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RELATED PATENT APPLICATIONS  
       [0001]     This application is a Continuation-In-Part of prior U.S. patent application Ser. No. 10/868,745, filed Jun. 9, 2004, which was a Continuation-In-Part of prior U.S. patent application Ser. No. 10/307,250, filed Nov. 30, 2002, which was a Continuation-In-Part of prior U.S. patent application Ser. No. 09/566,622, filed May 8, 2000, now U.S. Pat. No. 6,733,636B1 issued May 11, 2004, entitled WATER TREATMENT METHOD FOR HEAVY OIL PRODUCTION, which claimed priority from prior U.S. Provisional Patent Application Ser. No. 60/133,172, filed on May 7, 1999. Also, this application claims priority from U.S. Provisional Patent Application Ser. No. 60/578,810, filed Jun. 9, 2004. The disclosures of each of the above identified patents or patent applications are incorporated herein in their entirety by this reference, including the specification, drawing, and claims of each patent or application. 
     
    
     COPYRIGHT RIGHTS IN THE DRAWING  
       [0002]     A portion of the disclosure of this patent document contains material that is subject to copyright protection. The applicant no objection to the facsimile reproduction by anyone of the patent document or the patent disclosure, as it appears in the Patent and Trademark Office patent file or records, but otherwise reserves all copyright rights whatsoever.  
       TECHNICAL FIELD  
       [0003]     The invention disclosed and claimed herein relates to treatment of water to be used for steam generation in operations which utilize steam to recover oil from geological formations. More specifically, this invention relates to novel, improved techniques for efficiently and reliably generating from oil field produced waters, in high pressure steam generators, the necessary steam for down-hole use in heavy oil recovery operations.  
       BACKGROUND  
       [0004]     Steam generation is necessary in heavy oil recovery operations. This is because in order to recover heavy oil from certain geologic formations, steam is required to increase the mobility of the sought after oil within the formation. In prior art systems, oil producers have often utilized once-through type steam generators (“OTSG&#39;s). As generally utilized in the industry, once through steam generators—OTSG&#39;s—usually have high blowdown rates, often in the range of from about 20% to about 30% or thereabouts. Such a blowdown rate leads to significant thermal and chemical treatment inefficiencies. Also, once through steam generators are most commonly provided in a configuration and with process parameters so that steam is generated from a feedwater in a single-pass operation through boiler tubes that are heated by gas or oil burners. Typically, such once through steam generators operate at from about 1000 pounds per square inch gauge (psig) to about 1600 psig or so. In some cases, once through steam generators are operated at up to as much as about 1800 psig. Such OTSG&#39;s often operate with a feedwater that has from about 2000 mg/L to about 8000 mg/L of total dissolved solids. As noted in  FIG. 1 , which depicts the process flow sheet of a typical prior art water treatment system  10 , such a once through steam generator  12  provides a low quality or wet steam, wherein about eighty percent (80%) quality steam is produced. In other words, the 80% quality steam  14  is about 80% vapor, and about 20% liquid, by weight percent. The steam portion, or high pressure steam produced in the steam generators is injected via steam injection wells  16  to fluidize as indicated by reference arrows  18 , along or in combination with other injectants, the heavy oil formation  20 , such as oils in tar sands formations. The injected steam  14  eventually condenses and an oil/water mixture  22  results, and which mixture migrates through the formation  20  as indicated by reference arrows  24 . The oil/water mixture  22  is gathered as indicated by reference arrows  26  by oil/water gathering wells  30 , through which the oil/water mixture is pumped to the surface. Then, the sought-after oil is sent to an oil/water separator  32  in which the oil product  34  separated from the water  35  and recovered for sale. The produced water stream  36 , after separation from the oil, is further de-oiled in a de-oiling process step  40 , normally by addition of a de-oiling polymer  42  or by other appropriate processes. Such a de-oiling process usually results in generation of an undesirable waste oil/solids sludge  44 . However, the de-oiled produced water stream  46  is then further treated for reuse.  
         [0005]     The design and operation of the water treatment plant which treats the de-oiled produced water stream  46 , i.e., downstream of the de-oiling unit  40  and upstream of injection well  16  inlet  48 , is the key to the improvement(s) described herein.  
         [0006]     Most commonly in prior art plants such as plant  10 , the water is sent to the “once-through” steam generators  12  for creation of more steam  14  for oil recovery operations. The treated produced water stream  12 F which is the feed stream for the once through steam generator, at time of feed to the steam generator  12 , is typically required to have less than about 8000 parts per million (“PPM”) of total dissolved solids (“TDS”). Less frequently, the treated produced water stream  12 F may have up to about 12000 parts per million (as CaCO3 equivalent) of total dissolved solids, as noted in  FIG. 8 . Further, it is often necessary to meet other specific water treatment parameters before the water can be reused in such once-through steam generators  12  for the generation of high pressure steam.  
         [0007]     In most prior art water treatment schemes, the de-oiled recovered water  46  must be treated in a costly water treatment plant sub-system  101  before it can be sent to the steam generators  12 . Treatment of water before feed to the once-through steam generators  12  is often initially accomplished by using a warm lime softener  50 , which removes hardness, and which also removes some silica from the de-oiled produced water feedstream  46 . Various softening chemicals  52  are usually necessary, such as lime, flocculating polymer, and perhaps soda ash. The softener clarifier  54  underflow  56  produces a waste sludge  58  which must be further handled and disposed. Then, an “after-filter”  60  is often utilized on the clarate stream  59  from the softener clarifier  54 , to prevent carry-over from the softener clarifier  54  of any precipitate or other suspended solids, which substances are thus accumulated in a filtrate waste stream  62 . For polishing, an ion exchange step  64 , normally including a hardness removal step such as a weak acid cation (WAC) ion-exchange system that can be utilized to simultaneously remove hardness and the alkalinity associated with the hardness, is utilized. The ion exchange systems  64  require regeneration chemicals  66  as is well understood by those of ordinary skill in the art and to which this disclosure is directed. As an example, however, a WAC ion exchange system is usually regenerated with hydrochloric acid and caustic, resulting in the creation of a regeneration waste stream  68 . Overall, such prior art water treatment plants are relatively simple, but, result in a multitude of liquid waste streams or solid waste sludges that must be further handled, with significant additional expense.  
         [0008]     In one relatively new heavy oil recovery process, known as the steam assisted gravity drainage heavy oil recovery process (the “SAGD” process), it is preferred that one hundred percent (100%) quality steam be provided for injection into wells (i.e., no liquid water is to be provided with the steam to be injected into the formation). Such a typical prior art system  11  is depicted in  FIG. 2 . However, given conventional prior art water treatment techniques as just discussed in connection with  FIG. 1 , the 100% steam quality requirement presents a problem for the use of once through steam generators  12  in such a process. That is because in order to produce 100% quality steam  70  using a once-through type steam generator  12 , a vapor-liquid separator  72  is required to separate the liquid water from the steam. Then, the liquid blowdown  73  recovered from the separator is typically flashed several times in a series of flash tanks F 1 , F 2 , etc. through F N  (where N is a positive integer equal to the number of flash tanks) to successively recover as series of lower pressure steam flows S 1 , S 2 , etc. which may sometimes be utilized for other plant heating purposes. After the last flashing stage F N , a residual hot water final blowdown stream  74  must then be handled, by recycle and/or disposal. The 100% quality steam is then sent down the injection well  16  and injected into the desired formation  20 . Fundamentally, though, conventional treatment processes for produced water used to generate steam in a once-through steam generator produces a boiler blowdown which is roughly twenty percent (20%) of the feedwater volume. This results in a waste brine stream that is about fivefold the concentration of the steam generator feedwater. Such waste brine stream must be disposed of by deep well injection, or if there is limited or no deep well capacity, by further concentrating the waste brine in a crystallizer or similar system which produces a dry solid for disposal.  
         [0009]     As depicted in  FIG. 3 , another method which has been proposed for generating the required 100% quality steam for use in the steam assisted gravity drainage process involves the use of boilers  80 , which may be packaged, factory built boilers of various types or field assembled boilers with mud and steam drums and water wall piping. Various methods can be used for producing water of a sufficient quality to be utilized as feedwater  80 F to a boiler  80 . One method which has been developed for use in heavy oil recovery operations involves de-oiling  40  of the produced water  36 , followed by a series of physical-chemical treatment steps. Such treatment steps normally include a series of unit operations as warm lime softening  54 , followed by filtration  60  for removal of residual particulates, then an organic trap  84  (normally non-ionic ion exchange resin) for removal of residual organics. The organic trap  84  may require a regenerant chemical supply  85 , and, in any case, produces a waste  86 , such as a regenerant waste. Then, a pre-coat filter  88  can be used, which has a precoat filtrate waste  89 . In one alternate embodiment, an ultrafiltration (“UF”) unit  90  can be utilized, which unit produces a reject waste stream  91 . Then, effluent from the UF unit  90  or precoat filter  88  can be sent to a reverse osmosis (“RO”) system  92 , which in addition to the desired permeate  94 , produces a reject liquid stream  96  that must be appropriately handled. Permeate  94  from the RO system  92 , can be sent to an ion exchange unit  100 , typically but not necessarily a mixed bed demineralization unit, which of course requires regeneration chemicals  102  and which consequently produces a regeneration waste  104 . And finally, the boiler  80  produces a blowdown  110  which must be accommodated for reuse or disposal.  
         [0010]     The prior art process designs, such as depicted in  FIG. 3 , for utilizing packaged boilers in heavy oil recovery operations, have a high initial capital cost. Also, such a series of unit process steps involves significant ongoing chemical costs. Moreover, there are many waste streams to discharge, involving a high and ongoing sludge disposal cost. Further, where membrane systems such as ultrafiltration  90  or reverse osmosis  92  are utilized, relatively frequent replacement of membranes  106  or  108 , respectively, may be expected, with accompanying on-going periodic replacement costs. Also, such a process scheme can be labor intensive to operate and to maintain.  
         [0011]     In summary, the currently known and utilized methods for treating heavy oil field produced waters in order to generate high quality steam for down-hole use are not entirely satisfactory because: 
        such physical-chemical treatment process schemes are usually quite extensive, are relatively difficult to maintain, and require significant operator attention;     such physical-chemical treatment processes require many chemical additives which must be obtained at considerable expense, and many of which require special attention for safe handling;     such physical-chemical treatment processes produce substantial quantities of undesirable sludges and other waste streams, the disposal of which is increasingly difficult, due to stringent environmental and regulatory requirements.        
 
         [0015]     It is clear that the development of a simpler, more cost effective approach to produced water treatment would be desirable in the process of producing steam in heavy oil production operations. Thus, it can be appreciated that it would be advantageous to provide a new produced water treatment process which minimizes the production of undesirable waste streams, while minimizing the overall costs of owning and operating a heavy oil recovery plant.  
       SOME OBJECTS, ADVANTAGES, AND NOVEL FEATURES  
       [0016]     The new water treatment process(es) disclosed herein, and various embodiments thereof, can be applied to heavy oil production operations. Such embodiments are particularly advantageous in that they minimize the generation of waste products, and are otherwise superior to water treatment processes heretofore used or proposed in the recovery of bitumen from tar sands or other heavy oil recovery operations.  
         [0017]     From the foregoing, it will be apparent to the reader that one of the important and primary objectives resides in the provision of a novel process, including several variations thereof, for the treatment of produced waters, so that such waters can be re-used in producing steam for use in heavy oil recovery operations.  
         [0018]     Another important objective is to simplify process plant flow sheets, i.e., minimize the number of unit processes required in a water treatment train, which importantly simplifies operations and improves quality control in the manufacture of high purity water for down-hole applications.  
         [0019]     Other important but more specific objectives reside in the provision of various embodiments for an improved water treatment process for production of high purity water for down-hole use in heavy oil recovery, which embodiments may: 
        in one embodiment, eliminate the requirement for flash separation of the high pressure steam to be utilized downhole from residual hot pressurized liquids;     eliminate the generation of softener sludges;     minimize the production of undesirable liquid or solid waste streams;     minimize operation and maintenance labor requirements;     minimize maintenance materiel requirements;     minimize chemical additives and associated handling requirements;     increase reliability of the OTSG&#39;s, when used in the process;     decouple the de-oiling operations from steam production operations; and     reduce the initial capital cost of water treatment equipment.        
 
         [0029]     Other important objectives, features, and additional advantages of the various embodiments of the novel process disclosed herein will become apparent to the reader from the foregoing and from the appended claims and the ensuing detailed description, as the discussion below proceeds in conjunction with examination of the accompanying drawing. 
     
    
     BRIEF DESCRIPTION OF THE DRAWING  
       [0030]     In order to enable the reader to attain a more complete appreciation of the novel water treatment process disclosed and claimed herein, and the various embodiments thereof, and of the novel features and the advantages thereof over prior art processes, attention is directed to the following detailed description when considered in connection with the accompanying figures of the drawing, wherein:  
         [0031]      FIG. 1  shows one typical prior art process, namely a generalized process flow diagram for a physical-chemical water treatment process configured for use in heavy oil recovery operations.  
         [0032]      FIG. 2  shows another prior art process, namely a generalized process flow diagram for a physical-chemical water treatment process as used in a steam assisted gravity drainage (SAGD) type heavy oil operation.  
         [0033]      FIG. 3  shows yet another prior art physical-chemical treatment process scheme, also as it might be applied for use in steam assisted gravity drainage (SAGD) type heavy oil recovery operations.  
         [0034]      FIG. 4  shows one embodiment of an evaporation based water treatment process, illustrating the use of a seeded slurry evaporation based process in combination with the use of packaged boilers for steam production, as applied to heavy oil recovery operations.  
         [0035]      FIG. 5  shows another embodiment for an evaporation based water treatment process for heavy oil production, illustrating the use of a seeded slurry evaporation process in combination with the use of once-through steam generators for steam production, as applied to heavy oil recovery operations, which process is characterized by feed of evaporator distillate to once-through steam generators without the necessity of further pretreatment.  
         [0036]      FIG. 6  shows a common variation for the orientation of injection and gathering wells as utilized in heavy oil recovery, specifically showing the use of horizontal steam injection wells and of horizontal oil/water gathering wells, as often employed in a steam assisted gravity drainage heavy oil gathering project.  
         [0037]      FIG. 7  shows the typical feedwater quality requirements for steam generators which produce steam in the 1000 pounds per square inch gauge range, or thereabouts, for conventional steam boiler installations.  
         [0038]      FIG. 8  shows the typical feedwater quality requirements for steam generators which produce steam in the 1000 pounds per square inch gauge range, or thereabouts, for once-through type steam generator installations.  
         [0039]      FIG. 9  provides a simplified view of a vertical tube falling film evaporator operating in a seeded slurry mode in the treatment of produced water from heavy oil operations, for production of distillate for reuse in once through steam generators or in conventional steam boilers.  
         [0040]      FIG. 10  shows further details of the use of evaporators operating in a seeded slurry mode, illustrated by use of falling film evaporators, and indicates selected injection points for acidification of the feedwater and for control of pH in the evaporator via optional injection of a selected base such as sodium hydroxide.  
         [0041]      FIG. 11  illustrates the solubility of silica in water as a function of pH at 25° C. when such silica species are in equilibrium with amorphous silica, as well as the nature of such soluble silica species (molecule or ion) at various concentration and pH ranges.  
         [0042]      FIG. 12  diagrammatically illustrates functional internal details of the operation of a falling film evaporator operating in a seeded slurry mode, which evaporator type would be useful in the evaporation of produced waters from heavy oil production; details illustrated include the production of steam from a falling brine film, by a heat exchange relationship from condensation of steam on a heat exchange tube, and the downward flow of such steam condensate (distillate) by gravity for the collection of such condensate (distillate) above the bottom tube sheet of the evaporator. 
     
    
       [0043]     The foregoing figures, being merely exemplary, contain various elements that may be present or omitted from actual process implementations depending upon the circumstances. An attempt has been made to draw the figures in a way that illustrates at least those elements that are significant for an understanding of the various embodiments and aspects of the invention. However, various other elements of the unique process methods, and the combination of apparatus for carrying out the methods, are also shown and briefly described to enable the reader to understand how various features, including optional or alternate features, may be utilized in order to provide an efficient, low cost process design which can be implemented in a desired throughput size and physical configuration for providing optimum water treatment plant design and operation.  
       DESCRIPTION  
       [0044]     Many steam assisted heavy oil recovery schemes, such as a steam assisted gravity drainage (SAGD) heavy oil recovery process injection and recovery well arrangements of the type depicted in  FIG. 6 , most efficiently utilize a 100% quality steam supply  70 . It would therefore be desirable to produce such a steam supply by an efficient process scheme such as I have found may be provided by evaporation based heavy oil produced water treatment method(s). Various embodiments and details of such evaporation based produced water treatment method(s) are depicted in  FIGS. 4, 5 ,  6 ,  9 ,  10  and  12 .  
         [0045]     As depicted in  FIG. 6 , in a SAGD process, horizontal injection wells  16 ′ and horizontal oil/water gathering wells  30 ′ are advantageously utilized spaced apart within an oil bearing formation  20 . As particularly illustrated in  FIGS. 4 and 5 , a process for the use of an evaporation based water treatment system  120  has been developed to treat produced water, in order to produce high quality steam for use in further heavy oil recovery. Conceptually, such an evaporative water treatment process may, in one embodiment, be situated process wise—that is, water flow wise—between the point of receipt of a de-oiled produced water stream  46  and the point of steam injection at well head  48  of injection well  16 . The process, in combination with the steam injection well  16 , oil recovery well  30 , and related oil water separation equipment  32  and de-oiling equipment  40 , and boilers  80  as shown in  FIG. 4 , or alternately, once through steam generators  12  as shown in  FIG. 5 , can substantially reduce capital costs and can minimize ongoing operation and maintenance costs of heavy oil recovery installations. Boilers  80  may be packaged, factory built boilers of various types or field assembled boilers with mud and steam drums and water wall piping, or more generally, conventional steam boilers. In some locales, such as northern Canada, the possibility of elimination of the need for handling of waste sludges and other waste streams made possible by the evaporation based water treatment system  120  may be especially important, since it may be difficult to work with such waste materials during the extremely cold winter months.  
         [0046]     It has been observed that it may be desirable in some instances to use a packaged boiler  80  to produce the required steam  70 , rather than to utilize a traditional once-through type steam generator  12  to produce 80% quality steam  14  and then utilize separator(s)  130  to separate steam  132  from liquid  134 . It is noteworthy in such an economic process evaluation that packaged boilers  80  are often less expensive on a capital cost basis and on an operating cost basis than once-through type oil-field steam generators  12 . Also, package boilers can be utilized to produce pure steam  70 , and thus produce only a minimal liquid blowdown stream  110 . Also, as shown in  FIGS. 4 and 5 , boiler blowdown stream can be either sent to the evaporator feed tank  210 , or injected into the sump reservoir  152  of evaporator  140 , such as via line  111 , or into a recirculating brine via line  111 ′. One type of packaged boiler suitable for use in the process described herein is a water tube boiler having a lower mud drum and an upper steam drum and water cooled sidewalls substantially extending therebetween in a manner which encloses a combustion chamber. However, most such packaged boilers require a much higher quality feed water  80 F than is the case with requirements for feedwater  12 F for a once-through type steam generator. As a result, in one embodiment, the process disclosed herein includes an evaporation unit  140  based approach to packaged boiler  80  feedwater  80 F pretreatment. In other words, the de-oiled produced water  46  generated can be advantageously treated by an evaporative process operating in a seeded slurry mode, particularly if the oil in the de-oiled produced water is reduced reliably to a selected low level of less than about 20 parts per million, or more preferably to less than about 10 parts per million, and provides a significantly improved method for produced water treatment in heavy oil production.  
         [0047]     An oil/water mixture  22  is pumped up through oil gathering wells  30 . The oil water mixture  22  is sent to a series of oil/water separators  32 . An oil product  34  is gathered for further conditioning, transport, and sale. The produced water  36  which has been separated from the oil/water mixture  22  is then sent to a produced water de-oiling step  40 , which may be accomplished in dissolved air flotation units with the assistance of the addition of a de-oiling polymer  42 , or by other appropriate unit processes, to achieve a preselected low residual oil level such as less than 20 parts per million.  
         [0048]     In the water treatment method disclosed herein, the de-oiled produced water  46  is treated and conditioned for feed to one or more mechanical vapor recompression evaporator units  140  (normally, multiple redundant units) to concentrate the incoming produced water stream  46 . The necessary treatment and conditioning prior to the evaporator unit  140  can be efficiently accomplished, but may vary somewhat based on feedwater chemistry—i.e. the identity and distribution of various dissolved and suspended solids—and on the degree of concentration selected for accomplishment in evaporator units  140 .  
         [0049]     In one embodiment, it may be necessary or appropriate to add acid by line  144 , or at an appropriate point upstream of the feed tank  210  when desired such as via line  146 ′. A suitable acid may be sulfuric acid or hydrochloric acid, which is effective to lower the pH sufficiently so that bound carbonates are converted to free gaseous carbon dioxide, which is removed, along with other non-condensable gases  148  dissolved in the feedwater  46  such as oxygen and nitrogen, in an evaporator feedwater deaerator  150 . However, use of acid  144  is this manner is optional, and can sometimes be avoided if feedwater chemistry and the concentration limits of scale forming species are sufficiently low at the anticipated concentration factor utilized in evaporator  140 . For pH control, as seen in  FIG. 10 , it may be useful to add a selected base such as caustic  232  to the concentrated brine recirculating in the evaporator  140 , which can be accomplished by direct injection of a selected base such as caustic  232  into the sump  141 , as indicated by line  157 , or by feed of a selected base such as caustic  232  into the suction of recirculation pump  153 , as indicated by line  159 . However, if the produced water contains an appreciable amount of calcium and sulfate, the mechanical vapor recompression evaporator  140  may in one embodiment be operated using a calcium sulfate seeded-slurry technique, normally in a near neutral pH range. That mode of operation can be made possible by the substantial elimination of carbonate alkalinity before the feedwater is introduced into the evaporator  140 . Then, the evaporator  140  may be operated a seeded-slurry mode wherein calcium sulfate and silica co precipitated recirculating seed crystals, which avoids scaling of the heat transfer surfaces.  
         [0050]     At feedwater heat exchanger, the feedwater pump  149  is used to provide sufficient pressure to send feedwater from the evaporator feed tank  210  through the feedwater heat exchanger  148 , prior to the deaerator  150 . In the opposite direction, the distillate pump  143  moves distillate  180  through the feedwater heat exchanger  148 , so that the hot distillate is used to heat the feedwater stream directed toward the deaerator  150 .  
         [0051]     The conditioned feedwater  151  is sent as feedwater to evaporator  140 . The conditioned feedwater  151  may be directed to the inlet of recirculation pump  153 , or alternately, directed to the sump  141  of evaporator  140  as indicated by broken line  151 ′ in  FIG. 10 . Concentrated brine  152  in the evaporator  140  is recirculated via pump  153 , so only a small portion of the recirculating concentrated brine is removed on any one pass through the evaporator  140 . In the evaporator  140 , the solutes in the feedwater  46  are concentrated via removal of water from the feedwater  46 . As depicted in  FIGS. 10 and 12 , an evaporator  140  is in one embodiment provided in a falling film configuration wherein a thin brine film  154  is provided by distributors  155  and then falls inside of a heat transfer element, e.g. tube  156 . A small portion of the water in the thin brine film  154  is extracted in the form of steam  160 , via heat given up from heated, compressed steam  162  which is condensing on the outside of heat transfer tubes  156 . Thus, the water is removed in the form of steam  160 , and that steam is compressed through the compressor  164 , and the compressed steam  162  is condensed at a heat exchange tube  156  in order to produce yet more steam  160  to continue the evaporation process. The condensing steam on the outer wall  168  of heat transfer tubes  156 , which those of ordinary skill in the evaporation arts and to which this disclosure is directed may variously refer to as either condensate or distillate  180 , is in relatively pure form, low in total dissolved solids. In one embodiment, such distillate contains less than 10 parts per million of total dissolved solids of non-volatile components. Since, as depicted in the embodiments shown in  FIGS. 4, 5 ,  9 , and  10 , a single stage of evaporation is provided, such distillate  180  may be considered to have been boiled, or distilled, once, and thus condensed but once.  
         [0052]     Prior to the initial startup of the evaporator  140  in the seeded-slurry mode, the evaporator, which in such mode may be provided in a falling-film, mechanical vapor recompression configuration, the fluid contents of the unit are “seeded” by the addition of calcium sulfate (gypsum). The circulating solids within the brine slurry serve as nucleation sites for subsequent precipitation of calcium sulfate  272 , as well as silica  274 . Such substances both are precipitated as an entering feedwater is concentrated. Importantly, the continued concentrating process produces additional quantities of the precipitated species, and thus creates a continuing source of new “seed” material as these particles are broken up by the mechanical agitation, particularly by the action of the recirculation pump  153 .  
         [0053]     In order to avoid silica and calcium sulfate scale buildup in the evaporator  140 , calcium sulfate seed crystals  272  are continuously circulated over the wetted surfaces, i.e., the falling film evaporator tubes  156 , as well as other wetted surfaces in the evaporator  140 . Through control of slurry concentration, seed characteristics, and system geometry, the evaporator can operate in the otherwise scale forming environment. The thermo chemical operation within the evaporator  140  with regard to the scale prevention mechanism is depicted in  FIG. 12 . As the water is evaporated from the brine film  154  inside the tubes  156 , the remaining brine film becomes super saturated and calcium sulfate and silica start to precipitate. The precipitating material promotes crystal growth in the slurry rather than new nucleation that would deposit on the heat transfer surfaces; the silica crystals attach themselves to the calcium sulfate crystals. This scale prevention mechanism, called preferential precipitation, has a proven capability to promote clean heat transfer surfaces  260 . The details of one advantageous method for maintaining adequate seed crystals in preferentially precipitation systems is set forth in U.S. Pat. No. 4,618,429, issued Oct. 21, 1986 to Howard R. Herrigel, the disclosure of which is incorporated into this application in full by this reference.  
         [0054]     It is to be understood that the falling film evaporator  140  design is provided only for purposes of illustration and thus enabling the reader to understand the water treatment process(es) taught herein, and is not intended to limit the process to the use of such evaporator design, as those in the art will recognize that other designs, such as, for example, a forced circulation evaporator, or a rising film evaporator, may be alternately utilized with the accompanying benefits and/or drawbacks as inherent in such alternative evaporator designs.  
         [0055]     In any event, in a falling film evaporator embodiment, the distillate  180  descends by gravity along tubes  156  and accumulates above bottom tube sheet  172 , from where it is collected via condensate line  174 . A small portion of steam in equilibrium with distillate  180  may be sent via line  172  to the earlier discussed deaerator  150  for use in mass transfer, i.e, heating and steam stripping descending liquids in a packed tower to remove non-condensable gases  148  such as carbon dioxide. However, the bulk of the distillate  180  is removed as a liquid via line  180 ′, and may optionally be sent for further treatment in a distillate treatment plant, for example such as depicted in detail in  FIG. 4 , or as merely depicted in functional form as feed  181   F  for plant  181  in  FIG. 5 , to ultimately produce a product water  181   P  which is suitable for evaporator feedwater, such as feedwater  80 F′ in the case where packaged boilers  80  are utilized as depicted in  FIG. 4 . The plant  181  also normally produces a reject stream  181   R  which may be recycled to the evaporator feed tank  210  or other suitable location for reprocessing or reuse. As shown in the embodiment set forth in  FIG. 5 , the distillate treatment plant  181  is optional, especially in the case of the use of once through steam generators, and in such instance the distillate  180  may often be sent directly to once-through steam generators as feedwater  12 F′ (as distinguished from the higher quality from feedwater  12 F discussed hereinabove with respect to prior art processes) for generation of 80% quality steam  14 . Also, as shown in  FIG. 4 , a distillate treatment plant  181  may also be optional in some cases, depending on feedwater chemistry, and in such cases, distillate  180  may be fed directly to boiler  80  as indicated by broken line  81 .  
         [0056]     In an embodiment where boilers  80  are used rather than once through steam generators  12 , however, it may be necessary or desirable to remove the residual organics and other residual dissolved solids from the distillate  180  before feed of distillate  180  to the boilers  80 . For example, as illustrated in  FIG. 4 , in some cases, it may be necessary to remove residual ions from the relatively pure distillate  180  produced by the evaporator  140 . In most cases the residual dissolved solids in the distillate involve salts other than hardness. In one embodiment, removal of residual dissolved solids can be accomplished by passing the evaporator distillate  180 , after heat exchanger  200 , through an ion exchange system  202 . Such ion-exchange systems may be of mixed bed type or include an organic trap, and directed to remove the salts and/or organics of concern in a particular water being treated. In any event, regenerant chemicals  204  will ultimately be required, which regeneration results in a regeneration waste  206  that must be further treated. Fortunately, in the process scheme described herein, the regeneration waste  206  can be sent back to the evaporator feed tank  210  for a further cycle of treatment through the evaporator  140 .  
         [0057]     In another embodiment, removal of residual dissolved solids can be accomplished by passing the evaporator distillate  180  through a heat exchanger  200 ′ and then through electrodeionization (EDI) system  220 . The EDI reject  222  is also capable of being recycled to evaporator feed tank  210  for a further cycle of treatment through the evaporator  140 .  
         [0058]     The just described novel combination of process treatment steps produces feedwater of sufficient quality, and in economic quantity, for use in packaged boilers  80  in heavy oil recovery operations. Advantageously, when provided as depicted in  FIG. 4 a  single liquid waste stream is generated, namely evaporator blowdown  230 , which contains the concentrated solutes originally present in feedwater  46 , along with additional contaminants from chemical additives (such as regeneration chemicals  204 ). Also, in many cases, even the evaporator blowdown  230  can be disposed in an environmentally acceptable manner, which, depending upon locale, might involve injection in deep wells  240 . Alternately, evaporation to complete dryness in a zero discharge system  242 , such as a crystallizer or drum dryer, to produce dry solids  244  for disposal, may be advantageous in certain locales.  
         [0059]     Various embodiments for new process method(s), as set forth in  FIGS. 4 and 5  for example, are useful in heavy oil production since they generally offer one or more of the following advantages: (1) eliminate many physical-chemical treatment steps commonly utilized previously in handing produced water (for example, lime softening, filtrating, ion exchange systems, and certain de-oiling steps are eliminated); (2) result in lower capital equipment costs, since the evaporative approach to produced water treatment results in a zero liquid discharge system footprint size that is about 80% smaller than that required if a prior art physical-chemical treatment scheme is utilized, as well as eliminating vapor/liquid separators and reducing the size of the boiler feed system by roughly 20%; (3)-result in lower operating costs for steam generation; (4) eliminate the production of softener sludge, thus eliminating the need for the disposal of the same; (5) eliminate other waste streams, thus minimizing the number of waste streams requiring disposal; (6) minimize the materiel and labor required for maintenance; (7) reduce the size of water de-oiling equipment in most operations; and (8) decouple the de-oiling operations from the steam generation operations.  
         [0060]     One of the significant economic advantages of using a vertical tube, falling film evaporator such as of the type described herein is that the on-line reliability and redundancy available when multiple evaporators are utilized in the treatment of produced water. An evaporative based produced water treatment system can result in an increase of from about 2% to about 3% or more in overall heavy oil recovery plant availability, as compared to a produced water treatment system utilizing a conventional prior art lime and clarifier treatment process approach. Such an increase in on-line availability relates directly to increased oil production and thus provides a large economic advantage over the life of the heavy oil recovery plant.  
         [0061]     In the process disclosed herein, the evaporator  140  is designed to produce high quality distillate (typically 2-5 ppm non-volatile TDS) which, after temperature adjustment to acceptable levels in heat exchangers  200  or  200 ′ (typically by cooling to about 45° C., or lower) can be fed directly into polishing equipment (EDI system  220 , ion exchange system  202 , or reverse osmosis system  224 ) for final removal of dissolved solids. The reject stream  221  from the reverse osmosis system can be recycled to the evaporator feed tank  210  for further treatment. Likewise, the reject from the EDI system may be recycled to the evaporator feed tank  210  for further treatment. Similarly, the regenerant from most ion exchange processes  202  may be recycled to the evaporator feed tank  210  for further treatment. The water product produced by the polish equipment just mentioned is most advantageously used as feedwater for the packaged boiler  80 . That is because in the typical once-though steam generator  12  used in oil field operations, it is normally unnecessary to incur the additional expense of final polishing by removal of residual total dissolved solids from the evaporator distillate stream  180 . In some applications, final polishing is not necessary when using conventional boilers  80 . This can be further understood by reference to  FIG. 6 , where a typical boiler feed water chemistry specification is presented for (a) packaged boilers, and (b) once-through steam generators. It may be appropriate in some embodiments from a heat balance standpoint that the de-oiled produced waters  46  fed to the evaporator for treatment be heated by heat exchange with the distillate stream  180 . However, if the distillate stream is sent directly to once-through steam generators  12 , then no cooling of the distillate stream  180  may be appropriate. Also, in the case of once-through steam generators  12 , it may be necessary or appropriate to utilize a plurality of flash tanks F 1 , etc., in the manner described above with reference to  FIG. 2 .  
         [0062]     Also, as briefly noted above, but significantly bears repeating, in those cases where the EDI system  220  is utilized for polishing, the membrane reject stream includes an EDI reject stream  222  that is recycled to be mixed with the de-oiled produced water  46  in the evaporator feed tank  210  system, for reprocessing through the evaporator  140 . Similarly, when reverse osmosis is utilized the a membrane reject stream includes the RO reject stream which is recycled to be mixed with the de-oiled produced water  46  in the evaporator feed tank  210  system, for reprocessing through the evaporator  140 . Likewise, when ion-exchange system  202  is utilized, the regenerant waste stream  206  is recycled to be mixed with the de-oiled produced water  46  in the evaporator feed tank system, for reprocessing through the evaporator  140 .  
         [0063]     Again, it should be emphasized that the blowdown  230  from the evaporator  140  is often suitable for disposal by deep well  240  injection. Alternately, the blowdown stream can be further concentrated and/or crystallized using a crystallizing evaporator, or a crystallizer, in order to provide a zero liquid discharge  242  type operation. This is an important advantage, since zero liquid discharge operations may be required if the geological formation is too tight to allow water disposal by deep well injection, or if regulatory requirements do not permit deep well injection.  
         [0064]     Many produced waters encountered in heavy oil production are high in silica, with values that may range up to about 200 mg/l as SiO 2 , or higher. Use of a seeded slurry operational configuration in evaporator  140  co-precipitates silica with precipitating calcium sulfate, to provide a process design which prevents the scaling of the inner surfaces  260  of the heat transfer tubes  156  with the ever-present silica. This is important, since silica solubility must be accounted for in the design and operation of the evaporator  140 , in order to prevent silica scaling of the heat transfer surfaces  260 .  
         [0065]     Since the calcium hardness and sulfate concentrations of many produced waters is low (typically 20-50 ppm Ca as CaCO3), it is possible in many cases to operate the evaporators  140  with economically efficient concentration factors, while remaining below the solubility limit of calcium sulfate, assuming proper attention to feedwater quality and to pre-treatment processes.  
         [0066]     It is to be appreciated that the water treatment process described herein for preparing boiler feedwater in heavy oil recovery operations is an appreciable improvement in the state of the art of water treatment for oil recovery operations. The process eliminates numerous of the heretofore encountered waste streams, while processing water in reliable mechanical evaporators, and in one embodiment, in mechanical vapor recompression (“MVR”) evaporators. Polishing, if necessary, can be accomplished in ion exchange, electrodeionization, or reverse osmosis equipment. The process thus improves on currently used treatment methods by eliminating most treatment or regeneration chemicals, eliminating many waste streams, eliminating some types of equipment. Thus, the complexity associated with a high number of treatment steps involving different unit operations is avoided.  
         [0067]     In the improved water treatment method, the control over waste streams is focused on a the evaporator blowdown, which can be conveniently treated by deep well  240  injection, or in a zero discharge system  242  such as a crystallizer and/or spray dryer, to reduce all remaining liquids to dryness and producing a dry solid  244 . This contrasts sharply with the prior art processes, in which sludge from a lime softener is generated, and in which waste solids are gathered at a filter unit, and in which liquid wastes are generated at an ion exchange system and in the steam generators. Moreover, this waste water treatment process also reduces the chemical handling requirements associated with water treatment operations.  
         [0068]     It should also be noted that the process described herein can be utilized with once through steam generators, since due to the relatively high quality feedwater—treated produced water—provided to such once through steam generators, the overall blowdown rate of as low as about 5% or less may be achievable in the once through steam generator. Alternately, as shown in  FIG. 5 , at least a portion of the liquid blowdown  134  from the once through steam generator  12  can be recycled to the steam generator  12 , such as indicated by broken line  135  to feed stream  12 F′.  
         [0069]     In yet another embodiment, to further save capital and operating expense, industrial boilers of conventional design may be utilized since the distillate—treated produced water—may be of sufficiently good quality to be an acceptable feedwater to the boiler, even if it requires some polishing. It is important to observe that use of such boilers reduces the boiler feed system and evaporative produced water treatment system size by twenty percent (20%), eliminates vapor/liquid separation equipment as noted above, and reduces the boiler blowdown flow rate by about ninety percent (90%).  
         [0070]     In short, evaporative treatment of produced waters using a falling film, vertical tube evaporator is technically and economically superior to prior art water treatment processes for heavy oil production. It is possible to recover ninety five percent (95%) or more, and even up to ninety eight percent (98%) or more, of the produced water as high quality distillate  180  for use as high quality boiler feedwater (resulting in only a 2% boiler blowdown stream which can be recycled to the feed for evaporator  140 ). Such a high quality distillate stream may be utilized in SAGD and non-SAGD heavy oil recovery operations. Such a high quality distillate stream may have less than 10 mg/L of non-volatile inorganic TDS and is useful for feed either to OTSGs or to conventional boilers.  
         [0071]     The overall life cycle costs for the novel treatment process described herein are significantly less than for a traditional lime softening and ion exchange treatment system approach. And, an increase of about 2% to 3% in overall heavy oil recovery plant availability is achieved utilizing the treatment process described herein, which directly results in increased oil production from the facility. Since boiler blowdown is significantly reduced, by as much as 90% or more, the boiler feed system may be reduced in size by as much as fifteen percent (15%) or more. Finally, the reduced blowdown size results in a reduced crystallizer size when zero liquid discharge is achieved by treating blowdown streams to dryness.  
         [0072]     Although only several exemplary embodiments of this invention have been described in detail, it will be readily apparent to those skilled in the art that the novel produced waste treatment process, and the apparatus for implementing the process, may be modified from the exact embodiments provided herein, without materially departing from the novel teachings and advantages provided by this invention, and may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. Therefore, the disclosures presented herein are to be considered in all respects as illustrative and not restrictive. It will thus be seen that the objects set forth above, including those made apparent from the preceding description, are efficiently attained. Many other embodiments are also feasible to attain advantageous results utilizing the principles disclosed herein. Therefore, it will be understood that the foregoing description of representative embodiments of the invention have been presented only for purposes of illustration and for providing an understanding of the invention, and it is not intended to be exhaustive or restrictive, or to limit the invention only to the precise forms disclosed.  
         [0073]     All of the features disclosed in this specification (including any accompanying claims, and the drawing) may be combined in any combination, except combinations where at least some of the features are mutually exclusive. Alternative features serving the same or similar purpose may replace each feature disclosed in this specification (including any accompanying claims, and the drawing), unless expressly stated otherwise. Thus, each feature disclosed is only one example of a generic series of equivalent or similar features. Further, while certain process steps are described for the purpose of enabling the reader to make and use certain water treatment processes shown, such suggestions shall not serve in any way to limit the claims to the exact variation disclosed, and it is to be understood that other variations, including various treatment additives or alkalinity removal techniques, may be utilized in the practice of my method.  
         [0074]     The intention is to cover all modifications, equivalents, and alternatives falling within the scope and spirit of the invention, as expressed herein above and in any appended claims. The scope of the invention, as described herein and as indicated by any appended claims, is thus intended to include variations from the embodiments provided which are nevertheless described by the broad meaning and range properly afforded to the language of the claims, as explained by and in light of the terms included herein, or the legal equivalents thereof.

Summary:
A process for treating produced water to generate high pressure steam. Produced water from heavy oil recovery operations is treated by first removing oil and grease. Feedwater is then acidified and steam stripped to remove alkalinity and dissolved non-condensable gases. Pretreated produced water is then fed to an evaporator. Up to 95% or more of the pretreated produced water stream is evaporated to produce (1) a distillate having a trace amount of residual solutes therein, and (2) evaporator blowdown containing substantially all solutes from the produced water feed. The distillate may be directly used, or polished to remove the trace residual solutes before being fed to a steam generator. Steam generation in a packaged boiler, such as a water tube boiler having a steam drum and a mud drum with water cooled combustion chamber walls, produces 100% quality high pressure steam for down-hole use.