficial side effects of  the surfactant additive were to inhibit
  the crystallization of solutes, permitting concentration of the wastewaters to
  smaller volumes.  This work indicates feasibility and improved economics for renova-
  tion-recycle of each of the three types of wastewater examined.
       Industrial feasibility demonstration projects for each of the three wastewater
  types examined are recommended.  A method and flow diagram for the desalination-
  recycle of power plant cooling tower blowdown by interface-enhanced  VTE integrated
  with typical power plant coolant cycle  and utilizing waste heat from that cycle, is
17.
                               KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                              b.lDENTIFIERS/OPEN ENDED TERMS
                                                          c. COSATI Field/Group
  Heat  exchangers
  Evaporation*
  Heat  transfer*
  Waste water
                                Evaporation enhancement
                                Surfactant enhancement
                                Inorganic  brine concen-
                                tration
                                Foam fractionation
                                Waste water treatment
13B
20M
18. DISTRIBUTION STATEMENT
   Release to Public
                                              19. SECURITY CLASS (ThisReport)
                                                Unclassified
                                                                         21. NO.-O.F PAGES
                                                               67
                                              20. SECURITY CLASS (Thiipage)
                                                Unclassified
                                                                         22. PRICE
EPA Form 2220-1 (9-73)

. U. S. GOVHNMENT PUNTING OFFICE: 1976-657-635/538?  Reg I on No. 5- II
                              59

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