The present invention is generally directed toward the treatment of water and, more particularly, toward the treatment of water containing large amounts of dissolved solids as may result, for example, from use of the water as a fracking fluid used in drilling gas wells. However, the embodiment proposed herein may be used in any situation where impurities to be removed from water exist.
Ensuring a supply of potable water has been a frequent concern in many locations. Further concerns arise about the environmental impact of the disposal of contaminated water.
Conventional water treatment techniques for such purposes as, for example, municipal water treatment and/or obtaining potable water from sea water are known and are successful in many instances. However, some current activities show those techniques to have limited cost effectiveness.
For example, mining with water used to fracture rock or shale formations to recover natural gas (e.g., in the shale regions in the United States and western Canada including, but not limited to, Pennsylvania, Maryland, New York, Texas, Oklahoma, West Virginia and Ohio) requires a very large amount of water input and a significant amount of return (flowback) water that contains a great deal of contaminants and impurities. In order for this flowback water to be used in an environmentally responsible manner, it needs to be relatively free of contaminants/impurities. Water used, for example, in natural gas well drilling and production may contain organic materials, volatile and semi-volatile compounds, oils, metals, salts, etc. that have made economical treatment of the water to make it potable or reusable, or even readily and safely disposable, more difficult. It is desirable to remove or reduce the amount of such contaminants/impurities in the water to be re-used, and also to remove or reduce the amount of such contaminants/impurities in water that is disposed of.
The present invention is directed toward overcoming one or more of the above-identified problems.
The present invention can take numerous forms among which are those in which waste water containing a large amount of solids, including, for example, dissolved salts, is pressurized to allow considerable heat to be applied before the water evaporates, and is then subjected to separation and recovery apparatus to recover relatively clean water for reuse and to separate solids that include the afore-mentioned dissolved salts. In some instances, the concentrated solids may be disposed of as is, e.g., in a landfill. Where that is not acceptable (e.g., for reasons of leaching of contaminants), the concentrated solids may be supplied to a thermal, pyrolytic, reactor (referred to herein as a “crystallizer”) for transforming them into a vitrified mass which can be placed anywhere glass is acceptable.
Particular apparatus for systems and processes in accordance with the present invention can be adapted from apparatus that may be presently currently available, but which has not been previously applied in the same manner. As an example, conventional forms of flash evaporation equipment, such as are used for treating sea water, in one or in multiple stages, may be applied herein as a salts concentration apparatus. Likewise, conventional forms of gasification/vitrification reactors, such as are used for municipal solid waste (“MSW”) processing including, but not limited, to plasma gasification/vitrification reactors, may be applied for final separation of the contaminants from the water and for initial heating of the waste water.
The present disclosure presents examples of such systems and processes in which, in one or more successive concentration stages, steam output of a flash evaporator used to concentrate salts is raised in pressure by mechanical vapor compressors from a low level (e.g., 5 psia) to a substantially higher level (e.g., 150 psia), accompanied by elevation of the steam temperature. The steam is applied to heat incoming waste water for treatment and permits use of a smaller and less expensive heat exchanger than would be needed without such pressurization.
Additionally, in some examples, steam from one or more stages of salts concentration is pressurized (e.g., from 5 psia up to 150 psia) before applying the steam to a stripper to remove, for example, volatile organic compounds (“VOCs”), and making the water available for reuse in a prior or subsequent stage and the VOCs available for reaction in a pyrolytic (e.g., plasma) reactor or crystallizer.
In addition, examples can include use of a turbine to expand steam (e.g., having an input of steam exiting a reactor or crystallizer at 150 psia and an output of steam at 15 psia) which goes then to a VOC stripper for use as described above. A turbine, or the like, for steam pressure reduction generates power or mechanical energy that reduces overall energy consumption.
Such uses of compressors and turbines, while adding some additional initial costs, can save significant operating costs.
The present disclosure, among other things, also presents examples of such systems and processes in which, in one or more successive concentration stages, steam output from a flash evaporator used to concentrate salts is reduced in pressure from, for example, 150 psia input pressure to 25 psia output pressure, and the output steam is then sent to the stripper. The steam from the crystallizer (e.g., at 180 psia) is sent back to heat the pressurized waste water in each stage. A portion of the steam from the crystallizer is sent to the stripper after expanding in a turbine (e.g., a mechanical vapor turbine). A turbine is used to expand this steam before sending it to a stripper of volatile organic compounds (“VOCs”).
The system and process of the present invention also includes, for example, applying saturated steam from the crystallizer to a condenser prior to flash evaporation of waste water and, therefore, a heater stage can be avoided. A preheater is used to heat incoming waste water (e.g., from 60° F. to 134° F.) by use of the condensate from the condenser.
The present disclosure, among other things, further presents examples of such systems and processes in which, in one or more successive concentration stages, steam output of a flash evaporator used to concentrate salts is reduced in pressure from, for example, 150 psia input to 5 psia downstream. The output steam is then repressurized to, e.g., 180 psia, prior to being applied to a crystallizer.
The system and process of the present invention further includes, for example, that saturated steam from the reactor/crystallizer is applied to a condenser prior to flash evaporation of waste water and, therefore, an extra heater stage can be avoided. A preheater, provided before the condenser, is used to heat incoming waste water (e.g., from 60° F. to 134° F.) by use of the condensate from the condenser.
The present disclosure, among other things, further presents examples of such systems and processes in which, in one or more successive concentration stages, waste water with dissolved solids (salts) is pressurized (e.g., from 15 psia to 400 psia) and heated (e.g., to 445° F.) before flash evaporation to a significantly lower flash pressure and temperature (e.g., 15 psia and 212° F.) and brine water with more concentrated salts.
Steam output from the concentration stages is, at least in part, supplied to a stripper to remove volatile organic compounds (“VOCs”). Additional steam from the concentration stages is pressurized (e.g., to 665 psia) prior to recycling back to the concentration stages as a heating fluid for incoming waste water.
Brine water from the concentration stages may be disposed of as is, with a significant amount of clean water recovered (e.g., as distilled water from heat exchangers of the concentration stages). Brine water may alternatively be treated in a thermal (e.g., plasma) reactor or crystallizer in order to separate the salts and recover water included in the brine water from the concentration stages.
Present examples described herein include operation of a crystallizer at a significantly higher pressure (e.g., 665 psia) than in many other thermal reactor systems in order to achieve a large temperature difference in heat exchangers of the concentration stages.
Examples described herein also include supplying saturated steam from the crystallizer directly to condensers of the concentration stages, from each of which it is then applied as a heating fluid of a preheater for the waste water. Such a system will not normally require any additional heating of the waste water prior to flash evaporation.
The present disclosure, among other things, presents examples of such systems and processes in which, in one or more concentration stages, waste water with dissolved solids (salts) is pressurized (e.g., to 400 psia) and heated (e.g., to 445° F.) before flash evaporation in a single flash evaporator to which multiple concentration stages supply waste water in parallel. For example, the waste water is split into three equal flows that are individually pressurized and heated prior to being subjected to flash evaporation together.
The flash evaporator produces steam that is then usable as a heating medium and brine water with more concentrated salts than the original waste water.
The resulting combined brine water from the concentration stages may be disposed of as is, with a significant amount of clean water recovered (e.g., as distilled water from heat exchangers of the concentration stages). Brine water may alternatively be treated in a pyrolytic (e.g., plasma) reactor or crystallizer in order to separate the salts and recover water included in the brine water from the concentration stages.
Where a crystallizer is used, it can provide superheated steam (developed from steam from the single, or plural, flash evaporator(s)) that is applied directly to condensers of the concentration stages, from each of which it is then applied as a heating fluid of a preheater for the waste water. Such a system will not normally require additional heating of the waste water prior to flash evaporation.
While the another embodiment of the present invention is described with respect to
A system for treating waste water is disclosed, the system including: a pump receiving waste water at a first pressure and a first temperature and pressurizing the received waste water to a second pressure greater than the first pressure, the waste water comprising dissolved solids, volatile organic compounds and other components generally and collectively called impurities; first and second preheaters receiving the pressurized waste water from the pump and preheating the pressurized waste water in successive stages to a second temperature greater than the first temperature to produce pressurized/preheated waste water, each of the first and second preheaters producing distilled water without boiling of the waste water across heat transfer surfaces; a condenser receiving the pressurized/preheated waste water and further heating the pressurized/preheated waste water to a third temperature greater than the second temperature to produce a pressurized/further heated waste water without boiling of the waste water across heat transfer surfaces; a heater receiving the pressurized/further heated waste water and still further heating the pressurized/further heated waste water to a fourth temperature greater than the third temperature to produce pressurized/heated waste water without boiling of the waste water across heat transfer surfaces; and an evaporator, operated at a third pressure less than the second pressure, removing dissolved solids from the pressurized/heated waste water by evaporation caused by depressurization of the waste water to produce steam and brine water, wherein the brine water has a total dissolved solids content greater than a total dissolved solids content of the received waste water, wherein steam from the evaporator is superheated to a fifth temperature greater than the fourth temperature and is used as a heat source by at least one of the heater, condenser and second preheater without boiling of the waste water across heat transfer surfaces.
The second pressure may be approximately 120-180 psia, and the third pressure may be approximately 4-6 psia.
The fourth temperature may be approximately 286-430° F., and the firth temperature may be approximately 400-600° F.
In one form, the pump, first and second preheaters, condenser, heater and evaporator comprise a stage, and wherein the system comprises multiple stages with the brine water output by one stage used as the received waste water of a next stage. The brine water output by each stage has a total dissolved solids content that is higher than that of a previous stage.
In another form, the system further includes a crystallizer crystallizing the brine water to produce a solid mass of waste product and steam, which may be a vitrified glass. The steam from the crystallizer may be mixed with steam from the evaporator and superheated to the fifth temperature, wherein the mixed and superheated steam may be used as a heat source by at least one of the heater, condenser and second preheater without boiling of the waste water across heat transfer surfaces.
In a further form, the crystallizer includes a plasma crystallizer and includes a plasma torch for vaporizing the water from the brine water and producing the solid mass of waste product and steam. The system further includes a stripper initially receiving the waste water and removing volatile organic compounds from the waste water prior to the waste water being pressurized by the pump, wherein the removed volatile organic compounds are used as a heat source by the plasma torch to crystallize the brine water. The steam produced by the evaporator, when cooled, produces distilled water. Additionally, the steam produced by the evaporator may be used as a heat source by the stripper without boiling of the waste water across heat transfer surfaces. The steam produced by the evaporator may also be used as a heat source by the first preheater without boiling of the waste water across heat transfer surfaces.
In yet a further form, the pump, first and second preheaters, condenser, heater and evaporator comprise a stage, and wherein the system comprises multiple stages operating in parallel with each receiving a portion of the waste water. The brine water output by each stage has a total dissolved solids content that is higher than that of the received waste water. The brine water from each stage is combined and supplied to the crystallizer which crystallizes the brine water to produce a solid mass of waste product and steam.
In still a further form, the pump, first and second preheaters, condenser, heater and evaporator comprise a stage, wherein the system comprises multiple stages with the brine water output by one stage used as the received waste water of a next stage, and wherein the received waste water at stages subsequent to a first stage is at a third pressure less than the first pressure.
A system for treating waste water is also disclosed, the system including: a pump receiving waste water at a first pressure and a first temperature and pressurizing the received waste water to a second pressure greater than the first pressure, the waste water comprising dissolved solids, volatile organic compounds and other components generally and collectively called impurities; a preheater receiving the pressurized waste water from the pump and preheating the pressurized waste water to a second temperature greater than the first temperature to produce pressurized/preheated waste water without boiling of the waste water across heat transfer surfaces; a condenser receiving the pressurized/preheated waste water and further heating the pressurized/preheated waste water to a third temperature greater than the second temperature to produce a pressurized/heated waste water without boiling of the waste water across heat transfer surfaces; an evaporator, operated at a third pressure less than the second pressure, removing dissolved solids from the pressurized/heated waste water by evaporation caused by depressurization of the waste water to produce steam and brine water, wherein the brine water has a total dissolved solids content greater than a total dissolved solids content of the received waste water; and a crystallizer, operated at a fourth pressure greater than the second pressure, receiving the brine water and crystallizing the brine water to produce a solid mass of waste product and steam, wherein steam from the crystallizer, at the fourth pressure and a fourth temperature greater than the third temperature, is used as a heat source by at least one of the condenser and preheater without boiling of the waste water across heat transfer surfaces, and wherein steam from the evaporator is used as a heat source by the crystallizer without boiling of the waste water across heat transfer surfaces.
In one form, the first pressure may be approximately 11.8-17.6 psia, and the first temperature may be approximately 480-72° F.
In one form, the second pressure may be approximately 120-180 psia, and the third temperature may be approximately 288-432° F.
In one form, the second pressure may be approximately 320-480 psia, and the third temperature may be approximately 356-534° F.
In one form, the third pressure may be approximately 20-30 psia, the fourth pressure may be approximately 144-216 psia, and the fourth temperature may be approximately 298-448° F.
In one form, the third pressure may be approximately 4-6 psia, the fourth pressure may be approximately 144-216 psia, and the fourth temperature may be approximately 298-448° F.
In one form, the third pressure may be approximately 12-18 psia, the fourth pressure may be approximately 532-798 psia, and the fourth temperature may be approximately 400-600° F.
In another form, the crystallizer includes a plasma crystallizer and includes a plasma torch for vaporizing the water from the brine water and producing the solid mass of waste product and steam. The system further includes a stripper initially receiving the waste water and removing volatile organic compounds from the waste water prior to the waste water being pressurized by the pump, wherein the removed volatile organic compounds are used as a heat source by the plasma torch to crystallize the brine water without boiling of the waste water across heat transfer surfaces.
In a further form, the system further included a mechanical vapor turbine receiving the steam from the crystallizer and reducing its pressure to the third pressure, wherein the reduced pressure steam is combined with the steam from the evaporator and used as a heat source by the stripper.
In yet a further form, the system further includes a mechanical vapor compressor receiving the steam from the evaporator and increasing its pressure to the fourth pressure, wherein the increased pressure steam is combined with the steam from the crystallizer and used as a heat source by at least one of the condenser and preheater without boiling of the waste water across heat transfer surfaces.
In still a further form, the pump, preheater, condenser and evaporator comprise a stage, and wherein the system comprises multiple stages with the brine water output by one stage used as the received waste water of a next stage, and wherein the brine water output by a last stage is input to the crystallizer. The brine water output by each stage has a total dissolved solids content that is higher than that of a previous stage.
In an additional form, the pump, preheater, condenser and evaporator comprise a stage, and wherein the system comprises multiple stages operating in parallel with each stage receiving a portion of the waste water, and wherein the brine water from each stage is combined and supplied to the crystallizer. The brine water output by each stage has a total dissolved solids content that is higher than that of the received waste water.
In yet and additional form, the pump, preheater, condenser and evaporator comprise a stage, wherein the system comprises multiple stages with the brine water output by one stage used as the received waste water of a next stage, and wherein the received waste water at stages subsequent to a first stage is at the third pressure.
A method of treating waste water is also disclosed, the method including the steps of: (a) receiving waste water at a first pressure and a first temperature, the waste water comprising dissolved solids, volatile organic compounds and other components generally and collectively called impurities; (b) pressurizing the received waste water to a second pressure greater than the first pressure; (c) preheating the pressurized waste water to a second temperature greater than the first temperature, wherein said preheating step is performed by first and second preheaters in successive stages to produce pressurized/preheated waste water, each of the first and second preheaters producing distilled water without boiling of the waste water across heat transfer surfaces; (d) heating the pressurized/preheated waste water to a third temperature greater than the second temperature to produce a pressurized/heated waste water without boiling of the waste water across heat transfer surfaces; (e) further heating the pressurized/heated waste water to a fourth temperature greater than the third temperature to produce pressurized/further heated waste water without boiling of the waste water across heat transfer surfaces; and (f) removing, by evaporation caused by depressurization of the waste water, dissolved solids from the pressurized/further heated waste water by an evaporator operated at a third pressure less than the second pressure to produce steam and brine water, wherein the brine water has a total dissolved solids content greater than a total dissolved solids content of the received waste water, wherein steam from the evaporator is superheated to a fifth temperature greater than the fourth temperature and is used as a heat source in at least one of steps (c)—by the second preheater, (d) and (e) without boiling of the waste water across heat transfer surfaces.
The second pressure may be approximately 120-180 psia, and the third pressure may be approximately 4-6 psia.
The fourth temperature may be approximately 286-430° F., and the firth temperature may be approximately 400-600° F.
In one form, steps (a)-(f) comprise a stage, and wherein the method is performed in multiple stages with the brine water output by step (f) in one stage used as the received waste water in step (a) of a next stage. The brine water output in step (f) of each stage has a total dissolved solids content that is higher than that of a previous stage.
In another form, the method further includes the steps of: (g) crystallizing the brine water to produce a solid mass of waste product and steam. The steam produced by step (g) is mixed with steam produced by step (f) and superheated to the fifth temperature, wherein the mixed and superheated steam may be used as a heat source in at least one of steps (c)—by the second preheater, (d) and (e) without boiling of the waste water across heat transfer surfaces. A plasma crystallizer using a plasma torch may be used to crystallize the brine water. The solid mass may include a vitrified glass of the salts in the brine water.
In a further form, the method further includes the steps of: (b′) prior to step (b), removing the volatile organic compounds from the received waste water, wherein the removed volatile organic compounds are used as a heat source by the plasma torch to crystallize the brine water. The steam produced by step (f) may be used as a heat source in step (b′). The steam produced by step (f) may be used as a heat source in step (c)—by the first preheater.
In yet a further form, steps (a)-(f) comprise a stage, and wherein the method is performed in multiple stages operating in parallel with each stage receiving a portion of the waste water. The brine water output in step (f) of each stage has a total dissolved solids content that is higher than that of the received waste water. The brine water output in step (f) of each stage is combined and supplied to a crystallizer which crystallizes the combined brine water to produce a solid mass of waste product and steam.
In still a further form, steps (a)-(f) comprise a stage, and wherein the method is performed in multiple stages with the brine water output by step (f) in one stage used as the received waste water in step (a) of a next stage, and wherein the received waste water at step (a) in stages subsequent to a first stage is at a third pressure less than the first pressure.
A method of treating waste water is also disclosed, the method including the steps of: (a) receiving waste water at a first pressure and a first temperature, the waste water comprising dissolved solids, volatile organic compounds and other components generally and collectively called impurities; (b) pressurizing the received waste water to a second pressure greater than the first pressure; (c) preheating the pressurized waste water to a second temperature greater than the first temperature to produce distilled water and pressurized/preheated waste water without boiling of the waste water across heat transfer surfaces; (d) heating the pressurized/preheated to a third temperature greater than the second temperature to produce pressurized/heated waste water without boiling of the waste water across heat transfer surfaces; (e) removing, by evaporation caused by depressurization of the waste water, dissolved solids from the pressurized/heated water, by an evaporator operated at a third pressure less than the second pressure, to produce steam and brine water, wherein the brine water has a total dissolved solids content greater than a total dissolved solids content of the received waste water; and (f) crystallizing the brine water, by a crystallizer operated at a fourth pressure greater than the second pressure, to produce a solid mass of waste product and steam, wherein steam produced by step (f), at the fourth pressure and a fourth temperature greater than the third temperature, is used as a heat source in at least one of steps (c) and (d), and wherein steam produced by step (e) is used as a heat source in step (g).
In one form, the first pressure may be approximately 11.8-17.6 psia, and the first temperature may be approximately 480-72° F.
In one form, the second pressure may be approximately 120-180 psia, and the third temperature may be approximately 288-432° F.
In one form, the second pressure may be approximately 320-480 psia, and the third temperature may be approximately 356-534° F.
In one form, the third pressure may be approximately 20-30 psia, the fourth pressure may be approximately 144-216 psia, and the fourth temperature may be approximately 298-448° F.
In one form, the third pressure may be approximately 4-6 psia, the fourth pressure may be approximately 144-216 psia, and the fourth temperature may be approximately 298-448° F.
In one form, the third pressure may be approximately 12-18 psia, the fourth pressure may be approximately 532-798 psia, and the fourth temperature may be approximately 400-600° F.
In another form, step (f) uses a plasma torch to crystallize the brine water, and wherein the method further includes the steps of: (b′) prior to step (b), removing the volatile organic compounds from the received waste water, wherein the removed volatile organic compounds are used as a heat source by the plasma torch to crystallize the brine water.
In a further form, the steam produced by step (f) is reduced in pressure to the third pressure, and wherein the reduced pressure steam is combined with steam produced in step (e) and used as a heat source in step (b′).
In yet a further form, the steam produced in step (e) in increased in pressure to the fourth pressure, and wherein the increased pressure steam is combined with steam produced in step (f) and used as a heat source in at least one of steps (c) and (d).
In still a further form, steps (a)-(e) comprise a stage, and wherein the method is performed in multiple stages with the brine water output by step (e) in one stage used as the received waste water in step (a) of a next stage, and wherein the brine water output by step (e) in a last stage is input to the crystallizer at step (f). The brine water output by step (e) of each stage has a total dissolved solids content that is higher than that of a previous stage.
In yet another form, steps (a)-(e) comprise a stage, and wherein the method is performed in multiple stages operating in parallel with each stage receiving a portion of the waste water, and wherein the brine water output by step (e) in each stage is combined and supplied to the crystallizer at step (f). The brine water output by step (e) of each stage has a total dissolved solids content that is higher than that of the waste water received at that particular stage.
In still another form, steps (a)-(e) comprise a stage, and wherein the method is performed in multiple stages operating in parallel with each stage receiving a portion of the waste water, wherein the brine water output by step (e) in each stage is combined and supplied to the crystallizer at step (f), and wherein the received waste water at stages subsequent to a first stage is at the third pressure.
Further explanations and examples of various aspects of the present invention are presented in the following disclosure.
It is an object of the present invention to provide a system and method for the economic and environmental treatment of waste water.
Various other objects, aspects and advantages of the present invention can be obtained from a study of the specification, the drawings, and the appended claims.
Further possible embodiments are shown in the drawings. The present invention is explained in the following in greater detail as an example, with reference to exemplary embodiments depicted in drawings. In the drawings:
It will be seen and appreciated by one skilled in the art how the successive stages of
Each of the
Referring to
The pump 11 elevates the waste water pressure from approximately 14.7 psia (1 atm) to approximately 150 psia. The level of pressurization of waste water in all stages is such that there is no boiling of the waste water inside and across the heat exchanger surfaces of all heat exchangers used in this system. This is done to prevent formation of deposits (scales, fouling etc.) on the heat exchanger surfaces. The temperature is also raised by the successive preheaters 12a and 12, the condenser 13 and the heater 14, so the input waste water to the flash evaporator 15 at inlet 15a is at 150 psia and 358° F.
The elevation in temperature is the effect of steam from one steam output 80 of the crystallizer subsystem 90 of
The Stage #1 output 30 has the volume of waste water reduced from the input 10 with the salts more concentrated to 25% TDS, which is increased from the initial approximately 20% TDS in the exemplary waste water at the input 20.
Stage #2 of the system as shown in
The pump 31 elevates the waste water pressure from approximately 5 psia at its input to approximately 150 psia. The temperature is also raised by the successive preheaters 32a and 32, the condenser 33 and the heater 34, so the input waste water to the flash evaporator 35 at inlet 35a is at 150 psia and 358° F.
The elevation in temperature is the effect of steam from one steam output 80 of the crystallizer subsystem 90 of
The Stage #2 output 50 has the volume of waste water reduced from the input 30 with the salts more concentrated to 31% TDS, which is increased from the initial approximately 25% TDS in the exemplary brine water at the input 30.
Similarly, Stage #3 of
The pump 51 elevates the waste water pressure from approximately 5 psia at its input to approximately 150 psia. The temperature is also raised by the successive preheaters 52a and 52, the condenser 53 and the heater 54, so the input waste water to the flash evaporator 55 at inlet 55a is at 150 psia and 358° F.
The elevation in temperature is the effect of steam from one steam output 80 of the crystallizer subsystem 90 of
The Stage #3 output 70 has the volume of waste water reduced from the input 50 with the salts more concentrated to 39% TDS, which is increased from the initial approximately 31% TDS in the exemplary brine water at the input 50.
The exemplary system includes multiple (three) concentration stages (
The level of pressurization of waste water in all stages is such that there is no boiling (nucleate or other type) of the waste water inside and across the heat exchanger surfaces of the condensers, heaters and preheaters of each stage. This prevents the formation of deposits (scales, fouling etc.) on the heat exchanger surfaces and reduces the requirement for cleaning of the heat exchangers. This results in the reduction of the operating cost.
In general, for multistage operation, the plasma crystallizer 90 (or other reactor) is utilized after the final concentration stage when the output brine water has been concentrated to a desired level, as described in the above example. It can also be suitable to have a multistage system not only for salts concentration (as in
In general, any thermal reactor may be used to separate the salts and the water. A reactor operated to produce disposable salts (referred to herein as a “crystallizer”) is generally suitable. Where the salts have toxicity, it may be desirable to operate the reactor in a manner so they are vitrified or made into glass. Accordingly, any reference to a crystallizer herein can also include a vitrifier.
As shown in
Before treatment in the Stages shown in
The stripped wastewater is sent as feed to the input 20 to Stage #1 of
The steam exiting the plasma crystallizer 90 can be periodically vented to the atmosphere (not shown) to keep the levels of non-condensable gases low enough such that they do not degrade the performance of the heat exchangers used in the inventive system and process.
It is therefore seen that systems and processes in accordance with the present invention can make use of known and available components (such as, for example, flash evaporators for concentration of salts and plasma (or other) gasifier reactors for crystallization (or vitrification) of the salts) in particular innovative ways with insight as to both the capital cost and the operating cost. A need for such cost effective water treatment has been heightened by practices such as, for example, the use of large amounts of water in natural gas drilling. However, the present invention may be used in any situation where impurities to be removed exist.
In general summary, but without limitation, an embodiment of the present invention can be characterized in the following ways, for example: A system, and a corresponding method, in which waste water is supplied to one or more stages of equipment including a pump for pressurizing the water (e.g., to at least about 10 times atmospheric pressure), a heater that heats the pressurized waste water well above normal boiling temperature, a flash evaporator, or other device, that receives the heated, pressurized water and results in fluid evaporation and concentration of solids that were in the waste water. In for example, instances in which the waste (brine) water with concentrated solids cannot be otherwise readily and safely disposed of, a thermal or pyrolytic reactor is provided to crystallize or otherwise yield a form of the solids that can be readily and safely disposed of. In one form, such a reactor may also be applied as a heater for the original incoming waste water. Also, or alternatively, such a reactor may be used to form a vitrified glass of the salts output of any water treatment system that produces a brine water.
Furthermore, the examples of
It will be seen and appreciated by one skilled in the art how the successive stages of
Each of the
Referring to
In this example, the pump 201, preheater 202, and condenser 203 elevate the waste water pressure to 150 psia and the temperature to 360° F. at the inlet 206 to the flash evaporator 205 without use of any heater elements between the condenser 203 and flash evaporator 205. The pump 201 elevates the pressure from 14.7 psia (1 atm) to 150 psia. The level of pressurization of waste water in all stages is such that there is no boiling of the waste water inside and across the heat exchanger surfaces of all heat exchangers used in this system. This is done to prevent the formation of deposits (scales, fouling etc.) on the heat exchanger surfaces. The preheater 202 elevates the temperature from 60° F. to 134° F., while the condenser 202 further elevates the temperature to 360° F. Additionally, the preheater 202 produces distilled water at outlet 207.
For drawing convenience, each concentration Stage (
One aspect of Stage #1 of
The condenser 203 receives some saturated steam directly from the crystallizer 265 of
The Stage #1 output 220 has the volume of waste water reduced from the input 200 with the salts more concentrated to approximately 23% TDS, which is increased from the initial approximately 20% TDS in the exemplary waste water at the input 200.
Stages #2 and #3 in
Referring to
In this example, the pump 221, preheater 222, and condenser 223 elevate the waste water pressure to 150 psia and the temperature to 360° F. at the inlet 226 to the flash evaporator 225 without use of any heater elements between the condenser 223 and flash evaporator 225. The pump 221 elevates the pressure from 25 psia to 150 psia. The preheater 222 elevates the temperature from 239° F. to 253° F., while the condenser 222 further elevates the temperature to 360° F. Additionally, the preheater 222 produces distilled water at outlet 227.
One aspect of Stage #2 of
The condenser 223 receives some saturated steam directly from the crystallizer 265 of
The Stage #2 output 240 has the volume of waste water reduced from the input 220 with the salts more concentrated to approximately 26% TDS, which is increased from the initial approximately 23% TDS in the exemplary waste water at the input 220.
Referring to
In this example, the pump 241, preheater 242, and condenser 243 elevate the waste water pressure to 150 psia and the temperature to 360° F. at the inlet 246 to the flash evaporator 245 without use of any heater elements between the condenser 243 and flash evaporator 245. The pump 241 elevates the pressure from 25 psia to 150 psia. The preheater 242 elevates the temperature from 239° F. to 254° F., while the condenser 242 further elevates the temperature to 360° F. Additionally, the preheater 242 produces distilled water at outlet 247.
One aspect of Stage #3 of
The condenser 243 receives some saturated steam directly from the crystallizer 265 of
The Stage #3 output 260 has the volume of waste water reduced from the input 240 with the salts more concentrated to approximately 30% TDS, which is increased from the initial approximately 26% TDS in the exemplary waste water at the input 220.
The exemplary system includes multiple (three) concentration stages (
The level of pressurization of waste water in all stages is such that there is no boiling (nucleate or other type) of the waste water inside and across the heat exchanger surfaces of the condensers and preheaters of each stage. This prevents the formation of deposits (scales, fouling etc.) on the heat exchanger surfaces and reduces the requirement for cleaning of the heat exchangers. This results in the reduction of the operating cost.
In general, for multistage operation, the plasma crystallizer 265 (or other reactor) is utilized at the final concentration stage when the output brine water has been concentrated to a desired level, as described in the above example. It can also be suitable to have a multistage system not only for salts concentration (as in
In general, any thermal reactor may be used to separate the salts and the water. A reactor operated to produce disposable salts (referred to herein as a “crystallizer”) is generally suitable. Where the salts have toxicity, it may be desirable to operate the reactor in a manner so they are vitrified or made into glass. Accordingly, any reference to a crystallizer herein can also include a vitrifier.
As shown in
Before treatment in the Stages shown in
The steam exiting the plasma crystallizer 265 can be periodically vented to the atmosphere (not shown) to keep the levels of non-condensable gases low enough such that they do not degrade the performance of the heat exchangers used in the inventive system and process.
It is therefore seen that systems and processes in accordance with the further embodiment of the present invention can make use of known and available components, such as, for example, flash evaporators for concentration of salts and plasma (or other) gasifier reactors for crystallization (or vitrification) of the salts, in particular innovative ways with insight as to both the capital cost and the operating cost. A need for such cost effective water treatment has been heightened by practices such as the use of large amounts of water in natural gas drilling However, the present invention may be used in any situation where impurities to be removed exist.
In general summary, but without limitation, the further embodiment of the present invention can be characterized in the following ways, for example: A system, and a corresponding method, in which waste water is supplied to one or more stages of equipment including a pump for pressurizing the water (e.g., to at least about 10 times atmospheric pressure), a heater that heats the pressurized water well above normal boiling temperature, a flash evaporator, or other device, that receives the heated, pressurized water and results in fluid evaporation and concentration of solids that were in the wastewater, and, for instances in which the brine water with concentrated solids cannot be otherwise readily and safely disposed of, a thermal or pyrolytic reactor to crystallize or otherwise yield a form of the solids that can be readily and safely disposed of, such a reactor may also be applied as a heater for the original incoming waste water. Also, or alternatively, such a reactor may be used to form a vitrified glass of the salts output of any water treatment system that produces a brine water.
Furthermore, the examples provided herein show how use can be made of flash evaporators operated at reduced downstream pressure (e.g., 25 psia compared to 150 psia upstream pressure) along with an expander (e.g., turbine), for energy recovery from the steam output of a crystallizer. All of which is believed to contribute significantly to reduced operating costs which can be very beneficial, even though initial capital costs may be increased.
It will be seen and appreciated by one skilled in the art how the successive stages of
Each of the
Referring to
In this example, the pump 301, preheater 302, and condenser 303 elevate the waste water pressure to 150 psia and the temperature to 360° F. at the inlet 306 to the flash evaporator 305 without use of any heater elements between the condenser 303 and flash evaporator 305. The pump 301 elevates the pressure from 14.7 psia (1 atm) to 150 psia. The level of pressurization of waste water in all stages is such that there is no boiling of the waste water inside and across the heat exchanger surfaces of all heat exchangers used in this system. This is done to prevent the formation of deposits (scales, fouling, etc.) on the heat exchanger surfaces. The preheater 302 elevates the temperature from 60° F. to 134° F., while the condenser 302 further elevates the temperature to 360° F. Additionally, the preheater 302 produces distilled water at outlet 307.
For drawing convenience, each concentration Stage (
One aspect of Stage #1 of
The condenser 303 receives some saturated steam directly from the crystallizer 365 of
The Stage #1 output 320 has the volume of waste water reduced from the input 300 with the salts more concentrated to approximately 25% TDS, which is increased from the initial approximately 20% TDS in the exemplary waste water at the input 300.
Stages #2 and #3 in
Referring to
In this example, the pump 321, preheater 322, and condenser 323 elevate the waste water pressure to 150 psia and the temperature to 360° F. at the inlet 326 to the flash evaporator 325 without use of any heater elements between the condenser 323 and flash evaporator 325. The pump 321 elevates the pressure from 5 psia to 150 psia. The preheater 322 elevates the temperature from 162° F. to 197° F., while the condenser 322 further elevates the temperature to 360° F. Additionally, the preheater 322 produces distilled water at outlet 327.
One aspect of Stage #2 of
The condenser 323 receives some saturated steam directly from the crystallizer 365 of
The Stage #2 output 340 has the volume of waste water reduced from the input 320 with the salts more concentrated to approximately 31% TDS, which is increased from the initial approximately 25% TDS in the exemplary waste water at the input 320.
Referring to
In this example, the pump 341, preheater 342, and condenser 343 elevate the waste water pressure to 150 psia and the temperature to 360° F. at the inlet 346 to the flash evaporator 345 without use of any heater elements between the condenser 343 and flash evaporator 345. The pump 341 elevates the pressure from 5 psia to 150 psia. The preheater 342 elevates the temperature from 162° F. to 197° F., while the condenser 342 further elevates the temperature to 360° F. Additionally, the preheater 342 produces distilled water at outlet 347.
One aspect of Stage #3 of
The condenser 343 receives some saturated steam directly from the crystallizer 365 of
The Stage #3 output 360 has the volume of waste water reduced from the input 340 with the salts more concentrated to approximately 39% TDS, which is increased from the initial approximately 31% TDS in the exemplary waste water at the input 320.
The exemplary system includes multiple (three) concentration stages (
The level of pressurization of waste water in all stages is such that there is no boiling (nucleate or other type) of the waste water inside and across the heat exchanger surfaces of the condensers and preheaters of each stage. This prevents the formation of deposits (scales, fouling, etc.) on the heat exchanger surfaces and reduces the requirement for cleaning of the heat exchangers. This results in the reduction of the operating cost.
In general, for multistage operation, the plasma crystallizer 365 (or other reactor) is utilized at the final concentration stage when the output brine water has been concentrated to a desired level, as described in the above example. It can also be suitable to have a multistage system not only for salts concentration (as in
In general, any thermal reactor may be used to separate the salts and the water. A reactor operated to produce disposable salts (referred to herein as a “crystallizer”) is generally suitable. Where the salts have toxicity, it may be desirable to operate the reactor in a manner so they are vitrified or made into glass. Accordingly, any reference to a crystallizer herein can also include a vitrifier.
As shown in
Before treatment in the Stages shown in
The steam exiting the plasma crystallizer 365 can be periodically vented to the atmosphere (not shown) to keep the levels of non-condensable gases low enough such that they do not degrade the performance of the heat exchangers used in the inventive system and process.
It is therefore seen that systems and processes in accordance with the yet further embodiment of the present invention can make use of known and available components, such as, for example, flash evaporators for concentration of salts and plasma (or other) gasifier reactors for crystallization (or vitrification) of the salts, in particular innovative ways with insight as to both the capital cost and the operating cost. A need for such cost effective water treatment has been heightened by practices such as the use of large amounts of water in natural gas drilling However, the present invention may be used in any situation where impurities to be removed exist.
In general summary, but without limitation, the yet further embodiment of the present invention can be characterized in the following ways, for example: A system, and a corresponding method, in which waste water is supplied to one or more stages of equipment including a pump for pressurizing the water (e.g., to at least about 10 times atmospheric pressure), a heater that heats the pressurized water well above normal boiling temperature, a flash evaporator, or other device, that receives the heated, pressurized water and results in fluid evaporation and concentration of solids that were in the wastewater, and, for instances in which the brine water with concentrated solids cannot be otherwise readily and safely disposed of, a thermal or pyrolytic reactor to crystallize or otherwise yield a form of the solids that can be readily and safely disposed of, such a reactor may also be applied as a heater for the original incoming waste water. Also, or alternatively, such a reactor may be used to form a vitrified glass of the salts output of any water treatment system that produces a brine water.
Furthermore, the examples provided herein show how use can be made of flash evaporators operated at low downstream pressure (e.g., 5 psia or only about one-third of 1 atm) along with a compressor elevating the pressure of some steam from the flash evaporators to, e.g., 180 psia, before being added with steam from the reactor that goes back to the earlier concentrations Stages. All of which is believed to contribute significantly to reduced operating costs which can be very beneficial, even though initial capital costs may be increased.
It will be seen and appreciated by one skilled in the art how the successive stages of
Each of the
Referring to
In this example, the pump 401, preheater 402, and condenser 403 elevate the waste water pressure to 400 psia and the temperature to 445° F. at the inlet 406 to the flash evaporator 405 without use of any heater elements between the condenser 403 and flash evaporator 405. The pump 401 elevates the pressure from 14.7 psia (1 atm) to 400 psia. The level of pressurization of waste water in all stages is such that there is no boiling of the waste water inside and across the heat exchanger surfaces of all heat exchangers used in this system. This is done to prevent the formation of deposits (scales, fouling, etc.) on the heat exchanger surfaces. The preheater 402 elevates the temperature from 60° F. to 254° F., while the condenser 402 further elevates the temperature to 445° F. Additionally, the preheater 402 produces distilled water at outlet 407.
For drawing convenience, each concentration Stage (
One aspect of Stage #1 of
The condenser 403 receives some saturated steam directly from the crystallizer 465 of
The Stage #1 output 420 has the volume of waste water reduced from the input 400 with the salts more concentrated to approximately 27% TDS, which is increased from the initial approximately 20% TDS in the exemplary waste water at the input 400.
Stages #2 and #3 in
Referring to
In this example, the pump 421, preheater 422, and condenser 423 elevate the waste water pressure to 400 psia and the temperature to 445° F. at the inlet 426 to the flash evaporator 425 without use of any heater elements between the condenser 423 and flash evaporator 425. The pump 421 elevates the pressure from 15 psia to 400 psia. The preheater 422 elevates the temperature from 212° F. to 272° F., while the condenser 422 further elevates the temperature to 445° F. Additionally, the preheater 422 produces distilled water at outlet 427.
One aspect of Stage #2 of
The condenser 423 receives some saturated steam directly from the crystallizer 465 of
The Stage #2 output 440 has the volume of waste water reduced from the input 420 with the salts more concentrated to approximately 36% TDS, which is increased from the initial approximately 27% TDS in the exemplary waste water at the input 420.
Referring to
In this example, the pump 441, preheater 442, and condenser 443 elevate the waste water pressure to 400 psia and the temperature to 445° F. at the inlet 446 to the flash evaporator 445 without use of any heater elements between the condenser 443 and flash evaporator 445. The pump 441 elevates the pressure from 15 psia to 400 psia. The preheater 442 elevates the temperature from 212° F. to 273° F., while the condenser 442 further elevates the temperature to 445° F. Additionally, the preheater 442 produces distilled water at outlet 447.
One aspect of Stage #3 of
The condenser 443 receives some saturated steam directly from the crystallizer 465 of
The Stage #3 output 340 has the volume of waste water reduced from the input 440 with the salts more concentrated to approximately 48% TDS, which is increased from the initial approximately 36% TDS in the exemplary waste water at the input 420.
The exemplary system includes multiple (three) concentration stages (
The level of pressurization of waste water in all stages is such that there is no boiling (nucleate or other type) of the waste water inside and across the heat exchanger surfaces of the condensers and preheaters of each stage. This prevents the formation of deposits (scales, fouling, etc.) on the heat exchanger surfaces and reduces the requirement for cleaning of the heat exchangers. This results in the reduction of the operating cost.
In general, for multistage operation, the plasma crystallizer 465 (or other reactor) is utilized at the final concentration stage when the output brine water has been concentrated to a desired level, as described in the above example. It can also be suitable to have a multistage system not only for salts concentration (as in
In general, any thermal reactor may be used to separate the salts and the water. A reactor operated to produce disposable salts (referred to herein as a “crystallizer”) is generally suitable. Where the salts have toxicity, it may be desirable to operate the reactor in a manner so they are vitrified or made into glass. Accordingly, any reference to a crystallizer herein can also include a vitrifier.
As shown in
Before treatment in the Stages shown in
The steam exiting the plasma crystallizer 465 can be periodically vented to the atmosphere (not shown) to keep the levels of non-condensable gases low enough such that they do not degrade the performance of the heat exchangers used in the inventive system and process.
It is therefore seen that systems and processes in accordance with the still further embodiment of the present invention can make use of known and available components, such as, for example, flash evaporators for concentration of salts and plasma (or other) gasifier reactors for crystallization (or vitrification) of the salts, in particular innovative ways with insight as to both the capital cost and the operating cost. A need for such cost effective water treatment has been heightened by practices such as the use of large amounts of water in natural gas drilling However, the present invention may be used in any situation where impurities to be removed exist.
In general summary, but without limitation, the still further embodiment of the present invention can be characterized in the following ways, for example: A system, and a corresponding method, in which waste water is supplied to one or more stages of equipment including a pump for pressurizing the water (e.g., to about 400 psia), a preheater that heats the pressurized waste water well above normal boiling temperature, a condenser that effects further heating of the pressurized waste water, a flash evaporator, or other device, that receives the heated, pressurized waste water and results in fluid evaporation and concentration of solids that were in the waste water. In for example, instances in which the waste (brine) water with concentrated solids cannot be otherwise readily and safely disposed of, a thermal or pyrolytic reactor is provided to crystallize or otherwise yield a form of the solids that can be readily and safely disposed of. In one form, such a reactor may also be applied as a heater for the original incoming waste water. Also, or alternatively, such a reactor may be used to form a vitrified glass of the salts output of any water treatment system that produces a brine water.
Furthermore, the examples described herein show how use can be made of flash evaporators operated at a considerable difference of upstream pressure (e.g., 400 psia) and downstream pressure (e.g., 15 psia). To do so, the pyrolytic reactor of the inventive system is operated at a significantly higher pressure than is usual for such equipment (e.g., a plasma crystallizer operated at a pressure of 665 psia and steam developed in the reactor is supplied directly to the condensers of the earlier salts concentration Stages). All of which is believed to contribute significantly to reduced operating costs which can be very beneficial, even though initial capital costs may be increased.
Each of the
A separate batch of wastewater 500 is supplied to each of the inlets 510a, 510b, and 510c of
Referring to
For convenience, when referring to the same element in the various Stages, the reference letters a-c will be omitted and only the reference number will be used. It is to be understood that the element referred to is the same element in all three Stages.
Referring to
For drawing convenience, each concentration Stage (
One aspect of Stages #1A, #1B and #1C of
The condenser 513 receives some saturated steam directly from the crystallizer 565 of
The output 530 of the various parallel Stages has the volume of waste water reduced from the input 510 with the salts more concentrated to a brine water to approximately 27% TDS, which is increased from the initial approximately 20% TDS in the exemplary waste water at the input 510.
In each of
The exemplary system includes multiple (three) concentration stages (
The level of pressurization of waste water in all stages is such that there is no boiling (nucleate or other type) of the waste water inside and across the heat exchanger surfaces of the condensers and preheaters of each stage. This prevents the formation of deposits (scales, fouling, etc.) on the heat exchanger surfaces and reduces the requirement for cleaning of the heat exchangers. This results in the reduction of the operating cost.
The exemplary arrangement shown in
In general, any thermal reactor may be used to separate the salts and the water. A reactor operated to produce disposable salts (referred to herein as a “crystallizer”) is generally suitable. Where the salts have toxicity, it may be desirable to operate the reactor in a manner so they are vitrified or made into glass. Accordingly, any reference to a crystallizer herein can also include a vitrifier.
As shown in
Before treatment in the Stages shown in
The steam exiting the plasma crystallizer 565 can be periodically vented to the atmosphere (not shown) to keep the levels of non-condensable gases low enough such that they do not degrade the performance of the heat exchangers used in the inventive system and process.
It is therefore seen that systems and processes in accordance with the another embodiment of the present invention can make use of known and available components, such as, for example, flash evaporators for concentration of salts and plasma (or other) gasifier reactors for crystallization (or vitrification) of the salts, in particular innovative ways with insight as to both the capital cost and the operating cost. A need for such cost effective water treatment has been heightened by practices such as the use of large amounts of water in natural gas drilling However, the present invention may be used in any situation where impurities to be removed exist.
In general summary, but without limitation, the another embodiment of the present invention can be characterized in the following ways, for example: A system, and a corresponding method, in which waste water is supplied to one or more stages of equipment including a pump for pressurizing the water (e.g., about 400 psia), a preheater that heats the pressurized waste water well above normal boiling temperature, a condenser that effects further heating of the pressurized waste water, a single, or plural, flash evaporator(s), or other concentration device(s), that receives the heated, pressurized water flows from multiple parallel stages of pressurizing and heating elements and results in fluid evaporation and concentration of solids that were in the waste water. In, for example, instances in which the waste (brine) water with concentrated solids cannot be otherwise readily and safely disposed of, a thermal or pyrolytic reactor is provided to crystallize or otherwise yield a form of the solids that can be readily and safely disposed of. In one form, such a reactor may also be applied as a heater for the original incoming wastewater. Also, or alternatively, such a reactor may be used to form a vitrified glass of the salts output of any water treatment system that produces a brine water.
The examples described herein show how use can be made of a single flash evaporator receiving multiple heated and pressurized flows of waste water with the concentrated output of the flash evaporator subjected to final separation of salts and water in a single reactor.
It will be apparent to those skilled in the art that numerous modifications and variations of the described examples and embodiments are possible in light of the above teachings of the disclosure. The disclosed examples and embodiments are presented for purposes of illustration only. Other alternate embodiments may include some or all of the features disclosed herein. Therefore, it is the intent to cover all such modifications and alternate embodiments as may come within the true scope of this invention, which is to be given the full breadth thereof. Additionally, the disclosure of a range of values is a disclosure of every numerical value within that range.
This patent application is a continuation of, and claims the benefit under 35 U.S.C. § 120 of, co-pending U.S. patent application Ser. No. 13/613,388, filed on Sep. 13, 2012, which claims the benefit of U.S. Provisional Patent Application Nos. 61/573,900, 61/573,957, 61/573,958, 61/573,956, 61/573,955, 61/573,954, 61/573,953 and 61/573,952, all filed on Sep. 14, 2011, the disclosures of which are hereby incorporated by reference in their entireties. This patent application is also related to U.S. patent application Ser. Nos. 13/613,329, 13/613,442 and 13/613,478, all filed on Sep. 13, 2012, the disclosures of which are hereby incorporated by reference in their entireties.
Number | Name | Date | Kind |
---|---|---|---|
2441361 | Kirgan | May 1948 | A |
3119752 | Checkovich | Jan 1964 | A |
3186924 | Williamson | Jun 1965 | A |
3197387 | Lawrance | Jul 1965 | A |
3203464 | Kingma | Aug 1965 | A |
3213000 | Ewing | Oct 1965 | A |
3216910 | Langer et al. | Nov 1965 | A |
3285832 | Sephton | Nov 1966 | A |
3337419 | Kogan | Aug 1967 | A |
3342697 | Hammond | Sep 1967 | A |
3360442 | Starmer | Dec 1967 | A |
3396086 | Starmer | Aug 1968 | A |
3433717 | Loebel | Mar 1969 | A |
3434522 | Laurenty | Mar 1969 | A |
3442765 | Levite | May 1969 | A |
3487873 | Bromley et al. | Jan 1970 | A |
3488260 | Gilbert | Jan 1970 | A |
3488686 | Dunwoody et al. | Jan 1970 | A |
3586090 | Henderson | Jun 1971 | A |
3607135 | Gereth et al. | Sep 1971 | A |
3627646 | Osdor | Dec 1971 | A |
3634199 | Winkle | Jan 1972 | A |
3664145 | Johnson | May 1972 | A |
3690116 | Cheng et al. | Sep 1972 | A |
3734160 | Osdor | May 1973 | A |
3763014 | Barba et al. | Oct 1973 | A |
3844899 | Sager, Jr. | Oct 1974 | A |
3855072 | Liu | Dec 1974 | A |
3884767 | Pottharst, Jr. | May 1975 | A |
3912578 | Didycz et al. | Oct 1975 | A |
3926739 | Izumi | Dec 1975 | A |
3933597 | Barba et al. | Jan 1976 | A |
3946495 | Osdor | Mar 1976 | A |
3951753 | Roller | Apr 1976 | A |
3970820 | Mahl | Jul 1976 | A |
4010018 | Kantor | Mar 1977 | A |
4017421 | Othmer | Apr 1977 | A |
4035243 | Katz et al. | Jul 1977 | A |
4043130 | Brown et al. | Aug 1977 | A |
4055145 | Mager et al. | Oct 1977 | A |
4078976 | Spears, Jr. | Mar 1978 | A |
4083781 | Conger | Apr 1978 | A |
4105505 | Saari | Aug 1978 | A |
4136530 | Kantor | Jan 1979 | A |
4141825 | Conger | Feb 1979 | A |
4162945 | Hofstede et al. | Jul 1979 | A |
4186058 | Katz et al. | Jan 1980 | A |
4186060 | Katz et al. | Jan 1980 | A |
4282067 | Katz et al. | Aug 1981 | A |
4287019 | Standiford | Sep 1981 | A |
4312710 | Tanaka et al. | Jan 1982 | A |
4315402 | Sadhukhan | Feb 1982 | A |
4318780 | Bailie | Mar 1982 | A |
4319964 | Katz et al. | Mar 1982 | A |
4332642 | Cane et al. | Jun 1982 | A |
4334961 | Moen et al. | Jun 1982 | A |
4346490 | Katz et al. | Aug 1982 | A |
4367639 | Kantor | Jan 1983 | A |
4390670 | Walinsky | Jun 1983 | A |
4414341 | Williams | Nov 1983 | A |
4440601 | Katz et al. | Apr 1984 | A |
4441337 | Kantor | Apr 1984 | A |
4474142 | Bharathan | Oct 1984 | A |
4485223 | Walinsky | Nov 1984 | A |
4524587 | Kantor | Jun 1985 | A |
4547559 | Walinsky | Oct 1985 | A |
4591413 | Peterson | May 1986 | A |
4641607 | Balazs et al. | Feb 1987 | A |
4659475 | Liao et al. | Apr 1987 | A |
4710537 | Walinsky | Dec 1987 | A |
4731164 | Williamson | Mar 1988 | A |
4750983 | Foster et al. | Jun 1988 | A |
4795532 | Mizutani et al. | Jan 1989 | A |
4941330 | Williamson | Jul 1990 | A |
5032646 | Walinsky | Jul 1991 | A |
5133837 | Elmore et al. | Jul 1992 | A |
5167838 | Wilensky | Dec 1992 | A |
5211724 | Khan et al. | May 1993 | A |
5232603 | Denzinger et al. | Aug 1993 | A |
5346592 | Madani | Sep 1994 | A |
5453306 | Tatsumi et al. | Sep 1995 | A |
5493630 | Mariner et al. | Feb 1996 | A |
5495550 | Mariner et al. | Feb 1996 | A |
5513494 | Flynn et al. | May 1996 | A |
5537507 | Mariner et al. | Jul 1996 | A |
5622605 | Simpson et al. | Apr 1997 | A |
5637127 | McLaughlin et al. | Jun 1997 | A |
5658993 | Denzinger et al. | Aug 1997 | A |
5671322 | Finicle | Sep 1997 | A |
5681615 | Affinito et al. | Oct 1997 | A |
5755855 | Baker et al. | May 1998 | A |
5861049 | Lokhandwala | Jan 1999 | A |
5887117 | Desu et al. | Mar 1999 | A |
5902641 | Affinito et al. | May 1999 | A |
5925223 | Simpson et al. | Jul 1999 | A |
6187206 | Bernier et al. | Feb 2001 | B1 |
6229956 | Morris | May 2001 | B1 |
6404982 | Mariner et al. | Jun 2002 | B1 |
6622523 | Ludwig et al. | Sep 2003 | B2 |
6919000 | Klausner et al. | Jul 2005 | B2 |
7081205 | Gordon et al. | Jul 2006 | B2 |
7189436 | Kohler et al. | Mar 2007 | B2 |
7225620 | Klausner et al. | Jun 2007 | B2 |
7328591 | Holtzapple et al. | Feb 2008 | B2 |
7416666 | Gordon | Aug 2008 | B2 |
7455778 | Gordon | Nov 2008 | B2 |
7476323 | Gordon | Jan 2009 | B2 |
7510658 | Gordon | Mar 2009 | B2 |
7678227 | Alt | Mar 2010 | B2 |
7708865 | Holtzapple et al. | May 2010 | B2 |
7828883 | Aines et al. | Nov 2010 | B2 |
7850826 | Alt | Dec 2010 | B2 |
7922873 | St. Germain et al. | Apr 2011 | B2 |
7950250 | Holtzapple et al. | May 2011 | B2 |
7954322 | Henderson | Jun 2011 | B2 |
7967955 | Heins | Jun 2011 | B2 |
8097128 | Sherry | Jan 2012 | B1 |
20040038808 | Hampden-Smith et al. | Feb 2004 | A1 |
20090020481 | Bailie et al. | Jan 2009 | A1 |
Number | Date | Country |
---|---|---|
1 770 068 | Apr 2007 | EP |
1 775 265 | Apr 2007 | EP |
55059879 | May 1980 | JP |
2002050215 | Jun 2002 | WO |
2006123258 | Nov 2006 | WO |
2010133840 | Nov 2010 | WO |
2012085860 | Jun 2012 | WO |
2012127250 | Sep 2012 | WO |
Entry |
---|
Notification of Transmittal of the International Search Report and the Written Opinion of the International Searching Authority, International Search Report and Written Opinion of the International Searching Authority for PCT/US2012/055175, dated Jan. 9, 2013 (12 pages). |
Notification of Transmittal of the International Search Report and the Written Opinion of the International Searching Authority, International Search Report and Written Opinion of the International Searching Authority for PCT/US2012/055187, dated Dec. 17, 2012 (22 pages). |
Notification of Transmittal of the International Search Report and the Written Opinion of the International Searching Authority, International Search Report and Written Opinion of the International Searching Authority for PCT/US2012/055191, dated Jan. 15, 2013 (14 pages). |
Notification of Transmittal of the International Search Report and the Written Opinion of the International Searching Authority, International Search Report and Written Opinion of the International Searching Authority for PCT/US2012/055194, dated Jan. 22, 2013 (14 pages). |
Supplementary European Search Report and Annex to the European Search Report on European Patent Application No. EP 12 83 2155, dated Jun. 25, 2015 (8 pages). |
Supplementary European Search Report and Annex to the European Search Report on European Patent Application No. EP 12 83 2522, dated Jul. 20, 2015 (9 pages). |
Supplementary European Search Report and Annex to the European Search Report on European Patent Application No. EP 12 83 1074, dated Jul. 14, 2015 (7 pages). |
Supplementary European Search Report and Annex to the European Search Report on European Patent Application No. EP 12 83 1350, dated Jul. 14, 2015 (9 pages). |
Number | Date | Country | |
---|---|---|---|
20160272507 A1 | Sep 2016 | US |
Number | Date | Country | |
---|---|---|---|
61573952 | Sep 2011 | US | |
61573956 | Sep 2011 | US | |
61573957 | Sep 2011 | US | |
61573953 | Sep 2011 | US | |
61573954 | Sep 2011 | US | |
61573955 | Sep 2011 | US | |
61573958 | Sep 2011 | US | |
61573900 | Sep 2011 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 13613388 | Sep 2012 | US |
Child | 15165509 | US |